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...

Bio-inspired dewetted surfaces based on SiC/Si interlocked structures for enhanced-underwater stability and regenerative-drag reduction capability

PubMed Central

Lee, By Junghan; Zhang, Zhuo; Baek, Seunghyun; Kim, Sangkuk; Kim, Donghyung; Yong, Kijung

2016-01-01

Drag reduction has become a serious issue in recent years in terms of energy conservation and environmental protection. Among diverse approaches for drag reduction, superhydrophobic surfaces have been mainly researched due to their high drag reducing efficiency. However, due to limited lifetime of plastron (i.e., air pockets) on superhydrophobic surfaces in underwater, the instability of dewetted surfaces has been a sticking point for practical applications. This work presents a breakthrough in improving the underwater stability of superhydrophobic surfaces by optimizing nanoscale surface structures using SiC/Si interlocked structures. These structures have an unequaled stability of underwater superhydrophobicity and enhance drag reduction capabilities,with a lifetime of plastron over 18 days and maximum velocity reduction ratio of 56%. Furthermore, through photoelectrochemical water splitting on a hierarchical SiC/Si nanostructure surface, the limited lifetime problem of air pockets was overcome by refilling the escaping gas layer, which also provides continuous drag reduction effects. PMID:27095674

Reduction of surface leakage current by surface passivation of CdZn Te and other materials using hyperthermal oxygen atoms

DOEpatents

Hoffbauer, Mark A.; Prettyman, Thomas H.

2001-01-01

Reduction of surface leakage current by surface passivation of Cd.sub.1-x Zn.sub.x Te and other materials using hyperthermal oxygen atoms. Surface effects are important in the performance of CdZnTe room-temperature radiation detectors used as spectrometers since the dark current is often dominated by surface leakage. A process using high-kinetic-energy, neutral oxygen atoms (.about.3 eV) to treat the surface of CdZnTe detectors at or near ambient temperatures is described. Improvements in detector performance include significantly reduced leakage current which results in lower detector noise and greater energy resolution for radiation measurements of gamma- and X-rays, thereby increasing the accuracy and sensitivity of measurements of radionuclides having complex gamma-ray spectra, including special nuclear materials.

A continuum state variable theory to model the size-dependent surface energy of nanostructures.

PubMed

Jamshidian, Mostafa; Thamburaja, Prakash; Rabczuk, Timon

2015-10-14

We propose a continuum-based state variable theory to quantify the excess surface free energy density throughout a nanostructure. The size-dependent effect exhibited by nanoplates and spherical nanoparticles i.e. the reduction of surface energy with reducing nanostructure size is well-captured by our continuum state variable theory. Our constitutive theory is also able to predict the reducing energetic difference between the surface and interior (bulk) portions of a nanostructure with decreasing nanostructure size.

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

Kreutzer, Cory J.; Rugh, John; Tomerlin, Jeff

Increased market penetration of electric drive vehicles (EDVs) requires overcoming a number of hurdles, including limited vehicle range and the elevated cost in comparison to conventional vehicles. Climate control loads have a significant impact on range, cutting it by over 50% in both cooling and heating conditions. To minimize the impact of climate control on EDV range, the National Renewable Energy Laboratory has partnered with Hyundai America and key industry partners to quantify the performance of thermal load reduction technologies on a Hyundai Sonata plug-in hybrid electric vehicle. Technologies that impact vehicle cabin heating in cold weather conditions and cabinmore » cooling in warm weather conditions were evaluated. Tests included thermal transient and steady-state periods for all technologies, including the development of a new test methodology to evaluate the performance of occupant thermal conditioning. Heated surfaces demonstrated significant reductions in energy use from steady-state heating, including a 29%-59% reduction from heated surfaces. Solar control glass packages demonstrated significant reductions in energy use for both transient and steady-state cooling, with up to a 42% reduction in transient and 12.8% reduction in steady-state energy use for the packages evaluated. Technologies that demonstrated significant climate control load reduction were selected for incorporation into a complete thermal load reduction package. The complete package is set to be evaluated in the second phase of the ongoing project.« less

H 2 Desorption from MgH 2 Surfaces with Steps and Catalyst-Dopants

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

Reich, Jason M.; Wang, Lin-Lin; Johnson, Duane D.

2014-03-10

Light-metal hydrides, like MgH 2, remain under scrutiny as prototypes for reversible H-storage materials. For MgH 2, we assess hydrogen desorption/adsorption properties (enthalpy and kinetic barriers) for stepped, catalyst-doped surfaces occurring, e.g., from ball-milling in real samples. Employing density functional theory and simulated annealing in a slab model, we studied initial H 2 desorption from stepped surfaces with(out) titanium (Ti) catalytic dopant. Extensive simulated annealing studies were performed to find the dopant’s site preferences. For the most stable initial and final (possibly magnetic) states, nudged elastic band (NEB) calculations were performed to determine the H 2-desorption activation energy. We usedmore » a moment-transition NEB method to account for the dopant’s transition to the lowest-energy magnetic state at each image along the band. We identify a dopant-related surface-desorption mechanism that reloads via bulk H diffusion. While reproducing the observed bulk enthalpy of desorption, we find a decrease of 0.24 eV (a 14% reduction) in the activation energy on doped stepped surface; together with a 22% reduction on a doped flat surface, this brackets the assessed 18% reduction in kinetic barrier for ball-milled MgH 2 samples with low concentration of Ti from experiment.« less

Design and Implementation of a Thermal Load Reduction System in a Hyundai PHEV

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

Kreutzer, Cory J; Rugh, John P

Increased market penetration of electric drive vehicles (EDVs) requires overcoming a number of hurdles including limited vehicle range and the elevated cost of EDVs as compared to conventional vehicles. Climate control loads have a significant impact on range, cutting it by over 50% in both cooling and heating conditions. In order to minimize the impact of climate control on EDV range, the National Renewable Energy Laboratory has partnered with Hyundai America and key industry partners to quantify the performance of thermal load reduction technologies on a Hyundai Sonata PHEV. Technologies that impact vehicle cabin heating in cold weather conditions andmore » cabin cooling in warm weather conditions were evaluated. Tests included thermal transient and steady-state periods for all technologies, including the development of a new test methodology to evaluate the performance of occupant thermal conditioning. Heated surfaces and increased insulation demonstrated significant reductions in energy use from steady-state heating, including a 29% - 59% reduction from heated surfaces. Solar control glass packages demonstrated significant reductions in energy use for both transient and steady-state cooling, with up to a 42% reduction in transient and 12.8% reduction in steady-state energy use for the packages evaluated. Technologies that demonstrated significant climate control load reduction were selected for incorporation into a complete thermal load reduction package. The complete package is set to be evaluated in the second phase of the ongoing project.« less

Drag reduction using metallic engineered surfaces with highly ordered hierarchical topographies: nanostructures on micro-riblets

NASA Astrophysics Data System (ADS)

Kim, Taekyung; Shin, Ryung; Jung, Myungki; Lee, Jinhyung; Park, Changsu; Kang, Shinill

2016-03-01

Durable drag-reduction surfaces have recently received much attention, due to energy-saving and power-consumption issues associated with harsh environment applications, such as those experienced by piping infrastructure, ships, aviation, underwater vehicles, and high-speed ground vehicles. In this study, a durable, metallic surface with highly ordered hierarchical structures was used to enhance drag-reduction properties, by combining two passive drag-reduction strategies: an air-layer effect induced by nanostructures and secondary vortex generation by micro-riblet structures. The nanostructures and micro-riblet structures were designed to increase slip length. The top-down fabrication method used to form the metallic hierarchical structures combined laser interference lithography, photolithography, thermal reflow, nanoimprinting, and pulse-reverse-current electrochemical deposition. The surfaces were formed from nickel, which has high hardness and corrosion resistance, making it suitable for use in harsh environments. The drag-reduction properties of various metal surfaces were investigated based on the surface structure: a bare surface, a nanostructured surface, a micro-riblet surface, and a hierarchically structured surface of nanostructures on micro-riblets.

Surface nanocrystalline and hardening effects of Ti-Al-V alloy by electropulsing ultrasonic shock

NASA Astrophysics Data System (ADS)

Ye, Xiaoxin; Tang, Guoyi

2015-03-01

The effect of electropulsing ultrasonic shock (EUS) on the surface hardening and microstructure of Ti6Al4V alloy was studied. It was found that electropulsing improved the microhardness dramatically both in the influential depth and maximum value, compared with the only ultrasonic-shocked sample. It's indicated that refined surface layer with nanocrystalline and improved microhardness were obtained on account of surface severe plastic deformation, dynamic recrystallization (DRX) and phase change, which was implemented at relative low temperature and high strain rate/capacity due to the coupling of the thermal and athermal effects of EUS. It's different from conventional experiments and theory. It's discussed that the positive contributions of EPT in the thermodynamics and kinetics of microstructure and properties change were attributed to the reduction of nucleation energy barrier and acceleration of atomic diffusion. Therefore, it's supposed that EUS is an energy-saving and high-efficiency method of surface treatment technique with the help of high-energy electropulses, which is promising in cost reduction of the surface engineering and energy management. The work is supported by National Natural Science Foundation of China (No. 50571048) and Shenzhen science and technology research funding project of China (No. SGLH20121008144756946).

Energy for biologic sulfate reduction in a hydrothermally formed ocean on Europa

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Y.; Shock, Everett L.

2003-04-01

Formation of a sulfate-bearing ocean on Jupiter's satellite Europa by quenched hydrothermal fluids provides a source of metabolic energy for low-temperature sulfate-reducing organisms that use dissolved H2 as an electron donor. Inhibition of thermodynamically favorable sulfate reduction in cooled hydrothermal fluids creates the potential for biologic reduction. Both high temperature and reduced conditions of ocean-forming hydrothermal solutions favor sulfate reduction in quenched fluids. The maximum amount of energy available to support autotrophic sulfate reduction is on the order of a few kilojoules per kilogram of water and is limited by the low abundances of either H2 or sulfate in ocean-forming fluids. Although this irreplaceable energy source might have supported early life on Europa, maintenance of biologic sulfate reduction throughout the ocean's history would require a supply of organic compounds from endogenic sources or from the satellite's surface.

Energy output reduction and surface alteration of quartz and sapphire tips following Er:YAG laser contact irradiation for tooth enamel ablation.

PubMed

Eguro, Toru; Aoki, Akira; Maeda, Toru; Takasaki, Aristeo Atsushi; Hasegawa, Mitsuru; Ogawa, Masaaki; Suzuki, Takanori; Yonemoto, Kazuaki; Ishikawa, Isao; Izumi, Yuichi; Katsuumi, Ichiroh

2009-10-01

Despite the recent increase in application of Er:YAG laser for various dental treatments, limited information is available regarding the contact tips. This study examined the changes in energy output and surface condition of quartz and sapphire contact tips after Er:YAG laser contact irradiation for tooth enamel ablation. Ten sets of unused quartz or sapphire contact tips were employed for contact irradiation to sound enamel of extracted teeth. The teeth were irradiated with Er:YAG laser at approximately 75 J/cm(2)/pulse and 20 Hz under water spray for 60 minutes. The energy output was measured before and every 5 minutes after irradiation, and the changes in morphology and chemical composition of the contact surface were analyzed. The energy output significantly decreased with time in both tips. The energy output from the sapphire tips was generally higher on average than that of the quartz. The contact surfaces of all the used quartz tips were concave and irregular. Most of the sapphire tips also appeared rough with crater formation and fractures, except for a few tips in which a high energy output and the original smooth surface were maintained. Spots of melted tooth substances were seen attached to the surface of both tips. In contact enamel ablation, the sapphire tip appeared to be more resistant than the quartz tip. The quartz tips showed similar patterns of energy reduction and surface alteration, whereas the sapphire tips revealed a wider and more characteristic variation among tips. Lasers Surg. Med. 41:595-604, 2009. (c) 2009 Wiley-Liss, Inc.

A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

NASA Astrophysics Data System (ADS)

Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

2017-09-01

Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

Copoly(imide siloxane) Abhesive Materials with Varied Siloxane Oligomer Length

NASA Technical Reports Server (NTRS)

Wohl, Christoper J.; Atkins, Brad M.; Lin, Yi; Belcher, Marcus A.; Connell, John W.

2010-01-01

In this work, low surface energy copoly(imide siloxane)s were synthesized with various siloxane segment lengths. Characterization of these materials revealed that domain formation of the low surface energy component within the matrix was more prevalent for longer siloxane segments as indicated by increased opacity, decreased mechanical properties, and variation of the Tg. Incorporation of siloxanes lowered the polymer s surface energy as indicated by water contact angle values. Topographical modification of these materials by laser ablation patterning further reduced the surface energy, even generating superhydrophobic surfaces. Combined, the contact angle data and particle adhesion testing indicated that copoly(imide siloxane) materials may provide greater mitigation to particulate adhesion than polyimide materials alone. These enhanced surface properties for abhesive applications did result in a reduction of the tensile moduli of the copolymers. It is possible that lower siloxane loading levels would result in retention of the mechanical properties of the polyimide while still affording abhesive surface properties. This hypothesis is currently being investigated. Laser ablation patterning offers further reduction in particle retention as the available surface area for particle adhesion is reduced. Pattern variation and size dependencies are currently being evaluated. For the purposes of lunar dust adhesion mitigation, it is likely that this approach, termed passive due to the lack of input from an external energy source, would not be sufficient to mitigate surface contamination or clean contaminated surfaces for some lunar applications. It is feasible to combine these materials with active mitigation strategies - methods that utilize input from external energy sources - would broaden the applicability of such materials for abhesive purposes. Collaborative efforts along these lines have been initiated with researchers at NASA Kennedy Space Center where experiments are being conducted involving a series of embedded electrodes within polymeric matrices.

Surface analysis of 316 stainless steel treated with cold atmospheric plasma

NASA Astrophysics Data System (ADS)

Williams, David F.; Kellar, Ewen J. C.; Jesson, David A.; Watts, John F.

2017-05-01

The surface of 316 stainless steel has been modified using cold atmospheric plasma (CAP) to increase the surface free energy (by cleaning the and chemically activating the surface)IN preparation for subsequent processes such as painting, coating or adhesive bonding. The analyses carried out, on CAP treated 316 stainless steel surfaces, includes X-ray photoelectron spectroscopy (XPS), imaging XPS (iXPS), and surface free energy (SFE) analysis using contact angle measurements. The CAP treatment is shown to increase the SFE of as-received 316 stainless steel from ∼39 mJ m-1 to >72 mJ m-1 after a short exposure to the plasma torch. This was found to correlate to a reduction in adventitious carbon, as determined by XPS analysis of the surface. The reduction from ∼90 at% to ∼30% and ∼39 at%, after being plasma treated for 5 min and 15 s respectively, shows that the process is relatively quick at changing the surface. It is suggested that the mechanism that causes the increase in surface free energy is chain scission of the hydrocarbon contamination triggered by free electrons in the plasma plume followed by chemical functionalisation of the metal oxide surface and some of the remaining carbon contamination layer.

Atomic-scale luminescence measurement and theoretical analysis unveiling electron energy dissipation at a p-type GaAs(110) surface.

PubMed

Imada, Hiroshi; Miwa, Kuniyuki; Jung, Jaehoon; Shimizu, Tomoko K; Yamamoto, Naoki; Kim, Yousoo

2015-09-11

Luminescence of p-type GaAs was induced by electron injection from the tip of a scanning tunnelling microscope into a GaAs(110) surface. Atomically-resolved photon maps revealed a significant reduction in luminescence intensity at surface electronic states localized near Ga atoms. Theoretical analysis based on first principles calculations and a rate equation approach was performed to describe the perspective of electron energy dissipation at the surface. Our study reveals that non-radiative recombination through the surface states (SS) is a dominant process for the electron energy dissipation at the surface, which is suggestive of the fast scattering of injected electrons into the SS.

Effect of Various Material Properties on the Adhesive Stage of Fretting

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1974-01-01

Various properties of metals and alloys were studied with respect to their effect on the initial stage of the fretting process, namely adhesion. Crystallographic orientation, crystal structure, interfacial binding energies of dissimiliar metal, segregation of alloy constituents and the nature and structure of surface films were found to influence adhesion. High atomic density, low surface energy grain orientations exhibited lower adhesion than other orientations. Knowledge of interfacial surface binding energies assists in predicting adhesive transfer and wear. Selective surface segregation of alloy constituents accomplishes both a reduction in adhesion and improved surface oxidation characteristics. Equivalent surface coverages of various adsorbed species indicate that some are markedly more effective in inhibiting adhesion than others.

Energy, chemical disequilibrium, and geological constraints on Europa.

PubMed

Hand, Kevin P; Carlson, Robert W; Chyba, Christopher F

2007-12-01

Europa is a prime target for astrobiology. The presence of a global subsurface liquid water ocean and a composition likely to contain a suite of biogenic elements make it a compelling world in the search for a second origin of life. Critical to these factors, however, may be the availability of energy for biological processes on Europa. We have examined the production and availability of oxidants and carbon-containing reductants on Europa to better understand the habitability of the subsurface ocean. Data from the Galileo Near-Infrared Mapping Spectrometer were used to constrain the surface abundance of CO(2) to 0.036% by number relative to water. Laboratory results indicate that radiolytically processed CO(2)-rich ices yield CO and H(2)CO(3); the reductants H(2)CO, CH(3)OH, and CH(4) are at most minor species. We analyzed chemical sources and sinks and concluded that the radiolytically processed surface of Europa could serve to maintain an oxidized ocean even if the surface oxidants (O(2), H(2)O(2), CO(2), SO(2), and SO(4) (2)) are delivered only once every approximately 0.5 Gyr. If delivery periods are comparable to the observed surface age (30-70 Myr), then Europa's ocean could reach O(2) concentrations comparable to those found in terrestrial surface waters, even if approximately 10(9) moles yr(1) of hydrothermally delivered reductants consume most of the oxidant flux. Such an ocean would be energetically hospitable for terrestrial marine macrofauna. The availability of reductants could be the limiting factor for biologically useful chemical energy on Europa.

Final thickness reduction and development of Goss texture in C- and Al-free Fe-3%Si-0.1%Mn-0.012%S electrical steel

NASA Astrophysics Data System (ADS)

Oh, Eun Jee; Heo, Nam Hoe; Koo, Yang Mo

2017-11-01

The correlation between final thickness reduction and development of Goss texture has been investigated in a C- and Al-free Fe-3%Si electrical steel. During final annealing, the annealing texture is transited from {110}⊥ND to {100}⊥ND texture with increasing final thickness reduction. This is due to the decrease in primary grain size after pre-annealing with increasing final thickness reduction which accelerates the selective growth rate of the {100} grains at the expense of the other {hkl} grains. At an optimal final thickness reduction of 75.8%, the high magnetic induction of 1.95 Tesla, which arises from the sharp {110}<001> Goss texture and is comparable to that of conventional grain-oriented electrical steels, is obtained from the C- and Al-free Fe-3%Si-0.1%Mn electrical steel. Such a high magnetic property is produced through the surface-energy-induced selective grain growth of the Goss grains under the lower surface-segregated condition of sulfur which makes the surface energy of the {110} plane lowest among the {hkl} planes.

Enhanced radial growth of Mg doped GaN nanorods: A combined experimental and first-principles study

NASA Astrophysics Data System (ADS)

Nayak, Sanjay; Kumar, Rajendra; Pandey, Nidhi; Nagaraja, K. K.; Gupta, Mukul; Shivaprasad, S. M.

2018-04-01

We discuss the microstructural origin of enhanced radial growth in magnesium (Mg) doped single crystalline wurtzite gallium nitride (w-GaN) nanorods (NRs) grown by MBE, using electron microscopy and first-principles Density Functional Theory calculations. Experimentally, we observe that Mg incorporation increases the surface coverage of the grown samples as a consequence of an increase in the radial growth rate of the NRs. We also observe that the coalescence of NRs becomes prominent and the height at which coalescence between proximal rods occurs decreases with increase in Mg concentration. From first-principles calculations, we find that the surface free energy of the Mg doped surface reduces with increasing Mg concentration in the samples. The calculations further suggest a reduction in the adsorption energy and the diffusion barrier of Ga adatoms along [ 11 2 ¯ 0 ] on the side wall surface of the NRs as the underlying mechanism for the observed enhancement in the radial growth rate of GaN NRs. The physics and chemistry behind reduction of the adsorption energy of Ga ad-atoms on the doped surface are explained in the light of electronic structure of the relevant surfaces.

Spin Uncoupling in Chemisorbed OCCO and CO 2: Two High-Energy Intermediates in Catalytic CO 2 Reduction

DOE PAGES

Hedstrom, Svante; dos Santos, Egon Campos; Liu, Chang; ...

2018-05-08

Here, the production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO 2 covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spin-uncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an averagemore » gross interaction energy of –1.82 eV/bond. The energy cost for electronically exciting OCCO– to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO 2, conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of –2.07 eV. The 5.0 eV excitation energy to the CO 2 – quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.« less

Stabilization of MgAl 2O 4 spinel surfaces via doping

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

Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.

Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl 2O 4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y 3+, Gd 3+,more » La 3+) and one tetravalent dopant (Zr 4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.« less

Stabilization of MgAl2O4 spinel surfaces via doping

NASA Astrophysics Data System (ADS)

Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.; Uberuaga, Blas P.

2016-07-01

Surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. Here, we report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl2O4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y3+, Gd3+, La3+) and one tetravalent dopant (Zr4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.

Stabilization of MgAl 2O 4 spinel surfaces via doping

DOE PAGES

Hasan, Md. M.; Dholabhai, Pratik P.; Castro, Ricardo H. R.; ...

2016-02-06

Here, the surface structure of complex oxides plays a vital role in processes such as sintering, thin film growth, and catalysis, as well as being a critical factor determining the stability of nanoparticles. We report atomistic calculations of the low-index stoichiometric magnesium aluminate spinel (MgAl 2O 4) surfaces, each with two different chemical terminations. High temperature annealing was used to explore the potential energy landscape and provide more stable surface structures. We find that the lowest energy surface is {100} while the highest energy surface is {111}. The surfaces were subsequently doped with three trivalent dopants (Y 3+, Gd 3+,more » La 3+) and one tetravalent dopant (Zr 4+) and both the surface segregation energies of the dopants and surface energies of the doped surface were determined. All of the dopants reduce the surface energy of spinel, though this reduction in energy depends on both the size and valence of the dopant. Dopants with larger ionic radius tend to segregate to the surface more strongly and reduce the surface energy to a greater extent. Furthermore, the ionic valence of the dopants seems to have a stronger influence on the segregation than does ionic size. For both undoped and doped spinel, the predicted crystal shape is dominated by {100} surfaces, but the relative fraction of the various surfaces changes with doping due to the unequal changes in energy, which has implications on equilibrium nanoparticle shapes and therefore on applications sensitive to surface properties.« less

Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes

DOE PAGES

Feaster, Jeremy T.; Shi, Chuan; Cave, Etosha R.; ...

2017-06-22

Increases in energy demand and in chemical production, together with the rise in CO 2 levels in the atmosphere, motivate the development of renewable energy sources. Electrochemical CO 2 reduction to fuels and chemicals is an appealing alternative to traditional pathways to fuels and chemicals due to its intrinsic ability to couple to solar and wind energy sources. Formate (HCOO –) is a key chemical for many industries; however, greater understanding is needed regarding the mechanism and key intermediates for HCOO – production. This work reports a joint experimental and theoretical investigation of the electrochemical reduction of CO 2 tomore » HCOO – on polycrystalline Sn surfaces, which have been identified as promising catalysts for selectively producing HCOO –. Our results show that Sn electrodes produce HCOO –, carbon monoxide (CO), and hydrogen (H 2) across a range of potentials and that HCOO – production becomes favored at potentials more negative than –0.8 V vs RHE, reaching a maximum Faradaic efficiency of 70% at –0.9 V vs RHE. Scaling relations for Sn and other transition metals are examined using experimental current densities and density functional theory (DFT) binding energies. While *COOH was determined to be the key intermediate for CO production on metal surfaces, we suggest that it is unlikely to be the primary intermediate for HCOO – production. Instead, *OCHO is suggested to be the key intermediate for the CO 2RR to HCOO – transformation, and Sn’s optimal *OCHO binding energy supports its high selectivity for HCOO –. Lastly, these results suggest that oxygen-bound intermediates are critical to understand the mechanism of CO 2 reduction to HCOO – on metal surfaces.« less

Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes

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

Feaster, Jeremy T.; Shi, Chuan; Cave, Etosha R.

Increases in energy demand and in chemical production, together with the rise in CO 2 levels in the atmosphere, motivate the development of renewable energy sources. Electrochemical CO 2 reduction to fuels and chemicals is an appealing alternative to traditional pathways to fuels and chemicals due to its intrinsic ability to couple to solar and wind energy sources. Formate (HCOO –) is a key chemical for many industries; however, greater understanding is needed regarding the mechanism and key intermediates for HCOO – production. This work reports a joint experimental and theoretical investigation of the electrochemical reduction of CO 2 tomore » HCOO – on polycrystalline Sn surfaces, which have been identified as promising catalysts for selectively producing HCOO –. Our results show that Sn electrodes produce HCOO –, carbon monoxide (CO), and hydrogen (H 2) across a range of potentials and that HCOO – production becomes favored at potentials more negative than –0.8 V vs RHE, reaching a maximum Faradaic efficiency of 70% at –0.9 V vs RHE. Scaling relations for Sn and other transition metals are examined using experimental current densities and density functional theory (DFT) binding energies. While *COOH was determined to be the key intermediate for CO production on metal surfaces, we suggest that it is unlikely to be the primary intermediate for HCOO – production. Instead, *OCHO is suggested to be the key intermediate for the CO 2RR to HCOO – transformation, and Sn’s optimal *OCHO binding energy supports its high selectivity for HCOO –. Lastly, these results suggest that oxygen-bound intermediates are critical to understand the mechanism of CO 2 reduction to HCOO – on metal surfaces.« less

Promotional effect of surface hydroxyls on electrochemical reduction of CO2 over SnOx/Sn electrode

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

Cui, Chaonan; Han, Jinyu; Zhu, Xinli

Tin oxide (SnOx) formation on tin-based electrode surfaces during CO2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnOx in CO2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnOx. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface. CO2 energetically prefers to react with the hydroxyl, formingmore » a bicarbonate (HCO3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous C-O bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H2O via protonation. Whereas the oxygen vacancy (VO) in the monolayer maybe formed by the reduction of the monolayer, it can be recovered by H2O dissociation, resulting in two embedded hydroxyl groups. However, the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of -0.20 V (RHE), lower than that for the latter (-0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnOx monolayer on the electrode under the operating conditions promotes CO2 reduction more effectively by forming surface hydroxyls, thereby, providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product. The work was supported in part by National Natural Sciences Foundation of China (Grant #21373148 and #21206117). The High Performance Computing Center of Tianjin University is acknowledged for providing services to the computing cluster. CC acknowledges the support of 24 China Scholarship Council (CSC). QG acknowledges the support of NSF-CBET program (Award no. CBET-1438440). DM was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The computations were performed in part using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington.« less

Nanoscale Reactions In Opto-magneto-electric Systems

NASA Astrophysics Data System (ADS)

Zeng, Zheng

My research is interdisciplinary in the areas of chemistry, physics and biology for better understanding of synergies between nanomaterials and opto-magneto-electric systems aimed at the practical applications in biosensor, energy (energy storage and electrocatalysis), and biomimetics, in particular, the associated electron transfer, light-matter interactions in nanoscale, such as surface plasmon resonance (SPR) (nanoplasmonics), and magnetic field effect on these phenomena with targeted nanomaterials. Specific research thrusts include: (1) investigation of surface plasmon generation from a novel nanoledge structure on thin metal film. The results are used for the nanostructure optimization for a nanofluidic-nanoplasmonic platform that may function as a multiplexed biosensor for protein biomarker detection; (2) examination of magnetic field effect on uniformly deposited metal oxide on electrospun carbon nanofiber (ECNF) scaffold for efficient energy storage (supercapacitor) and electrocatalytic energy conversion (oxygen reduction reduction). (3) magnetic response of cryptochrome 1 (CRY1) in photoinduced heterogeneous electron transfer (PHET).

On the theory of compliant wall drag reduction in turbulent boundary layers

NASA Technical Reports Server (NTRS)

Ash, R. L.

1974-01-01

A theoretical model has been developed which can explain how the motion of a compliant wall reduces turbulent skin friction drag. Available experimental evidence at low speeds has been used to infer that a compliant surface selectively removes energy from the upper frequency range of the energy containing eddies and through resulting surface motions can produce locally negative Reynolds stresses at the wall. The theory establishes a preliminary amplitude and frequency criterion as the basis for designing effective drag reducing compliant surfaces.

Significant thermal conductivity reduction of silicon nanowire forests through discrete surface doping of germanium

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

Pan, Ying; Hong, Guo; Raja, Shyamprasad N.

2015-03-02

Silicon nanowires (SiNWs) are promising materials for the realization of highly-efficient and cost effective thermoelectric devices. Reduction of the thermal conductivity of such materials is a necessary and viable pathway to achieve sufficiently high thermoelectric efficiencies, which are inversely proportional to the thermal conductivity. In this article, vertically aligned forests of SiNW and germanium (Ge)-doped SiNW with diameters around 100 nm have been fabricated, and their thermal conductivity has been measured. The results show that discrete surface doping of Ge on SiNW arrays can lead to 23% reduction in thermal conductivity at room temperature compared to uncoated SiNWs. Such reduction canmore » be further enhanced to 44% following a thermal annealing step. By analyzing the binding energy changes of Ge-3d and Si-2p using X-ray photoelectron spectroscopy, we demonstrate that surface doped Ge interacts strongly with Si, enhancing phonon scattering at the Si-Ge interface as has also been shown in non-equilibrium molecular dynamics studies of single nanowires. Overall, our results suggest a viable pathway to improve the energy conversion efficiency of nanowire-forest thermoelectric nanomaterials.« less

Multi-functional foot use during running in the zebra-tailed lizard (Callisaurus draconoides).

PubMed

Li, Chen; Hsieh, S Tonia; Goldman, Daniel I

2012-09-15

A diversity of animals that run on solid, level, flat, non-slip surfaces appear to bounce on their legs; elastic elements in the limbs can store and return energy during each step. The mechanics and energetics of running in natural terrain, particularly on surfaces that can yield and flow under stress, is less understood. The zebra-tailed lizard (Callisaurus draconoides), a small desert generalist with a large, elongate, tendinous hind foot, runs rapidly across a variety of natural substrates. We use high-speed video to obtain detailed three-dimensional running kinematics on solid and granular surfaces to reveal how leg, foot and substrate mechanics contribute to its high locomotor performance. Running at ~10 body lengths s(-1) (~1 m s(-1)), the center of mass oscillates like a spring-mass system on both substrates, with only 15% reduction in stride length on the granular surface. On the solid surface, a strut-spring model of the hind limb reveals that the hind foot saves ~40% of the mechanical work needed per step, significant for the lizard's small size. On the granular surface, a penetration force model and hypothesized subsurface foot rotation indicates that the hind foot paddles through fluidized granular medium, and that the energy lost per step during irreversible deformation of the substrate does not differ from the reduction in the mechanical energy of the center of mass. The upper hind leg muscles must perform three times as much mechanical work on the granular surface as on the solid surface to compensate for the greater energy lost within the foot and to the substrate.

Surface Plasmon-Assisted Solar Energy Conversion.

PubMed

Dodekatos, Georgios; Schünemann, Stefan; Tüysüz, Harun

2016-01-01

The utilization of localized surface plasmon resonance (LSPR) from plasmonic noble metals in combination with semiconductors promises great improvements for visible light-driven photocatalysis, in particular for energy conversion. This review summarizes the basic principles of plasmonic photocatalysis, giving a comprehensive overview about the proposed mechanisms for enhancing the performance of photocatalytically active semiconductors with plasmonic devices and their applications for surface plasmon-assisted solar energy conversion. The main focus is on gold and, to a lesser extent, silver nanoparticles in combination with titania as semiconductor and their usage as active plasmonic photocatalysts. Recent advances in water splitting, hydrogen generation with sacrificial organic compounds, and CO2 reduction to hydrocarbons for solar fuel production are highlighted. Finally, further improvements for plasmonic photocatalysts, regarding performance, stability, and economic feasibility, are discussed for surface plasmon-assisted solar energy conversion.

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.

The Dye Sensitized Photoelectrosynthesis Cell (DSPEC) for Solar Water Splitting and CO2 Reduction

NASA Astrophysics Data System (ADS)

Meyer, Thomas; Alibabaei, Leila; Sherman, Benjamin; Sheridan, Matthew; Ashford, Dennis; Lapides, Alex; Brennaman, Kyle; Nayak, Animesh; Roy, Subhangi; Wee, Kyung-Ryang; Gish, Melissa; Meyer, Jerry; Papanikolas, John

The dye-sensitized photoelectrosynthesis cell (DSPEC) integrates molecular level light absorption and catalysis with the bandgap properties of stable oxide materials such as TiO2 and NiO. Excitation of surface-bound chromophores leads to excited state formation and rapid electron or hole injection into the conduction or valence bands of n or p-type oxides. Addition of thin layers of TiO2 or NiO on the surfaces of mesoscopic, nanoparticle films of semiconductor or transparent conducting oxides to give core/shell structures provides a basis for accumulating multiple redox equivalents at catalysts for water oxidation or CO2 reduction. UNC EFRC Center for Solar Fuels, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001011.

Coupling molecular catalysts with nanostructured surfaces for efficient solar fuel production

NASA Astrophysics Data System (ADS)

Jin, Tong

Solar fuel generation via carbon dioxide (CO2) reduction is a promising approach to meet the increasing global demand for energy and to minimize the impact of energy consumption on climate change. However, CO2 is thermodynamically stable; its activation often requires the use of appropriate catalysts. In particular, molecular catalysts with well-defined structures and tunability have shown excellent activity in photochemical CO2 reduction. These homogenous catalysts, however, suffer from poor stability under photochemical conditions and difficulty in recycling from the reaction media. Heterogenized molecular catalysts, particularly those prepared by coupling molecular catalysts with solid-state surfaces, have attracted more attention in recent years as potential solutions to address the issues associated with molecular catalysts. In this work, solar CO2 reduction is investigated using systems coupling molecular catalysts with robust nanostructured surfaces. In Chapter 2, heterogenization of macrocyclic cobalt(III) and nickel (II) complexes on mesoporous silica surface was achieved by different methods. Direct ligand derivatization significantly lowered the catalytic activity of Co(III) complex, while grafting the Co(III) complex onto silica surface through Si-O-Co linkage resulted in hybrid catalysts with excellent activity in CO2 reduction in the presence of p-terphenyl as a molecular photosensitizer. An interesting loading effect was observed, in which the optimal activity was achieved at a medium Co(III) surface density. Heterogenization of the Ni(II) complex on silica surface has also been implemented, the poor photocatalytic activity of the hybrid catalyst can be attributed to the intrinsic nature of the homogeneous analogue. This study highlighted the importance of appropriate linking strategies in preparing functional heterogenized molecular catalysts. Coupling molecular complexes with light-harvesting surfaces could avoid the use of expensive molecular photosensitizers. In Chapter 3, effective coupling of the macrocyclic Co(III) complex with titanium dioxide (TiO¬2) nanoparticles was achieved by two deposition methods. The synthesized hybrid photocatalysts were thoroughly characterized with a variety of techniques. Upon UV light irradiation, photoexcited electrons in TiO2 nanoparticles were transferred to the surface Co(III) catalyst for CO2 reduction. Production of carbon monoxide (CO) from CO2 was confirmed by isotope labeling combined with infrared spectroscopy. Deposition of the Co(III) catalyst through Ti-O-Co linkages was essential for the photo-induced electron transfer and CO2-reduction activity using the hybrid photocatalysts. In Chapter 4, molecular Re(I) and Co(II) catalysts were coupled with silicon-based photoelectrodes, including a silicon nanowire (SiNW) photoelectrode, to achieve photoelectrochemical CO2 reduction. Photovoltages between 300-600 mV were obtained using the molecular catalysts on the silicon photoelectrodes. SiNWs exhibited enhanced properties, including significantly higher photovoltages than a planar silicon photoelectrode, the ability to protect one of the molecular catalysts from photo-induced decomposition, and excellent selectivity towards CO production in CO2 reduction. Recent theoretical and experimental work have demonstrated low-energy, binuclear pathways for CO2-to-CO conversion using several molecular catalysts. In such binuclear pathways, two metal centers work cooperatively to achieve two-electron CO2 reduction. Chapter 5 describes our effort to promote the binuclear pathway by grafting the molecular Co(III) catalyst onto silica surfaces. Different linking strategies were attempted to achieve this goal by planting the surface Co(III) sites in close proximity.

Descriptors and Thermodynamic Limitations of Electrocatalytic Carbon Dioxide Reduction on Rutile Oxide Surfaces.

PubMed

Bhowmik, Arghya; Vegge, Tejs; Hansen, Heine A

2016-11-23

A detailed understanding of the electrochemical reduction of CO 2 into liquid fuels on rutile metal oxide surfaces is developed by using DFT calculations. We consider oxide overlayer structures on RuO 2 (1 1 0) surfaces as model catalysts to elucidate the trends and limitations in the CO 2 reduction reaction (CO2RR) based on thermodynamic analysis. We aim to specify the requirements for CO2RR catalysts to establish adsorbate scaling relations and use these to derive activity volcanoes. Computational results show that the OH* binding free energy is a good descriptor of the thermodynamic limitations and it defines the left leg of the activity volcano for CO2RR. HCOOH* is a key intermediate for products formed through further reduction, for example, methanediol, methanol, and methane. The surfaces that do not bind HCOOH* are selective towards formic acid (HCOOH) production, but hydrogen evolution limits their suitability. We determine the ideal binding free energy for H* and OH* to facilitate selective CO2RR over H 2 /CO evolution to be ΔG B [H]>0.5 eV and -0.5 eV<ΔG B [OH]<0.1 eV. The Re-containing overlayers considered in this work display excellent promise for selectivity, although they are active at a highly reducing potential. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A unified view of energetic efficiency in active drag reduction, thrust generation and self-propulsion through a loss coefficient with some applications

NASA Astrophysics Data System (ADS)

Arakeri, Jaywant H.; Shukla, Ratnesh K.

2013-08-01

An analysis of the energy budget for the general case of a body translating in a stationary fluid under the action of an external force is used to define a power loss coefficient. This universal definition of power loss coefficient gives a measure of the energy lost in the wake of the translating body and, in general, is applicable to a variety of flow configurations including active drag reduction, self-propulsion and thrust generation. The utility of the power loss coefficient is demonstrated on a model bluff body flow problem concerning a two-dimensional elliptical cylinder in a uniform cross-flow. The upper and lower boundaries of the elliptic cylinder undergo continuous motion due to a prescribed reflectionally symmetric constant tangential surface velocity. It is shown that a decrease in drag resulting from an increase in the strength of tangential surface velocity leads to an initial reduction and eventual rise in the power loss coefficient. A maximum in energetic efficiency is attained for a drag reducing tangential surface velocity which minimizes the power loss coefficient. The effect of the tangential surface velocity on drag reduction and self-propulsion of both bluff and streamlined bodies is explored through a variation in the thickness ratio (ratio of the minor and major axes) of the elliptical cylinders.

Reducing adhesion energy of micro-relay electrodes by ion beam synthesized oxide nanolayers

DOE PAGES

Saha, Bivas; Peschot, Alexis; Osoba, Benjamin; ...

2017-03-09

Reduction in the adhesion energy of contacting metal electrode surfaces in nano-electro-mechanical switches is crucial for operation with low hysteresis voltage. We demonstrate that by forming thin layers of metal-oxides on metals such as Ru and W, the adhesion energy can be reduced by up to a factor of ten. We employ a low-energy ion-beam synthesis technique and subsequent thermal annealing to form very thin layers (~2 nm) of metal-oxides (such as RuO 2 and WO x) on Ru and W metal surfaces and quantify the adhesion energy using an atomic force microscope with microspherical tips.

Application of response surface methodology for optimization of parameters for microwave heating of rare earth carbonates

NASA Astrophysics Data System (ADS)

Yin, Shaohua; Lin, Guo; Li, Shiwei; Peng, Jinhui; Zhang, Libo

2016-09-01

Microwave heating has been applied in the field of drying rare earth carbonates to improve drying efficiency and reduce energy consumption. The effects of power density, material thickness and drying time on the weight reduction (WR) are studied using response surface methodology (RSM). The results show that RSM is feasible to describe the relationship between the independent variables and weight reduction. Based on the analysis of variance (ANOVA), the model is in accordance with the experimental data. The optimum experiment conditions are power density 6 w/g, material thickness 15 mm and drying time 15 min, resulting in an experimental weight reduction of 73%. Comparative experiments show that microwave drying has the advantages of rapid dehydration and energy conservation. Particle analysis shows that the size distribution of rare earth carbonates after microwave drying is more even than those in an oven. Based on these findings, microwave heating technology has an important meaning to energy-saving and improvement of production efficiency for rare earth smelting enterprises and is a green heating process.

First principles investigation of heterogeneous catalysis on metal oxide surfaces

NASA Astrophysics Data System (ADS)

Ghoussoub, Mireille

Metal oxides possess unique electronic and structural properties that render them highly favourable for applications in heterogeneous catalysis. In this study, computational atomistic modelling based on Density Functional Theory was used to investigate the reduction of carbon dioxide over hydroxylated indium oxide nanoparticles, as well at the activation of methane over oxygen-covered bimetallic surfaces. The first study employed metadynamics-biased ab initio molecular dynamics to obtain the free energy surface of the various reaction steps at finite temperature. In the second study, the nudged elastic band method was used to probe the C-H activation mechanisms for different surface configurations. In both cases, activation energies, reaction energies, transition state structures, and charge analysis results are used to explain the underlying mechanistic pathways.

Vapor shielding effects on energy transfer from plasma-gun generated ELM-like transient loads to material surfaces

NASA Astrophysics Data System (ADS)

Kikuchi, Y.; Sakuma, I.; Asai, Y.; Onishi, K.; Isono, W.; Nakazono, T.; Nakane, M.; Fukumoto, N.; Nagata, M.

2016-02-01

Energy transfer processes from ELM-like pulsed helium (He) plasmas with a pulse duration of ˜0.1 ms to aluminum (Al) and tungsten (W) surfaces were experimentally investigated by the use of a magnetized coaxial plasma gun device. The surface absorbed energy density of the He pulsed plasma on the W surface measured with a calorimeter was ˜0.44 MJ m-2, whereas it was ˜0.15 MJ m-2 on the Al surface. A vapor layer in front of the Al surface exposed to the He pulsed plasma was clearly identified by Al neutral emission line (Al i) measured with a high time resolution spectrometer, and fast imaging with a high-speed visible camera filtered around the Al i emission line. On the other hand, no clear evaporation in front of the W surface exposed to the He pulsed plasma was observed in the present condition. Discussions on the reduction in the surface absorbed energy density on the Al surface are provided by considering the latent heat of vaporization and radiation cooling due to the Al vapor cloud.

Surface energy modification for biomedical material by corona streamer plasma processing to mitigate bacterial adhesion

NASA Astrophysics Data System (ADS)

Alhamarneh, Ibrahim; Pedrow, Patrick

2011-10-01

Bacterial adhesion initiates biofouling of biomedical material but the processes can be reduced by adjusting the material's surface energy. The surface of surgical-grade 316L stainless steel (316L SS) had its hydrophilic property enhanced by processing in a corona streamer plasma reactor using atmospheric pressure Ar mixed with O2. Reactor excitation was 60 Hz ac high-voltage (<= 10 kV RMS) applied to a multi-needle-to-grounded-torus electrode configuration. Applied voltage and streamer current pulses were monitored with a broadband sensor system. When Ar/O2 plasma was used, the surface energy was enhanced more than with Ar plasma alone. Composition of the surface before and after plasma treatment was characterized by XPS. As the hydrophilicity of the treated surface increased so did percent of oxygen on the surface thus we concluded that reduction in contact angle was mainly due to new oxygen-containing functionalities. FTIR was used to identify oxygen containing groups on the surface. The aging effect that accompanies surface free energy adjustments was also observed.

“Feathered” fractal surfaces to minimize secondary electron emission for a wide range of incident angles

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

Swanson, Charles; Kaganovich, Igor D.

Complex structures on a material surface can significantly reduce the total secondary electron emission from that surface. The reduction occurs due to the capture of low-energy, true secondary electrons emitted at one point of the structure and intersecting another. We performed Monte Carlo calculations to demonstrate that fractal surfaces can reduce net secondary electron emission produced by the surface as compared to the flat surface. Specifically, we describe one surface, a “feathered” surface, which reduces the secondary electron emission yield more effectively than other previously considered configurations. Specifically, feathers grown onto a surface suppress secondary electron emission from shallow anglesmore » of incidence more effectively than velvet. Here, we find that, for the surface simulated, secondary electron emission yield remains below 20% of its un-suppressed value, even for shallow incident angles, where the velvet-only surface gives reduction factor of only 50%.« less

“Feathered” fractal surfaces to minimize secondary electron emission for a wide range of incident angles

DOE PAGES

Swanson, Charles; Kaganovich, Igor D.

2017-07-24

Complex structures on a material surface can significantly reduce the total secondary electron emission from that surface. The reduction occurs due to the capture of low-energy, true secondary electrons emitted at one point of the structure and intersecting another. We performed Monte Carlo calculations to demonstrate that fractal surfaces can reduce net secondary electron emission produced by the surface as compared to the flat surface. Specifically, we describe one surface, a “feathered” surface, which reduces the secondary electron emission yield more effectively than other previously considered configurations. Specifically, feathers grown onto a surface suppress secondary electron emission from shallow anglesmore » of incidence more effectively than velvet. Here, we find that, for the surface simulated, secondary electron emission yield remains below 20% of its un-suppressed value, even for shallow incident angles, where the velvet-only surface gives reduction factor of only 50%.« less

"Feathered" fractal surfaces to minimize secondary electron emission for a wide range of incident angles

NASA Astrophysics Data System (ADS)

Swanson, Charles; Kaganovich, Igor D.

2017-07-01

Complex structures on a material surface can significantly reduce the total secondary electron emission from that surface. The reduction occurs due to the capture of low-energy, true secondary electrons emitted at one point of the structure and intersecting another. We performed Monte Carlo calculations to demonstrate that fractal surfaces can reduce net secondary electron emission produced by the surface as compared to the flat surface. Specifically, we describe one surface, a "feathered" surface, which reduces the secondary electron emission yield more effectively than other previously considered configurations. Specifically, feathers grown onto a surface suppress secondary electron emission from shallow angles of incidence more effectively than velvet. We find that, for the surface simulated, secondary electron emission yield remains below 20% of its un-suppressed value, even for shallow incident angles, where the velvet-only surface gives reduction factor of only 50%.

Oxygen reduction on a Pt(111) catalyst in HT-PEM fuel cells by density functional theory

NASA Astrophysics Data System (ADS)

Sun, Hong; Li, Jie; Almheiri, Saif; Xiao, Jianyu

2017-08-01

The oxygen reduction reaction plays an important role in the performance of high-temperature proton exchange membrane (HT-PEM) fuel cells. In this study, a molecular dynamics model, which is based on the density functional theory and couples the system's energy, the exchange-correlation energy functional, the charge density distribution function, and the simplified Kohn-Sham equation, was developed to simulate the oxygen reduction reaction on a Pt(111) surface. Additionally, an electrochemical reaction system on the basis of a four-electron reaction mechanism was also developed for this simulation. The reaction path of the oxygen reduction reaction, the product structure of each reaction step and the system's energy were simulated. It is found that the first step reaction of the first hydrogen ion with the oxygen molecule is the controlling step of the overall reaction. Increasing the operating temperature speeds up the first step reaction rate and slightly decreases its reaction energy barrier. Our results provide insight into the working principles of HT-PEM fuel cells.

Halo-substituted azobenzenes adsorbed at Ag(111) and Au(111) interfaces: Structures and optical properties

NASA Astrophysics Data System (ADS)

Hughes, Zak E.; Baev, Alexander; Prasad, Paras N.; Walsh, Tiffany R.

2017-05-01

The adsorption of azobenzene (AB), ortho fluoro-azobenzene (FAB) and ortho chlor-azobenzol (ClAB), in both the cis and trans isomers, at the Au(111) and Ag(111) surfaces is investigated using plane-wave density functional calculations with the revPBE-vdW-DF functional. The resulting adsorption energies and internal structures of AB adsorbed to both metal surfaces are in broad agreement with available experimental data. In the gas phase, FAB and ClAB feature a significant reduction in the energy difference between the two isomeric states, compared with AB. This relative reduction in the energy difference is still significant for the adsorbed form of FAB but is only weakly apparent for ClAB. The absorption spectra of the molecules have also been calculated, with the halogen substituents generating significant changes in the gas phase, but only a modest difference for the adsorbed molecules.

Engineering Transition-Metal-Coated Tungsten Carbides for Efficient and Selective Electrochemical Reduction of CO2 to Methane.

PubMed

Wannakao, Sippakorn; Artrith, Nongnuch; Limtrakul, Jumras; Kolpak, Alexie M

2015-08-24

The design of catalysts for CO2 reduction is challenging because of the fundamental relationships between the binding energies of the reaction intermediates. Metal carbides have shown promise for transcending these relationships and enabling low-cost alternatives. Herein, we show that directional bonding arising from the mixed covalent/metallic character plays a critical role in governing the surface chemistry. This behavior can be described by consideration of individual d-band components. We use this model to predict efficient catalysts based on tungsten carbide with a sub-monolayer of iron adatoms. Our approach can be used to predict site-preference and binding-energy trends for complex catalyst surfaces. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The reduction mechanism of a natural chromite at 1416 °C

NASA Astrophysics Data System (ADS)

Soykan, O.; Eric, R. H.; King, R. P.

1991-02-01

The behavior of a natural chromite from the Bushveld Complex, Transvaal, South Africa, during reduction at 1416 °C by graphite was studied by means of thermogravimetric analysis, X-ray diffraction (XRD) analysis, energy-dispersive X-ray analysis (EDAX), and metallographic analysis. Experimental runs were allowed to proceed up to 120 minutes, resulting in 99 pct reduction. The specific objective of this study was to delineate the reduction mechanism of chromite by graphite. Zoning was observed in partially reduced chromites with degrees of reduction of up to about 70 pct. The inner cores were rich in iron, while the outer cores were depleted of iron. Energy-dispersive X-ray analysis revealed that Fe2+ and Cr3+ ions had diffused outward, whereas Cr2+, Al3+, and Mg2+ ions had diffused inward. The following mechanism of reduction, which is based on the assumption that the composition of the spinel phase remains stoichiometric with increasing degree of reduction, is proposed, (a) Initially, Fe3+ and Fe2+ ions at the surface of the chromite particle are reduced to the metallic state. This is followed immediately by the reduction of Cr3+ ions to the divalent state, (b) Cr2+ ions diffusing toward the center of the particle reduce the Fe3+ ions in the spinel under the surface of the particle to Fe2+ at the interface between the inner and outer cores. Fe2+ ions diffuse toward the surface, where they are reduced to metallic iron, (c) After the iron has been completely reduced, Cr3+ and any Cr2+ that is present are reduced to the metallic state, leaving an iron- and chromium-free spinel, MgAl2O4.

Improving the Thermodynamic Stability of Aluminate Spinel Nanoparticles with Rare Earths

DOE PAGES

Hasan, M. M.; Dey, Sanchita; Nafsin, Nazia; ...

2016-06-29

Surface energy is a key parameter to understand and predict the stability of catalysts. In this work, the surface energy of MgAl 2O 4, an important base material for catalyst support, was reduced by using dopants prone to form surface excess (surface segregation): Y 3+, Gd 3+, and La 3+. The energy reduction was predicted by atomistic simulations of spinel surfaces and experimentally demonstrated by using microcalorimetry. The surface energy of undoped MgAl 2O 4 was directly measured as 1.65 ± 0.04 J/m 2 and was reduced by adding 2 mol % of the dopants to 1.55 ± 0.04 J/mmore » 2 for Y-doping, 1.45 ± 0.05 J/m 2 for Gd-doping, and 1.26 ± 0.06 J/m 2 for La-doping. Atomistic simulations are qualitatively consistent with the experiments, reinforcing the link between the role of dopants in stabilizing the surface and the energy of segregation. Surface segregation was experimentally assessed using electron energy loss spectroscopy mapping in a scanning transmission electron microscopy image. Finally, the reduced energy resulted in coarsening inhibition for the doped samples and, hence, systematically smaller particle sizes (larger surface areas), meaning increased stability for catalytic applications. Moreover, both experiment and modeling reveal preferential dopant segregation to specific surfaces, which leads to the preponderance of {111} surface planes and suggests a strategy to enhance the area of desired surfaces in nanoparticles for better catalyst support activity.« less

Structural transformation in monolayer materials: a 2D to 1D transformation.

PubMed

Momeni, Kasra; Attariani, Hamed; LeSar, Richard A

2016-07-20

Reducing the dimensions of materials to atomic scales results in a large portion of atoms being at or near the surface, with lower bond order and thus higher energy. At such scales, reduction of the surface energy and surface stresses can be the driving force for the formation of new low-dimensional nanostructures, and may be exhibited through surface relaxation and/or surface reconstruction, which can be utilized for tailoring the properties and phase transformation of nanomaterials without applying any external load. Here we used atomistic simulations and revealed an intrinsic structural transformation in monolayer materials that lowers their dimension from 2D nanosheets to 1D nanostructures to reduce their surface and elastic energies. Experimental evidence of such transformation has also been revealed for one of the predicted nanostructures. Such transformation plays an important role in bi-/multi-layer 2D materials.

Methods and energy storage devices utilizing electrolytes having surface-smoothing additives

DOEpatents

Xu, Wu; Zhang, Jiguang; Graff, Gordon L; Chen, Xilin; Ding, Fei

2015-11-12

Electrodeposition and energy storage devices utilizing an electrolyte having a surface-smoothing additive can result in self-healing, instead of self-amplification, of initial protuberant tips that give rise to roughness and/or dendrite formation on the substrate and anode surface. For electrodeposition of a first metal (M1) on a substrate or anode from one or more cations of M1 in an electrolyte solution, the electrolyte solution is characterized by a surface-smoothing additive containing cations of a second metal (M2), wherein cations of M2 have an effective electrochemical reduction potential in the solution lower than that of the cations of M1.

Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

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

Matanovic, Ivana; Garzon, Fernando H.

We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate formore » the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.« less

Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

DOE PAGES

Matanovic, Ivana; Garzon, Fernando H.

2018-04-26

We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate formore » the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.« less

Options for reducing carbon dioxide emissions

NASA Astrophysics Data System (ADS)

Rosenfeld, Arthur H.; Price, Lynn

1992-03-01

Improvements in energy efficiency can significantly reduce the annual growth in greenhouse gas emissions. Such improvements occur when energy intensity is reduced; no reduction in energy services is required. Using the concept of ``cost of conserved energy'' to develop conservation supply curves similar to resource supply curves, researchers consistently find that electricity and natural gas savings of nearly 50% of current consumption are possible for U.S. buildings. Such reductions in energy consumption directly reduce emissions of greenhouse gases. To capture these savings, we must continue to develop energy-efficient technologies and strategies. This paper describes three recent energy-efficient technologies that benefitted from energy conservation research and development (R&D) funding: high-frequency ballasts, compact fluorescent lamps, and low-emissivity windows. Other advanced technologies and strategies of spectrally selective windows, superwindows, electrochromic windows, advanced insulation, low-flow showerheads, improved recessed lamp fixtures, whitening surfaces and planting urban trees, daylighting, and thermal energy storage are also discussed.

Retrospective analysis of pulsed radiofrequency energy therapy use in the treatment of chronic pressure ulcers.

PubMed

Conner-Kerr, Teresa; Isenberg, Richard A

2012-06-01

: The purpose of the study was to evaluate the benefit of using pulsed radiofrequency energy (PRFE) therapy in the treatment of chronic pressure ulcers. : A retrospective analysis was performed using case series data from the Provant Wound Registry, which consists of demographic characteristics and wound healing outcomes for patients treated with the Provant Therapy System. : The analysis subset consisted of data from 39 distinct centers, including both residential and ambulatory care facilities. : The analysis included data from 89 patients. The majority of patients (89%) were cared for in residential facilities, whereas 11% of patients were cared for in ambulatory care facilities. : Specific outcomes that assessed wound healing between the initial time point and at the 4-week follow-up were as follows: percent wound surface area reduction (PWAR), proportion of wounds achieving 50% reduction or greater in wound surface area (50% PWAR), and the rate of wound healing (wound healing trajectory in centimeters squared per day). : Overall, there was a 51% median reduction in wound surface area (PWAR) after 4 weeks of PRFE therapy for wounds in the study, with 51% of wounds (56/110) achieving 50% reduction or greater in wound surface area (50% PWAR). Rate of healing measurements for the overall study group showed a median wound healing trajectory of 0.13 cm/d at 4 weeks. : Compared with historical controls and other studies using similar surrogate wound healing markers, these results suggest PRFE therapy is a beneficial adjuvant treatment option for healing chronic pressure ulcers.

Linking atmospheric synoptic transport, cloud phase, surface energy fluxes, and sea-ice growth: observations of midwinter SHEBA conditions

NASA Astrophysics Data System (ADS)

Persson, P. Ola G.; Shupe, Matthew D.; Perovich, Don; Solomon, Amy

2017-08-01

Observations from the Surface Heat Budget of the Arctic Ocean (SHEBA) project are used to describe a sequence of events linking midwinter long-range advection of atmospheric heat and moisture into the Arctic Basin, formation of supercooled liquid water clouds, enhancement of net surface energy fluxes through increased downwelling longwave radiation, and reduction in near-surface conductive heat flux loss due to a warming of the surface, thereby leading to a reduction in sea-ice bottom growth. The analyses provide details of two events during Jan. 1-12, 1998, one entering the Arctic through Fram Strait and the other from northeast Siberia; winter statistics extend the results. Both deep, precipitating frontal clouds and post-frontal stratocumulus clouds impact the surface radiation and energy budget. Cloud liquid water, occurring preferentially in stratocumulus clouds extending into the base of the inversion, provides the strongest impact on surface radiation and hence modulates the surface forcing, as found previously. The observations suggest a minimum water vapor threshold, likely case dependent, for producing liquid water clouds. Through responses to the radiative forcing and surface warming, this cloud liquid water also modulates the turbulent and conductive heat fluxes, and produces a thermal wave penetrating into the sea ice. About 20-33 % of the observed variations of bottom ice growth can be directly linked to variations in surface conductive heat flux, with retarded ice growth occurring several days after these moisture plumes reduce the surface conductive heat flux. This sequence of events modulate pack-ice wintertime environmental conditions and total ice growth, and has implications for the annual sea-ice evolution, especially for the current conditions of extensive thinner ice.

Unifying the 2e(-) and 4e(-) Reduction of Oxygen on Metal Surfaces.

PubMed

Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan; Nørskov, Jens K

2012-10-18

Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2e(-) versus 4e(-) reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculations, we show that to a first approximation an activity descriptor, ΔGOH*, the free energy of adsorbed OH*, can be used to describe trends for the 2e(-) and 4e(-) reduction of oxygen. While the weak binding of OOH* on Au(111) makes it an unsuitable catalyst for the 4e(-) reduction, this weak binding is optimal for the 2e(-) reduction to H2O2. We find quite a remarkable agreement between the predictions of the model and experimental results spanning nearly 30 years.

Modelling energy efficiency of an integrated anaerobic digestion and photodegradation of distillery effluent using response surface methodology.

PubMed

Apollo, Seth; Onyango, Maurice S; Ochieng, Aoyi

2016-10-01

Anaerobic digestion (AD) is efficient in organic load removal and bioenergy recovery when applied in treating distillery effluent; however, it is ineffective in colour reduction. In contrast, ultraviolet (UV) photodegradation post-treatment for the AD-treated distillery effluent is effective in colour reduction but has high energy requirement. The effects of operating parameters on bioenergy production and energy demand of photodegradation were modelled using response surface methodology (RSM) with a view of developing a sustainable process in which the biological step could supply energy to the energy-intensive photodegradation step. The organic loading rate (OLRAD) and hydraulic retention time (HRTAD) of the initial biological step were the variables investigated. It was found that the initial biological step removed about 90% of COD and only about 50% colour while photodegradation post-treatment removed 98% of the remaining colour. Maximum bioenergy production of 180.5 kWh/m(3) was achieved. Energy demand of the UV lamp was lowest at low OLRAD irrespective of HRTAD, with values ranging between 87 and 496 kWh/m(3). The bioenergy produced formed 93% of the UV lamp energy demand when the system was operated at OLRAD of 3 kg COD/m(3) d and HRT of 20 days. The presumed carbon dioxide emission reduction when electricity from bioenergy was used to power the UV lamp was 28.8 kg CO2 e/m(3), which could reduce carbon emission by 31% compared to when electricity from the grid was used, leading to environmental conservation.

Multi-heme cytochromes provide a pathway for survival in energy-limited environments

PubMed Central

Deng, Xiao; Dohmae, Naoshi; Nealson, Kenneth H.; Hashimoto, Kazuhito; Okamoto, Akihiro

2018-01-01

Bacterial reduction of oxidized sulfur species (OSS) is critical for energy production in anaerobic marine subsurfaces. In organic-poor sediments, H2 has been considered as a major energy source for bacterial respiration. We identified outer-membrane cytochromes (OMCs) that are broadly conserved in sediment OSS-respiring bacteria and enable cells to directly use electrons from insoluble minerals via extracellular electron transport. Biochemical, transcriptomic, and microscopic analyses revealed that the identified OMCs were highly expressed on the surface of cells and nanofilaments in response to electron donor limitation. This electron uptake mechanism provides sufficient but minimum energy to drive the reduction of sulfate and other OSS. These results suggest a widespread mechanism for survival of OSS-respiring bacteria via electron uptake from solid minerals in energy-poor marine sediments. PMID:29464208

Single-Cell Imaging and Spectroscopic Analyses of Cr(VI) Reduction on the Surface of Bacterial Cells

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

Wang, Yuanmin; Sevinc, Papatya C.; Belchik, Sara M.

2013-01-22

We investigate single-cell reduction of toxic Cr(VI) by the dissimilatory metal-reducing bacterium Shewanella oneidensis MR-1 (MR-1), an important bioremediation process, using Raman spectroscopy and scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDX). Our experiments indicate that the toxic and highly soluble Cr(VI) can be efficiently reduced to the less toxic and non-soluble Cr2O3 nanoparticles by MR-1. Cr2O3 is observed to emerge as nanoparticles adsorbed on the cell surface and its chemical nature is identified by EDX imaging and Raman spectroscopy. Co-localization of Cr2O3 and cytochromes by EDX imaging and Raman spectroscopy suggests a terminal reductase role for MR-1more » surface-exposed cytochromes MtrC and OmcA. Our experiments revealed that the cooperation of surface proteins OmcA and MtrC makes the reduction reaction most efficient, and the sequence of the reducing reactivity of the MR-1 is: wild type > single mutant @mtrC or mutant @omcA > double mutant (@omcA-@mtrC). Moreover, our results also suggest that the direct microbial Cr(VI) reduction and Fe(II) (hematite)-mediated Cr(VI) reduction mechanisms may co-exist in the reduction processes.« less

Investigation of the changes in aerosolization behavior between the jet-milled and spray-dried colistin powders through surface energy characterization

PubMed Central

Jong, Teresa; Li, Jian; Mortonx, David A.V.; Zhou, Qi (Tony); Larson, Ian

2016-01-01

This study aimed to investigate the surface energy factors behind improved aerosolization performance of spray-dried colistin powder formulations compared to those produced by jet-milling. Inhalable colistin powder formulations were produced by jet-milling or spray-drying (with or without L-leucine). Scanning electron micrographs showed the jet-milled particles had irregularly angular shapes, while the spray-dried particles were more spherical. Significantly higher fine particle fractions (FPFs) were measured for the spray-dried (43.8-49.6%) vs. the jet-milled formulation (28.4 %) from a Rotahaler at 60L/min; albeit the size distribution of the jet-milled powder was smaller. Surprisingly, addition of L-leucine in the spray drying feed-solution gave no significant improvement in FPF. As measured by inverse gas chromatography, spray-dried formulations had significantly (p<0.001) lower dispersive, specific and total surface energy values and more uniform surface energy distributions than the jet-milled powder. Interestingly, no significant difference was measured in the specific and total surface energy values between the spray-dried formulation with or without L-leucine. Based upon our previous findings in the self-assembling behavior of colistin in aqueous solution and the surface energy data obtained here, we propose the self-assembly of colistin molecules during spray-drying, contributed significantly to the reduction of surface free energy and the superior aerosolization performance. PMID:26886330

Boron-doped diamond semiconductor electrodes: Efficient photoelectrochemical CO2 reduction through surface modification

NASA Astrophysics Data System (ADS)

Roy, Nitish; Hirano, Yuiri; Kuriyama, Haruo; Sudhagar, Pitchaimuthu; Suzuki, Norihiro; Katsumata, Ken-Ichi; Nakata, Kazuya; Kondo, Takeshi; Yuasa, Makoto; Serizawa, Izumi; Takayama, Tomoaki; Kudo, Akihiko; Fujishima, Akira; Terashima, Chiaki

2016-11-01

Competitive hydrogen evolution and multiple proton-coupled electron transfer reactions limit photoelectrochemical CO2 reduction in aqueous electrolyte. Here, oxygen-terminated lightly boron-doped diamond (BDDL) thin films were synthesized as a semiconductor electron source to accelerate CO2 reduction. However, BDDL alone could not stabilize the intermediates of CO2 reduction, yielding a negligible amount of reduction products. Silver nanoparticles were then deposited on BDDL because of their selective electrochemical CO2 reduction ability. Excellent selectivity (estimated CO:H2 mass ratio of 318:1) and recyclability (stable for five cycles of 3 h each) for photoelectrochemical CO2 reduction were obtained for the optimum silver nanoparticle-modified BDDL electrode at -1.1 V vs. RHE under 222-nm irradiation. The high efficiency and stability of this catalyst are ascribed to the in situ photoactivation of the BDDL surface during the photoelectrochemical reaction. The present work reveals the potential of BDDL as a high-energy electron source for use with co-catalysts in photochemical conversion.

Pipeline Corrosion and Friction Reduction Coatings.

DTIC Science & Technology

1986-06-01

surface energy, i.e., a lower friction surface. Due to the toxic nature of fluorine cas we elected to have Air Products and Chemicals , Inc . perform...Research and Chemical Corp. PR-319 A.P. 8717-21 (1) - 6.9 +19.0 +32.5 +14.9 (1) Indicates Air Products and Chemicals , Inc . proprietary exposure method

Dynamics of ice nucleation on water repellent surfaces.

PubMed

Alizadeh, Azar; Yamada, Masako; Li, Ri; Shang, Wen; Otta, Shourya; Zhong, Sheng; Ge, Liehui; Dhinojwala, Ali; Conway, Ken R; Bahadur, Vaibhav; Vinciquerra, A Joseph; Stephens, Brian; Blohm, Margaret L

2012-02-14

Prevention of ice accretion and adhesion on surfaces is relevant to many applications, leading to improved operation safety, increased energy efficiency, and cost reduction. Development of passive nonicing coatings is highly desirable, since current antiicing strategies are energy and cost intensive. Superhydrophobicity has been proposed as a lead passive nonicing strategy, yet the exact mechanism of delayed icing on these surfaces is not clearly understood. In this work, we present an in-depth analysis of ice formation dynamics upon water droplet impact on surfaces with different wettabilities. We experimentally demonstrate that ice nucleation under low-humidity conditions can be delayed through control of surface chemistry and texture. Combining infrared (IR) thermometry and high-speed photography, we observe that the reduction of water-surface contact area on superhydrophobic surfaces plays a dual role in delaying nucleation: first by reducing heat transfer and second by reducing the probability of heterogeneous nucleation at the water-substrate interface. This work also includes an analysis (based on classical nucleation theory) to estimate various homogeneous and heterogeneous nucleation rates in icing situations. The key finding is that ice nucleation delay on superhydrophobic surfaces is more prominent at moderate degrees of supercooling, while closer to the homogeneous nucleation temperature, bulk and air-water interface nucleation effects become equally important. The study presented here offers a comprehensive perspective on the efficacy of textured surfaces for nonicing applications.

Global potential energy surface of ground state singlet spin O4

NASA Astrophysics Data System (ADS)

Mankodi, Tapan K.; Bhandarkar, Upendra V.; Puranik, Bhalchandra P.

2018-02-01

A new global potential energy for the singlet spin state O4 system is reported using CASPT2/aug-cc-pVTZ ab initio calculations. The geometries for the six-dimensional surface are constructed using a novel point generation scheme that employs randomly generated configurations based on the beta distribution. The advantage of this scheme is apparent in the reduction of the number of required geometries for a reasonably accurate potential energy surface (PES) and the consequent decrease in the overall computational effort. The reported surface matches well with the recently published singlet surface by Paukku et al. [J. Chem. Phys. 147, 034301 (2017)]. In addition to the O4 PES, the ground state N4 PES is also constructed using the point generation scheme and compared with the existing PES [Y. Paukku et al., J. Chem. Phys. 139, 044309 (2013)]. The singlet surface is constructed with the aim of studying high energy O2-O2 collisions and predicting collision induced dissociation cross section to be used in simulating non-equilibrium aerothermodynamic flows.

Locating landmarks on high-dimensional free energy surfaces

PubMed Central

Chen, Ming; Yu, Tang-Qing; Tuckerman, Mark E.

2015-01-01

Coarse graining of complex systems possessing many degrees of freedom can often be a useful approach for analyzing and understanding key features of these systems in terms of just a few variables. The relevant energy landscape in a coarse-grained description is the free energy surface as a function of the coarse-grained variables, which, despite the dimensional reduction, can still be an object of high dimension. Consequently, navigating and exploring this high-dimensional free energy surface is a nontrivial task. In this paper, we use techniques from multiscale modeling, stochastic optimization, and machine learning to devise a strategy for locating minima and saddle points (termed “landmarks”) on a high-dimensional free energy surface “on the fly” and without requiring prior knowledge of or an explicit form for the surface. In addition, we propose a compact graph representation of the landmarks and connections between them, and we show that the graph nodes can be subsequently analyzed and clustered based on key attributes that elucidate important properties of the system. Finally, we show that knowledge of landmark locations allows for the efficient determination of their relative free energies via enhanced sampling techniques. PMID:25737545

Sputtering yields and surface chemical modification of tin-doped indium oxide in hydrocarbon-based plasma etching

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

Li, Hu; Karahashi, Kazuhiro; Hamaguchi, Satoshi, E-mail: hamaguch@ppl.eng.osaka-u.ac.jp

2015-11-15

Sputtering yields and surface chemical compositions of tin-doped indium oxide (or indium tin oxide, ITO) by CH{sup +}, CH{sub 3}{sup +}, and inert-gas ion (He{sup +}, Ne{sup +}, and Ar{sup +}) incidence have been obtained experimentally with the use of a mass-selected ion beam system and in-situ x-ray photoelectron spectroscopy. It has been found that etching of ITO is chemically enhanced by energetic incidence of hydrocarbon (CH{sub x}{sup +}) ions. At high incident energy incidence, it appears that carbon of incident ions predominantly reduce indium (In) of ITO and the ITO sputtering yields by CH{sup +} and CH{sub 3}{sup +}more » ions are found to be essentially equal. At lower incident energy (less than 500 eV or so), however, a hydrogen effect on ITO reduction is more pronounced and the ITO surface is more reduced by CH{sub 3}{sup +} ions than CH{sup +} ions. Although the surface is covered more with metallic In by low-energy incident CH{sub 3}{sup +} ions than CH{sup +} ions and metallic In is in general less resistant against physical sputtering than its oxide, the ITO sputtering yield by incident CH{sub 3}{sup +} ions is found to be lower than that by incident CH{sup +} ions in this energy range. A postulation to account for the relation between the observed sputtering yield and reduction of the ITO surface is also presented. The results presented here offer a better understanding of elementary surface reactions observed in reactive ion etching processes of ITO by hydrocarbon plasmas.« less

Fabrication of Nb/Pb structures through ultrashort pulsed laser deposition

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

Gontad, Francisco; Lorusso, Antonella, E-mail: antonella.lorusso@le.infn.it; Perrone, Alessio

This work reports the fabrication of Nb/Pb structures with an application as photocathode devices. The use of relatively low energy densities for the ablation of Nb with ultrashort pulses favors the reduction of droplets during the growth of the film. However, the use of laser fluences in this ablation regime results in a consequent reduction in the average deposition rate. On the other hand, despite the low deposition rate, the films present a superior adherence to the substrate and an excellent coverage of the irregular substrate surface, avoiding the appearance of voids or discontinuities on the film surface. Moreover, themore » low energy densities used for the ablation favor the growth of nanocrystalline films with a similar crystalline structure to the bulk material. Therefore, the use of low ablation energy densities with ultrashort pulses for the deposition of the Nb thin films allows the growth of very adherent and nanocrystalline films with adequate properties for the fabrication of Nb/Pb structures to be included in superconducting radiofrequency cavities.« less

Comparative life cycle assessment of standard and green roofs.

PubMed

Saiz, Susana; Kennedy, Christopher; Bass, Brad; Pressnail, Kim

2006-07-01

Life cycle assessment (LCA) is used to evaluate the benefits, primarily from reduced energy consumption, resulting from the addition of a green roof to an eight story residential building in Madrid. Building energy use is simulated and a bottom-up LCA is conducted assuming a 50 year building life. The key property of a green roof is its low solar absorptance, which causes lower surface temperature, thereby reducing the heat flux through the roof. Savings in annual energy use are just over 1%, but summer cooling load is reduced by over 6% and reductions in peak hour cooling load in the upper floors reach 25%. By replacing the common flat roof with a green roof, environmental impacts are reduced by between 1.0 and 5.3%. Similar reductions might be achieved by using a white roof with additional insulation for winter, but more substantial reductions are achieved if common use of green roofs leads to reductions in the urban heat island.

Rutile (β-)MnO2 surfaces and vacancy formation for high electrochemical and catalytic performance.

PubMed

Tompsett, David A; Parker, Stephen C; Islam, M Saiful

2014-01-29

MnO2 is a technologically important material for energy storage and catalysis. Recent investigations have demonstrated the success of nanostructuring for improving the performance of rutile MnO2 in Li-ion batteries and supercapacitors and as a catalyst. Motivated by this we have investigated the stability and electronic structure of rutile (β-)MnO2 surfaces using density functional theory. A Wulff construction from relaxed surface energies indicates a rod-like equilibrium morphology that is elongated along the c-axis, and is consistent with the large number of nanowire-type structures that are obtainable experimentally. The (110) surface dominates the crystallite surface area. Moreover, higher index surfaces than considered in previous work, for instance the (211) and (311) surfaces, are also expressed to cap the rod-like morphology. Broken coordinations at the surface result in enhanced magnetic moments at Mn sites that may play a role in catalytic activity. The calculated formation energies of oxygen vacancy defects and Mn reduction at key surfaces indicate facile formation at surfaces expressed in the equilibrium morphology. The formation energies are considerably lower than for comparable structures such as rutile TiO2 and are likely to be important to the high catalytic activity of rutile MnO2.

Effects of a TiC substrate on the catalytic activity of Pt for NO reduction.

PubMed

Chu, Xingli; Fu, Zhaoming; Li, Shasha; Zhang, Xilin; Yang, Zongxian

2016-05-11

Density functional theory calculations are used to elucidate the catalytic properties of a Pt monolayer supported on a TiC(001) substrate (Pt/TiC) toward NO reduction. It is found that the compound system of Pt/TiC has a good stability due to the strong Pt-TiC interaction. The diverse dissociation paths (namely the direct dissociation mechanism and the dimeric mechanism) are investigated. The transition state searching calculations suggest that NO has strong diffusion ability and small activation energy for dissociation on the Pt/TiC. For NO reduction on the Pt/TiC surface, we have found that the direct dissociation mechanisms (NO + N + O → NO2 + N and NO + N + O → N2 + O + O) are easier with a smaller dissociation barrier than those on the Pt(111) surface; and the dimeric process (NO + NO → (NO)2 → N2O + O → N2 + O + O) is considered to be dominant or significant with even a lower energy barrier than that of the direct dissociation. The results show that Pt/TiC can serve as an efficient catalyst for NO reduction.

Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges

NASA Astrophysics Data System (ADS)

Ma, Tao; Fan, Qun; Tao, Hengcong; Han, Zishan; Jia, Mingwen; Gao, Yunnan; Ma, Wangjing; Sun, Zhenyu

2017-11-01

Electrochemical CO2 reduction (ECR) offers an important pathway for renewable energy storage and fuels production. It still remains a challenge in designing highly selective, energy-efficient, robust, and cost-effective electrocatalysts to facilitate this kinetically slow process. Metal-free carbon-based materials have features of low cost, good electrical conductivity, renewability, diverse structure, and tunability in surface chemistry. In particular, surface functionalization of carbon materials, for example by doping with heteroatoms, enables access to unique active site architectures for CO2 adsorption and activation, leading to interesting catalytic performances in ECR. We aim to provide a comprehensive review of this category of metal-free catalysts for ECR, providing discussions and/or comparisons among different nonmetallic catalysts, and also possible origin of catalytic activity. Fundamentals and some future challenges are also described.

Drag Reduction On Multiscale Superhydrophobic Surfaces

NASA Astrophysics Data System (ADS)

Jenner, Elliot; Barbier, Charlotte; D'Urso, Brian

2013-11-01

Fluid drag reduction is of great interest in a variety of fields, including hull engineering, microfluidics, and drug delivery. We fabricated samples with multi-scale superhydrophobic surfaces, which consist of hexagonally self-ordered microscopic spikes grown via anodization on macroscopic grooves cut in aluminum. The hydrodynamic drag properties were studied with a cone-and-plate rheometer, showing significant drag reduction near 15% in turbulent flow and near 30% in laminar flow. In addition to these experiments, numerical simulations were performed in order to estimate the slip length at high speeds. Furthermore, we will report on the progress of experiments with a new type of surface combining superhydrophobic surfaces like those discussed above with Slippery Liquid Infused Porous Surfaces (SLIPS), which utilize an oil layer to create a hydrophobic self-repairing surface. These ``Super-SLIPS'' may combine the best properties of both superhydrophobic surfaces and SLIPS, by combining a drag reducing air-layer and an oil layer which may improve durability and biofouling resistance. This research was supported by the ORNL Seed Money Program. Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for the U.S. Dept. of Energy under contract DE-AC05-00OR22725.

Nanocrystalline copper films are never flat

NASA Astrophysics Data System (ADS)

Zhang, Xiaopu; Han, Jian; Plombon, John J.; Sutton, Adrian P.; Srolovitz, David J.; Boland, John J.

2017-07-01

We used scanning tunneling microscopy to study low-angle grain boundaries at the surface of nearly planar copper nanocrystalline (111) films. The presence of grain boundaries and their emergence at the film surface create valleys composed of dissociated edge dislocations and ridges where partial dislocations have recombined. Geometric analysis and simulations indicated that valleys and ridges were created by an out-of-plane grain rotation driven by reduction of grain boundary energy. These results suggest that in general, it is impossible to form flat two-dimensional nanocrystalline films of copper and other metals exhibiting small stacking fault energies and/or large elastic anisotropy, which induce a large anisotropy in the dislocation-line energy.

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2.

PubMed

Favaro, Marco; Xiao, Hai; Cheng, Tao; Goddard, William A; Yano, Junko; Crumlin, Ethan J

2017-06-27

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2

PubMed Central

Favaro, Marco; Yano, Junko; Crumlin, Ethan J.

2017-01-01

A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO2 in the presence of water as the first step toward CO2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts. PMID:28607092

Fabricating Superhydrophobic and Superoleophobic Surfaces with Multiscale Roughness Using Airbrush and Electrospray

NASA Astrophysics Data System (ADS)

AL-Milaji, Karam N.

Examples of superhydrophobic surfaces found in nature such as self-cleaning property of lotus leaf and walking on water ability of water strider have led to an extensive investigation in this area over the past few decades. When a water droplet rests on a textured surface, it may either form a liquid-solid-vapor composite interface by which the liquid droplet partially sits on air pockets or it may wet the surface in which the water replaces the trapped air depending on the surface roughness and the surface chemistry. Super water repellent surfaces have numerous applications in our daily life such as drag reduction, anti-icing, anti-fogging, energy conservation, noise reduction, and self-cleaning. In fact, the same concept could be applied in designing and producing surfaces that repel organic contaminations (e.g. low surface tension liquids). However, superoleophobic surfaces are more challenging to fabricate than superhydrophobic surfaces since the combination of multiscale roughness with re-entrant or overhang structure and surface chemistry must be provided. In this study, simple, cost-effective and potentially scalable techniques, i.e., airbrush and electrospray, were employed for the sake of making superhydrophobic and superoleophobic coatings with random and patterned multiscale surface roughness. Different types of silicon dioxide were utilized in this work to in order to study and to characterize the effect of surface morphology and surface roughness on surface wettability. The experimental findings indicated that super liquid repellent surfaces with high apparent contact angles and extremely low sliding angles were successfully fabricated by combining re-entrant structure, multiscale surface roughness, and low surface energy obtained from chemically treating the fabricated surfaces. In addition to that, the experimental observations regarding producing textured surfaces in mask-assisted electrospray were further validated by simulating the actual working conditions and geometries using COMSOL Multiphysics.

Energetics of the formation of Cu-Ag core–shell nanoparticles

DOE PAGES

Chandross, Michael

2014-10-06

Our work presents molecular dynamics and Monte Carlo simulations aimed at developing an understanding of the formation of core–shell Cu-Ag nanoparticles. The effects of surface and interfacial energies were considered and used to form a phenomenological model that calculates the energy gained upon the formation of a core–shell structure from two previously distinct, non-interacting nanoparticles. In most cases, the core–shell structure was found to be energetically favored. Specifically, the difference in energy as a function of the radii of the individual Cu and Ag particles was examined, with the assumption that a core–shell structure forms. In general, it was foundmore » that the energetic gain from forming such a structure increased with increasing size of the initial Ag particle. This result was interpreted as a result of the reduction in surface energy. Moreover, for two separate particles, both Cu and Ag contribute to the surface energy; however, for a core–shell structure, the only contribution to the surface energy is from the Ag shell and the Cu contribution is changed to a Cu–Ag interfacial energy, which is always smaller.« less

Kinetics and mechanisms of iron sulfide reductions in hydrogen and in carbon monoxide

USGS Publications Warehouse

Wiltowski, T.; Hinckley, C.C.; Smith, Gerard V.; Nishizawa, T.; Saporoschenko, Mykola; Shiley, R.H.; Webster, J.R.

1987-01-01

The reduction of iron sulfides by hydrogen and by carbon monoxide has been studied using plug flow and thermogravimetric methods. The reactions were studied in the 523-723??K temperature range and were found to be first-order processes. Plug flow studies were used to correlate reaction rates between pyrite and the gases as a function of the surface area of the pyrite. The rate of H2S formation increases with the surface area of the pyrite sample. The results of thermogravimetric experiments indicate that the reactions consist of several steps. Rate constants for the pyrite reduction by H2 and by CO were obtained. The activation energies increased with degree of reduction. Values of Ea were 113.2 (step I) and 122.5 kJ/mole (step II) for pyrite reduction with CO and 99.4 (step I), 122.4 (step II), 125.2 (step III), and 142.6 kJ/mole (step IV) for pyrite reduction with hydrogen. ?? 1987.

Aircraft surface coatings study: Energy efficient transport program. [sprayed and adhesive bonded coatings for drag reduction

NASA Technical Reports Server (NTRS)

1979-01-01

Surface coating materials for application on transport type aircraft to reduce drag, were investigated. The investigation included two basic types of materials: spray on coatings and adhesively bonded films. A cost/benefits analysis was performed, and recommendations were made for future work toward the application of this technology.

Fe-porphyrin-based metal–organic framework films as high-surface concentration, heterogeneous catalysts for electrochemical reduction of CO 2

DOE PAGES

Hod, Idan; Sampson, Matthew D.; Deria, Pravas; ...

2015-09-18

Realization of heterogeneous electrochemical CO 2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal–organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO 2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (~10 15 sites/cm 2). The chemical products of the reduction, obtained withmore » ~100% Faradaic efficiency, are mixtures of CO and H 2. The results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.« less

Microbial reduction of uranium

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Gorby, Y.A.; Landa, E.R.

1991-01-01

REDUCTION of the soluble, oxidized form of uranium, U(VI), to insoluble U(IV) is an important mechanism for the immobilization of uranium in aquatic sediments and for the formation of some uranium ores1-10. U(VI) reduction has generally been regarded as an abiological reaction in which sulphide, molecular hydrogen or organic compounds function as the reductant1,2,5,11. Microbial involvement in U(VI) reduction has been considered to be limited to indirect effects, such as microbial metabolism providing the reduced compounds for abiological U(VI) reduction and microbial cell walls providing a surface to stimulate abiological U(VI) reduction1,12,13. We report here, however, that dissimilatory Fe(III)-reducing microorganisms can obtain energy for growth by electron transport to U(VI). This novel form of microbial metabolism can be much faster than commonly cited abiological mechanisms for U(VI) reduction. Not only do these findings expand the known potential terminal electron acceptors for microbial energy transduction, they offer a likely explanation for the deposition of uranium in aquatic sediments and aquifers, and suggest a method for biological remediation of environments contaminated with uranium.

Toward 10 meV electron energy-loss spectroscopy resolution for plasmonics.

PubMed

Bellido, Edson P; Rossouw, David; Botton, Gianluigi A

2014-06-01

Energy resolution is one of the most important parameters in electron energy-loss spectroscopy. This is especially true for measurement of surface plasmon resonances, where high-energy resolution is crucial for resolving individual resonance peaks, in particular close to the zero-loss peak. In this work, we improve the energy resolution of electron energy-loss spectra of surface plasmon resonances, acquired with a monochromated beam in a scanning transmission electron microscope, by the use of the Richardson-Lucy deconvolution algorithm. We test the performance of the algorithm in a simulated spectrum and then apply it to experimental energy-loss spectra of a lithographically patterned silver nanorod. By reduction of the point spread function of the spectrum, we are able to identify low-energy surface plasmon peaks in spectra, more localized features, and higher contrast in surface plasmon energy-filtered maps. Thanks to the combination of a monochromated beam and the Richardson-Lucy algorithm, we improve the effective resolution down to 30 meV, and evidence of success up to 10 meV resolution for losses below 1 eV. We also propose, implement, and test two methods to limit the number of iterations in the algorithm. The first method is based on noise measurement and analysis, while in the second we monitor the change of slope in the deconvolved spectrum.

Multiscale modeling and experimental interpretation of perovskite oxide materials in thermochemical energy storage and conversion for application in concentrating solar power

NASA Astrophysics Data System (ADS)

Albrecht, Kevin J.

Decarbonization of the electric grid is fundamentally limited by the intermittency of renewable resources such as wind and solar. Therefore, energy storage will play a significant role in the future of grid-scale energy generation to overcome the intermittency issues. For this reason, concentrating solar power (CSP) plants have been a renewable energy generation technology of interest due to their ability to participate in cost effective and efficient thermal energy storage. However, the ability to dynamically dispatch a CSP plant to meet energy demands is currently limited by the large quantities of sensible thermal energy storage material needed in a molten salt plant. Perovskite oxides have been suggested as a thermochemical energy storage material to enhance the energy storage capabilities of particle-based CSP plants, which combine sensible and chemical modes of energy storage. In this dissertation, computational models are used to establish the thermochemical energy storage potential of select perovskite compositions, identify system configurations that promote high values of energy storage and solar-to-electric efficiency, assess the kinetic and transport limitation of the chemical mode of energy storage, and create receiver and reoxidation reactor models capable of aiding in component design. A methodology for determining perovskite thermochemical energy storage potential is developed based on point defect models to represent perovskite non-stoichiometry as a function of temperature and gas phase oxygen partial pressure. The thermodynamic parameters necessary for the model are extracted from non-stoichiometry measurements by fitting the model using an optimization routine. The procedure is demonstrated for Ca0.9Sr0.1MnO 3-d which displayed combined energy storage values of 705.7 kJ/kg -1 by cycling between 773 K and 0.21 bar oxygen to 1173 K and 10 -4 bar oxygen. Thermodynamic system-level models capable of exploiting perovskite redox chemistry for energy storage in CSP plants are presented. Comparisons of sweep gas and vacuum pumping reduction as well as hot storage conditions indicate that solar-to-electric efficiencies are higher for sweep gas reduction system at equivalent values of energy storage if the energy parasitics of commercially available devices are considered. However, if vacuum pump efficiency between 15% and 30% can be achieved, the reduction methods will be approximately equal. Reducing condition oxygen partial pressures below 10-3 bar for sweep gas reduction and 10-2 bar for vacuum pumping reduction result in large electrical parasitics, which significantly reduce solar-to-electric efficiency. A model based interpretation of experimental measurements made for perovskite redox cycling using sweep gas in a packed bed is presented. The model indicates that long reduction times for equilibrating perovskites with low oxygen partial pressure sweep gas, compared to reoxidation, are primarily due to the oxygen carrying capacity of high purity sweep gas and not surface kinetic limitations. Therefore, achieving rapid reduction in the limited receiver residence time will be controlled by the quantity of sweep gas introduced. Effective kinetic parameters considering surface reaction and radial particle diffusion are fit to the experimental data. Variable order rate expressions without significant particle radial diffusion limitations are shown to be capable of representing the reduction and oxidation data. Modeling of a particle reduction receiver using continuous flow of perovskite solid and sweep gas in counter-flow configuration has identified issues with managing the oxygen evolved by the solid as well as sweep gas flow rates. Introducing sweep gas quantities necessary for equilibrating the solid with oxygen partial pressures below 10-2 are shown to result in gas phase velocities above the entrainment velocity of 500 um particles. Receiver designs with considerations for gas management are investigated and the results indicate that degrees of reduction corresponding to only oxygen partial pressures of 10-2 bar are attained. Numerical investigation into perovskite thermochemical energy storage indicates that achieving high levels of reduction through sweep gas or vacuum pumping to lower gas phase oxygen partial pressure below 10-2 bar display issues with parasitic energy consumption and gas phase management. Therefore, focus on material development should place a premium on thermal reduction and reduction by shifting oxygen partial pressure between ambient and 10-2 bar. Such a material would enable the development of a system with high solar-to-electric efficiencies and degrees of reduction which are attainable in realistic component geometries.

Generating Converged Accurate Free Energy Surfaces for Chemical Reactions with a Force-Matched Semiempirical Model.

PubMed

Kroonblawd, Matthew P; Pietrucci, Fabio; Saitta, Antonino Marco; Goldman, Nir

2018-04-10

We demonstrate the capability of creating robust density functional tight binding (DFTB) models for chemical reactivity in prebiotic mixtures through force matching to short time scale quantum free energy estimates. Molecular dynamics using density functional theory (DFT) is a highly accurate approach to generate free energy surfaces for chemical reactions, but the extreme computational cost often limits the time scales and range of thermodynamic states that can feasibly be studied. In contrast, DFTB is a semiempirical quantum method that affords up to a thousandfold reduction in cost and can recover DFT-level accuracy. Here, we show that a force-matched DFTB model for aqueous glycine condensation reactions yields free energy surfaces that are consistent with experimental observations of reaction energetics. Convergence analysis reveals that multiple nanoseconds of combined trajectory are needed to reach a steady-fluctuating free energy estimate for glycine condensation. Predictive accuracy of force-matched DFTB is demonstrated by direct comparison to DFT, with the two approaches yielding surfaces with large regions that differ by only a few kcal mol -1 .

Generating Converged Accurate Free Energy Surfaces for Chemical Reactions with a Force-Matched Semiempirical Model

DOE PAGES

Kroonblawd, Matthew P.; Pietrucci, Fabio; Saitta, Antonino Marco; ...

2018-03-15

Here, we demonstrate the capability of creating robust density functional tight binding (DFTB) models for chemical reactivity in prebiotic mixtures through force matching to short time scale quantum free energy estimates. Molecular dynamics using density functional theory (DFT) is a highly accurate approach to generate free energy surfaces for chemical reactions, but the extreme computational cost often limits the time scales and range of thermodynamic states that can feasibly be studied. In contrast, DFTB is a semiempirical quantum method that affords up to a thousandfold reduction in cost and can recover DFT-level accuracy. Here, we show that a force-matched DFTBmore » model for aqueous glycine condensation reactions yields free energy surfaces that are consistent with experimental observations of reaction energetics. Convergence analysis reveals that multiple nanoseconds of combined trajectory are needed to reach a steady-fluctuating free energy estimate for glycine condensation. Predictive accuracy of force-matched DFTB is demonstrated by direct comparison to DFT, with the two approaches yielding surfaces with large regions that differ by only a few kcal mol –1.« less

Generating Converged Accurate Free Energy Surfaces for Chemical Reactions with a Force-Matched Semiempirical Model

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

Kroonblawd, Matthew P.; Pietrucci, Fabio; Saitta, Antonino Marco

Here, we demonstrate the capability of creating robust density functional tight binding (DFTB) models for chemical reactivity in prebiotic mixtures through force matching to short time scale quantum free energy estimates. Molecular dynamics using density functional theory (DFT) is a highly accurate approach to generate free energy surfaces for chemical reactions, but the extreme computational cost often limits the time scales and range of thermodynamic states that can feasibly be studied. In contrast, DFTB is a semiempirical quantum method that affords up to a thousandfold reduction in cost and can recover DFT-level accuracy. Here, we show that a force-matched DFTBmore » model for aqueous glycine condensation reactions yields free energy surfaces that are consistent with experimental observations of reaction energetics. Convergence analysis reveals that multiple nanoseconds of combined trajectory are needed to reach a steady-fluctuating free energy estimate for glycine condensation. Predictive accuracy of force-matched DFTB is demonstrated by direct comparison to DFT, with the two approaches yielding surfaces with large regions that differ by only a few kcal mol –1.« less

Surface profile control of FeNiPt/Pt core/shell nanowires for oxygen reduction reaction

DOE PAGES

Zhu, Huiyuan; Zhang, Sen; Su, Dong; ...

2015-03-18

The ever-increasing energy demand requires renewable energy schemes with low environmental impacts. Electrochemical energy conversion devices, such as fuel cells, combine fuel oxidization and oxygen reduction reactions and have been studied extensively for renewable energy applications. However, their energy conversion efficiency is often limited by kinetically sluggish chemical conversion reactions, especially oxygen reduction reaction (ORR). [1-5] To date, extensive efforts have been put into developing efficient ORR catalysts with controls on catalyst sizes, compositions, shapes and structures. [6-12] Recently, Pt-based catalysts with core/shell and one-dimensional nanowire (NW) morphologies were found to be promising to further enhance ORR catalysis.more » With the core/shell structure, the ORR catalysis of a nanoparticle (NP) catalyst can be tuned by both electronic and geometric effects at the core/shell interface. [10,13,14] With the NW structure, the catalyst interaction with the conductive support can be enhanced to facilitate electron transfer between the support and the NW catalyst and to promote ORR. [11,15,16]« less

Synthesis of ZnO nanoparticles for oil-water interfacial tension reduction in enhanced oil recovery

NASA Astrophysics Data System (ADS)

Soleimani, Hassan; Baig, Mirza Khurram; Yahya, Noorhana; Khodapanah, Leila; Sabet, Maziyar; Demiral, Birol M. R.; Burda, Marek

2018-02-01

Nanoparticles show potential use in applications associated with upstream oil and gas engineering to increase the performance of numerous methods such as wettability alteration, interfacial tension reduction, thermal conductivity and enhanced oil recovery operations. Surface tension optimization is an important parameter in enhanced oil recovery. Current work focuses on the new economical method of surface tension optimization of ZnO nanofluids for oil-water interfacial tension reduction in enhanced oil recovery. In this paper, zinc oxide (ZnO) nanocrystallites were prepared using the chemical route and explored for enhanced oil recovery (EOR). Adsorption of ZnO nanoparticles (NPs) on calcite (111) surface was investigated using the adsorption locator module of Materials Studio software. It was found that ZnO nanoparticles show maximum adsorption energy of - 253 kcal/mol. The adsorption of ZnO on the rock surface changes the wettability which results in capillary force reduction and consequently increasing EOR. The nanofluids have been prepared by varying the concentration of ZnO nanoparticles to find the optimum value for surface tension. The surface tension (ST) was calculated with different concentration of ZnO nanoparticles using the pendant drop method. The results show a maximum value of ST 35.57 mN/m at 0.3 wt% of ZnO NPs. It was found that the nanofluid with highest surface tension (0.3 wt%) resulted in higher recovery efficiency. The highest recovery factor of 11.82% at 0.3 wt% is due to the oil/water interfacial tension reduction and wettability alteration.

Bismuth Passivation Technique for High-Resolution X-Ray Detectors

NASA Technical Reports Server (NTRS)

Chervenak, James; Hess, Larry

2013-01-01

The Athena-plus team requires X-ray sensors with energy resolution of better than one part in 3,000 at 6 keV X-rays. While bismuth is an excellent material for high X-ray stopping power and low heat capacity (for large signal when an X-ray is stopped by the absorber), oxidation of the bismuth surface can lead to electron traps and other effects that degrade the energy resolution. Bismuth oxide reduction and nitride passivation techniques analogous to those used in indium passivation are being applied in a new technique. The technique will enable improved energy resolution and resistance to aging in bismuth-absorber-coupled X-ray sensors. Elemental bismuth is lithographically integrated into X-ray detector circuits. It encounters several steps where the Bi oxidizes. The technology discussed here will remove oxide from the surface of the Bi and replace it with nitridized surface. Removal of the native oxide and passivating to prevent the growth of the oxide will improve detector performance and insulate the detector against future degradation from oxide growth. Placing the Bi coated sensor in a vacuum system, a reduction chemistry in a plasma (nitrogen/hydrogen (N2/H2) + argon) is used to remove the oxide and promote nitridization of the cleaned Bi surface. Once passivated, the Bi will perform as a better X-ray thermalizer since energy will not be trapped in the bismuth oxides on the surface. A simple additional step, which can be added at various stages of the current fabrication process, can then be applied to encapsulate the Bi film. After plasma passivation, the Bi can be capped with a non-diffusive layer of metal or dielectric. A non-superconducting layer is required such as tungsten or tungsten nitride (WNx).

External Acoustic Liners for Multi-Functional Aircraft Noise Reduction

NASA Technical Reports Server (NTRS)

Jones, Michael G. (Inventor); Czech, Michael J. (Inventor); Howerton, Brian M. (Inventor); Thomas, Russell H. (Inventor); Nark, Douglas M. (Inventor)

2017-01-01

Acoustic liners for aircraft noise reduction include one or more chambers that are configured to provide a pressure-release surface such that the engine noise generation process is inhibited and/or absorb sound by converting the sound into heat energy. The size and shape of the chambers can be selected to inhibit the noise generation process and/or absorb sound at selected frequencies.

Turbulent flows over superhydrophobic surfaces with shear-dependent slip length

NASA Astrophysics Data System (ADS)

Khosh Aghdam, Sohrab; Seddighi, Mehdi; Ricco, Pierre

2015-11-01

Motivated by recent experimental evidence, shear-dependent slip length superhydrophobic surfaces are studied. Lyapunov stability analysis is applied in a 3D turbulent channel flow and extended to the shear-dependent slip-length case. The feedback law extracted is recognized for the first time to coincide with the constant-slip-length model widely used in simulations of hydrophobic surfaces. The condition for the slip parameters is found to be consistent with the experimental data and with values from DNS. The theoretical approach by Fukagata (PoF 18.5: 051703) is employed to model the drag-reduction effect engendered by the shear-dependent slip-length surfaces. The estimated drag-reduction values are in very good agreement with our DNS data. For slip parameters and flow conditions which are potentially realizable in the lab, the maximum computed drag reduction reaches 50%. The power spent by the turbulent flow on the walls is computed, thereby recognizing the hydrophobic surfaces as a passive-absorbing drag-reduction method, as opposed to geometrically-modifying techniques that do not consume energy, e.g. riblets, hence named passive-neutral. The flow is investigated by visualizations, statistical analysis of vorticity and strain rates, and quadrants of the Reynolds stresses. Part of this work was funded by Airbus Group. Simulations were performed on the ARCHER Supercomputer (UKTC Grant).

Significant and stable drag reduction with air rings confined by alternated superhydrophobic and hydrophilic strips

PubMed Central

Hu, Haibao; Wen, Jun; Bao, Luyao; Jia, Laibing; Song, Dong; Song, Baowei; Pan, Guang; Scaraggi, Michele; Dini, Daniele; Xue, Qunji; Zhou, Feng

2017-01-01

Superhydrophobic surfaces have the potential to reduce the viscous drag of liquids by significantly decreasing friction at a solid-liquid interface due to the formation of air layers between solid walls and interacting liquids. However, the trapped air usually becomes unstable due to the finite nature of the domain over which it forms. We demonstrate for the first time that a large surface energy barrier can be formed to strongly pin the three-phase contact line of air/water/solid by covering the inner rotor of a Taylor-Couette flow apparatus with alternating superhydrophobic and hydrophilic circumferential strips. This prevents the disruption of the air layer, which forms stable and continuous air rings. The drag reduction measured at the inner rotor could be as much as 77.2%. Moreover, the air layers not only significantly reduce the strength of Taylor vortexes but also influence the number and position of the Taylor vortex pairs. This has strong implications in terms of energy efficiency maximization for marine applications and reduction of drag losses in, for example, fluid transport in pipelines and carriers. PMID:28879234

Interaction at the silicon/transition metal oxide heterojunction interface and its effect on the photovoltaic performance.

PubMed

Liang, Zhimin; Su, Mingze; Zhou, Yangyang; Gong, Li; Zhao, Chuanxi; Chen, Keqiu; Xie, Fangyan; Zhang, Weihong; Chen, Jian; Liu, Pengyi; Xie, Weiguang

2015-11-07

The interfacial reaction and energy level alignment at the Si/transition metal oxide (TMO, including MoO3-x, V2O5-x, WO3-x) heterojunction are systematically investigated. We confirm that the interfacial reaction appears during the thermal deposition of TMO, with the reaction extent increasing from MoO3-x, to V2O5-x, and to WO3-x. The reaction causes the surface oxidation of silicon for faster electron/hole recombination, and the reduction of TMO for effective hole collection. The photovoltaic performance of the Si/TMO heterojunction devices is affected by the interface reaction. MoO3-x are the best hole selecting materials that induce least surface oxidation but strongest reduction. Compared with H-passivation, methyl group passivation is an effective way to reduce the interface reaction and improve the interfacial energy level alignment for better electron and hole collection.

Photo-illuminated diamond as a solid-state source of solvated electrons in water for nitrogen reduction.

PubMed

Zhu, Di; Zhang, Linghong; Ruther, Rose E; Hamers, Robert J

2013-09-01

The photocatalytic reduction of N₂ to NH₃ is typically hampered by poor binding of N₂ to catalytic materials and by the very high energy of the intermediates involved in this reaction. Solvated electrons directly introduced into the reactant solution can provide an alternative pathway to overcome such limitations. Here we demonstrate that illuminated hydrogen-terminated diamond yields facile electron emission into water, thus inducing reduction of N₂ to NH₃ at ambient temperature and pressure. Transient absorption measurements at 632 nm reveal the presence of solvated electrons adjacent to the diamond after photoexcitation. Experiments using inexpensive synthetic diamond samples and diamond powder show that photocatalytic activity is strongly dependent on the surface termination and correlates with the production of solvated electrons. The use of diamond to eject electrons into a reactant liquid represents a new paradigm for photocatalytic reduction, bringing electrons directly to reactants without requiring molecular adsorption to the surface.

Dimension Reduction for the Landau-de Gennes Model in Planar Nematic Thin Films

NASA Astrophysics Data System (ADS)

Golovaty, Dmitry; Montero, José Alberto; Sternberg, Peter

2015-12-01

We use the method of Γ -convergence to study the behavior of the Landau-de Gennes model for a nematic liquid crystalline film in the limit of vanishing thickness. In this asymptotic regime, surface energy plays a greater role, and we take particular care in understanding its influence on the structure of the minimizers of the derived two-dimensional energy. We assume general weak anchoring conditions on the top and the bottom surfaces of the film and the strong Dirichlet boundary conditions on the lateral boundary of the film. The constants in the weak anchoring conditions are chosen so as to enforce that a surface-energy-minimizing nematic Q-tensor has the normal to the film as one of its eigenvectors. We establish a general convergence result and then discuss the limiting problem in several parameter regimes.

Surface wettability of an atomically heterogeneous system and the resulting intermolecular forces

NASA Astrophysics Data System (ADS)

Chatterjee, Sanghamitro; Bhattacharjee, Sudeep; Maurya, Sanjeev K.; Srinivasan, Vyas; Khare, Krishnacharya; Khandekar, Sameer

2017-06-01

We present the effect of 0.5 keV Ar+ beam irradiation on the wetting properties of metallic thin films. Observations reveal a transition from hydrophilic to hydrophobic nature at higher beam fluences which can be attributed to a reduction in net surface free energy. In this low-energy regime, ion beams do not induce significant surface roughness and chemical heterogeneity. However, they cause implantation of atomic impurities in the near surface region of the target and thus form a heterogeneous system at atomic length scales. Interestingly, the presence of implanted Ar atoms in the near surface region modifies the dispersive intermolecular interaction near the surface but induces no chemical modification due to their inert nature. On this basis, we have developed a theoretical model consistent with the experimental observations that reproduces the effective Hamaker constant with a reasonable accuracy.

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

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

Lu, Fang; Zhang, Yu; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Surface Proton Transfer Promotes Four-Electron Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Solution

DOE PAGES

Lu, Fang; Zhang, Yu; Liu, Shizhong; ...

2017-05-11

Four-electron oxygen reduction reaction (4e-ORR), as a key pathway in energy conversion, is preferred over the two-electron reduction pathway that falls short in dissociating dioxygen molecules. Gold (Au) surfaces exhibit high sensitivity of the ORR pathway to its atomic structures. The long-standing puzzle remains unsolved why the Au surfaces with {100} sub-facets were exceptionally capable to catalyze the 4e-ORR in alkaline solution, though limited within a narrow potential window. Herein we report the discovery of a dominant 4e-ORR over the whole potential range on {310} surface of Au nanocrystal shaped as truncated ditetragonal prism (TDP). In contrast, ORR pathways onmore » single-crystalline facets of shaped nanoparticles, including {111} on nano-octahedra and {100} on nano-cubes, are similar to their single-crystal counterparts. Combining our experimental results with density functional theory calculations, we elucidate the key role of surface proton transfers from co-adsorbed H 2O molecules in activating the facet- and potential-dependent 4e ORR on Au in alkaline solutions. These results elucidate how surface atomic structures determine the reaction pathways via bond scission and formation among weakly adsorbed water and reaction intermediates. The new insight helps in developing facet-specific nanocatalysts for various reactions.« less

Effect of Groove Surface Texture on Tribological Characteristics and Energy Consumption under High Temperature Friction.

PubMed

Wu, Wei; Chen, Guiming; Fan, Boxuan; Liu, Jianyou

2016-01-01

Energy consumption and tribological properties could be improved by proper design of surface texture in friction. However, some literature focused on investigating their performance under high temperature. In the study, different groove surface textures were fabricated on steels by a laser machine, and their tribological behaviors were experimentally studied with the employment of the friction and wear tester under distinct high temperature and other working conditions. The friction coefficient was recorded, and wear performance were characterized by double light interference microscope, scanning electron microscope (SEM) and x-ray energy dispersive spectrometry (EDS). Then, the performances of energy consumptions were carefully estimated. Results showed that friction coefficient, wear, and energy consumption could almost all be reduced by most textures under high temperature conditions, but to a different extent which depends on the experimental conditions and texture parameters. The main improvement mechanisms were analyzed, such as the hardness change, wear debris storage, thermal stress release and friction induced temperature reduction by the textures. Finally, a scattergram of the relatively reduced ratio of the energy consumption was drawn for different surface textures under four distinctive experimental conditions to illustrate the comprehensive energy consumption improving ability of textures, which was of benefit for the application of texture design.

Effect of Groove Surface Texture on Tribological Characteristics and Energy Consumption under High Temperature Friction

PubMed Central

Wu, Wei; Chen, Guiming; Fan, Boxuan; Liu, Jianyou

2016-01-01

Energy consumption and tribological properties could be improved by proper design of surface texture in friction. However, some literature focused on investigating their performance under high temperature. In the study, different groove surface textures were fabricated on steels by a laser machine, and their tribological behaviors were experimentally studied with the employment of the friction and wear tester under distinct high temperature and other working conditions. The friction coefficient was recorded, and wear performance were characterized by double light interference microscope, scanning electron microscope (SEM) and x-ray energy dispersive spectrometry (EDS). Then, the performances of energy consumptions were carefully estimated. Results showed that friction coefficient, wear, and energy consumption could almost all be reduced by most textures under high temperature conditions, but to a different extent which depends on the experimental conditions and texture parameters. The main improvement mechanisms were analyzed, such as the hardness change, wear debris storage, thermal stress release and friction induced temperature reduction by the textures. Finally, a scattergram of the relatively reduced ratio of the energy consumption was drawn for different surface textures under four distinctive experimental conditions to illustrate the comprehensive energy consumption improving ability of textures, which was of benefit for the application of texture design. PMID:27035658

Surface-structured diffuser by iterative down-size molding with glass sintering technology.

PubMed

Lee, Xuan-Hao; Tsai, Jung-Lin; Ma, Shih-Hsin; Sun, Ching-Cherng

2012-03-12

In this paper, a down-size sintering scheme for making high-performance diffusers with micro structure to perform beam shaping is presented and demonstrated. By using down-size sintering method, a surface-structure film is designed and fabricated to verify the feasibility of the sintering technology, in which up to 1/8 dimension reduction has been achieved. Besides, a special impressing technology has been applied to fabricate diffuser film with various materials and the transmission efficiency is as high as 85% and above. By introducing the diffuser into possible lighting applications, the diffusers have been shown high performance in glare reduction, beam shaping and energy saving.

Availability of surface boron species in improved oxygen reduction activity of Pt catalysts: A first-principles study

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

Zhang, Libo; Zhou, Gang, E-mail: gzhou@mail.buct.edu.cn

2016-04-14

The oxidation process of boron (B) species on the Pt(111) surface and the beneficial effects of boron oxides on the oxygen reduction activity are investigated by first-principles calculations. The single-atom B anchored on the Pt surface has a great attraction for the oxygen species in the immediate environment. With the dissociation of molecular oxygen, a series of boron oxides is formed in succession, both indicating exothermic oxidation reactions. After BO{sub 2} is formed, the subsequent O atom immediately participates in the oxygen reduction reaction. The calculated O adsorption energy is appreciably decreased as compared to Pt catalysts, and more approximatemore » to the optimal value of the volcano plot, from which is clear that O hydrogenation kinetics is improved. The modulation mechanism is mainly based on the electron-deficient nature of stable boron oxides, which normally reduces available electronic states of surface Pt atoms that bind the O by facilitating more electron transfer. This modification strategy from the exterior opens the new way, different from the alloying, to efficient electrocatalyst design for PEMFCs.« less

Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2, the first step in reduction of CO 2

DOE PAGES

Favaro, Marco; Xiao, Hai; Cheng, Tao; ...

2017-06-12

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide ismore » essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.« less

Dynamical significance of tides over the Bay of Bengal

NASA Astrophysics Data System (ADS)

Bhagawati, Chirantan; Pandey, Suchita; Dandapat, Sumit; Chakraborty, Arun

2018-06-01

Tides play a significant role in the ocean surface circulations and vertical mixing thereby influencing the Sea Surface Temperatures (SST) as well. This, in turn, plays an important role in the global circulation when used as a lower boundary condition in a global atmospheric general circulation model. Therefore in the present study, the dynamics of tides over the Bay of Bengal (BoB) is investigated through numerical simulations using a high resolution (1/12°) Regional Ocean Modeling System (ROMS). Based on statistical analysis it is observed that incorporation of explicit tidal forcing improves the model performance in simulating the basin averaged monthly surface circulation features by 64% compared to the simulation without tides. The model simulates also Mixed Layer Depth (MLD) and SST realistically. The energy exchange between tidal oscillations and eddies leads to redistribution of surface kinetic energy density with a net decrease of 0.012 J m-3 in the western Bay and a net increase of 0.007 J m-3 in the eastern Bay. The tidal forcing also affects the potential energy anomaly and vertical mixing thereby leading to a fall in monthly MLD over the BoB. The mixing due to tides leads to a subsequent reduction in monthly SST and a corresponding reduction in surface heat exchange. These results from the numerical simulation using ROMS reveal that tides have a significant influence over the air-sea heat exchange which is the most important parameter for prediction of Tropical Cyclone frequency and its future variability over the BoB.

Effect of vegetation on the energy balance and evapotranspiration in tallgrass prairie: a paired study with eddy covariance systems

NASA Astrophysics Data System (ADS)

Sun, X.; Zou, C.; Wilcox, B. P.; Stebler, E.

2017-12-01

Whole-year measurement with eddy covariance system was carried out over two adjoining plots with contrasting vegetation coverage in tallgrass prairie, one was treated with herbicide and mowing while the other one kept as undisturbed control. The magnitude and phase difference between soil heat storage and ground heat flux were explicitly examined for its relative weights and energy balance. Surface turbulent flux (sensible heat and latent heat) accounted for about 85% of available energy at both sites, implying that vegetation coverage didn't significantly influence the closure scenario of energy imbalance. The seasonal and daily pattern of energy partitioning were dramatically different between the contrasting sites during growing season. The treated site received slightly lower net radiation due to high albedo, had higher sensible heat, and reduced latent heat due to reduction on transpiration. Annual evapotranspiration (ET) in treated site was only accounts for about 73% of annual ET in control. Meanwhile, lower surface conductance and decoupling factor showed that vegetation removal would increase the sensibility of ET to vapor pressure deficit and soil drought. ET dynamics is controlled by leaf area and net radiation when soil moisture is high, while soil drought caused stomata closure and subdued ET during drought. Stomata closure and transpiration reduction caused decline in ET, surface conductance, and decoupling factor. Soil moisture storage served as an important reservoir to meet peak ET demand during growing season. In summary, ET was the dominant component of water balance in tallgrass prairie, and any land management alterring the albedo, soil mositure storage, or canopy phenology (e.g., NDVI) could significantly affect energy and water budgets in .

Screening effect on the polaron by surface plasmons

NASA Astrophysics Data System (ADS)

Xu, Xiaoying; Xu, Xiaoshan; Seal, Katyayani; Guo, Hangwen; Shen, Jian; Low Dimensional Materials Physics, Oak Ridge National Lab Team; University of Tennessee Team; Physics Department, Fudan University Team

2011-03-01

Surface plasmons occur when the conduction electrons at a metal/dielectric interface resonantly interact with external electromagnetic fields. While surface plasmons in vicinity of a polaron in the dielectric material, a strong screening effect on polaron characteristics is introduced. In this work, we observed the reduction of polarons in multiferroic LuFe2O4, which is mainly contributed by surface plasmons. Research sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U. S. Department of Energy.

Dimension Reduction for the Landau-de Gennes Model on Curved Nematic Thin Films

NASA Astrophysics Data System (ADS)

Golovaty, Dmitry; Montero, José Alberto; Sternberg, Peter

2017-12-01

We use the method of Γ -convergence to study the behavior of the Landau-de Gennes model for a nematic liquid crystalline film attached to a general fixed surface in the limit of vanishing thickness. This paper generalizes the approach in Golovaty et al. (J Nonlinear Sci 25(6):1431-1451, 2015) where we considered a similar problem for a planar surface. Since the anchoring energy dominates when the thickness of the film is small, it is essential to understand its influence on the structure of the minimizers of the limiting energy. In particular, the anchoring energy dictates the class of admissible competitors and the structure of the limiting problem. We assume general weak anchoring conditions on the top and the bottom surfaces of the film and strong Dirichlet boundary conditions on the lateral boundary of the film when the surface is not closed. We establish a general convergence result to an energy defined on the surface that involves a somewhat surprising remnant of the normal component of the tensor gradient. Then we exhibit one effect of curvature through an analysis of the behavior of minimizers to the limiting problem when the substrate is a frustum.

Surface modification of ceramic and metallic alloy substrates by laser raster-scanning

NASA Astrophysics Data System (ADS)

Ramos Grez, Jorge Andres

This work describes the feasibility of continuous wave laser-raster scan-processing under controlled atmospheric conditions as employed in three distinct surface modification processes: (a) surface roughness reduction of indirect-Selective Laser Sintered 420 martensitic stainless steel-40 wt. % bronze infiltrated surfaces; (b) Si-Cr-Hf-C coating consolidation over 3D carbon-carbon composites cylinders; (c) dendritic solidification structures of Mar-M 247 confined powder precursor grown from polycrystalline Alloy 718 substrates. A heat transfer model was developed to illustrate that the aspect ratio of the laser scanned pattern and the density of scanning lines play a significant role in determining peak surface temperature, heating and cooling rates and melt resident times. Comprehensive characterization of the surface of the processed specimens was performed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), optical metallography, X-ray diffraction (XRD), and, in certain cases, tactile profilometry. In Process (a), it was observed that a 24% to 37% roughness Ra reduction could be accomplished from the as-received value of 2.50+/-0.10 microns for laser energy densities ranging from 350 to 500 J/cm2. In Process (b), complete reactive wetting of carbon-carbon composite cylinders surface was achieved by laser melting a Si-Cr-Hf-C slurry. Coatings showed good thermal stability at 1000°C in argon, and, when tested in air, a percent weight reduction rate of -6.5 wt.%/hr was achieved. A soda-glass overcoat applied over the coated specimens by conventional means revealed a percent weight reduction rate between -1.4 to -2.2 wt.%/hr. Finally, in Process (c), microstructure of the Mar-M 247 single layer deposits, 1 mm in height, grown on Alloy 718 polycrystalline sheets, resulted in a sound metallurgical bond, low porosity, and uniform thickness. Polycrystalline dendrites grew preferentially along the [001] direction from the substrate up to 400 microns. Above that height, dendrites appear to shift towards the [100] growth direction driven by the thermal gradient and solidification front velocity. This research demonstrated that surface modification by high speed raster-scanning a high power laser beam under controlled atmospheric conditions is a feasible and versatile technique that can accomplish diverse purposes involving metallic as well as ceramic surfaces.

Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Electrolyte: Evidence for Surface Proton Transfer Effects

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

Zhang, Yu; Lu, Fang; Liu, Shizhong

Four-electron oxygen reduction reaction (4e-ORR) pathway, as a key high-performance reaction pathway in energy conversion, has been sought after in numerous investigations on metal surfaces over the last decades. Although the surfaces of the most noble metals, including platinum and palladium, demonstrate the fullpotential- range 4e-ORR, this is not the case, for gold (Au) surfaces. The 4e-ORR is only operative on Au surfaces with {100} subfacets, e.g. Au(100), in alkaline solution, however restricted to a certain potential region at low overpotentials, while reverting to a 2e-ORR at high overpotentials. This ORR on Au(100) has been a long-standing puzzle of electrocatalysis.more » Hereby we review the ORR studies on Au, along with the studies of water effects on Au catalysts, and present our electrochemical results with monofacet Au nanocrystals. Finally, combining with theoretical calculations we demonstrate that surface proton transfer from co-adsorbed water plays the key role in determining the ORR mechanism on Au surfaces in base.« less

Oxygen Reduction on Gold Nanocrystal Surfaces in Alkaline Electrolyte: Evidence for Surface Proton Transfer Effects

DOE PAGES

Zhang, Yu; Lu, Fang; Liu, Shizhong; ...

2018-04-01

Four-electron oxygen reduction reaction (4e-ORR) pathway, as a key high-performance reaction pathway in energy conversion, has been sought after in numerous investigations on metal surfaces over the last decades. Although the surfaces of the most noble metals, including platinum and palladium, demonstrate the fullpotential- range 4e-ORR, this is not the case, for gold (Au) surfaces. The 4e-ORR is only operative on Au surfaces with {100} subfacets, e.g. Au(100), in alkaline solution, however restricted to a certain potential region at low overpotentials, while reverting to a 2e-ORR at high overpotentials. This ORR on Au(100) has been a long-standing puzzle of electrocatalysis.more » Hereby we review the ORR studies on Au, along with the studies of water effects on Au catalysts, and present our electrochemical results with monofacet Au nanocrystals. Finally, combining with theoretical calculations we demonstrate that surface proton transfer from co-adsorbed water plays the key role in determining the ORR mechanism on Au surfaces in base.« less

Understanding pH Effects on Trichloroethylene and Perchloroethylene Adsorption to Iron in Permeable Reactive Barriers for Groundwater Remediation.

PubMed

Luo, Jing; Farrell, James

2013-01-01

Metallic iron filings are becoming increasing used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for TCE and PCE were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated TCE and PCE complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of TCE complexes more than those for PCE. Attractions between atomic hydrogen and iron atoms were more favorable when TCE versus PCE was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect TCE reaction rates more than those for PCE.

Soil Erodibility Parameters Under Various Cropping Systems of Maize

NASA Astrophysics Data System (ADS)

van Dijk, P. M.; van der Zijp, M.; Kwaad, F. J. P. M.

1996-08-01

For four years, runoff and soil loss from seven cropping systems of fodder maize have been measured on experimental plots under natural and simulated rainfall. Besides runoff and soil loss, several variables have also been measured, including rainfall kinetic energy, degree of slaking, surface roughness, aggregate stability, soil moisture content, crop cover, shear strength and topsoil porosity. These variables explain a large part of the variance in measured runoff, soil loss and splash erosion under the various cropping systems. The following conclusions were drawn from the erosion measurements on the experimental plots (these conclusions apply to the spatial level at which the measurements were carried out). (1) Soil tillage after maize harvest strongly reduced surface runoff and soil loss during the winter; sowing of winter rye further reduced winter erosion, though the difference with a merely tilled soil is small. (2) During spring and the growing season, soil loss is reduced strongly if the soil surface is partly covered by plant residues; the presence of plant residue on the surface appeared to be essential in achieving erosion reduction in summer. (3) Soil loss reductions were much higher than runoff reductions; significant runoff reduction is only achieved by the straw system having flat-lying, non-fixed plant residue on the soil surface; the other systems, though effective in reducing soil loss, were not effective in reducing runoff.

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

Benson, Stephen V.; Marhauser, Frank; Douglas, David R.

A method for the suppression of upstream-directed field emission in RF accelerators. The method is not restricted to a certain number of cavity cells, but requires similar operating field levels in all cavities to efficiently annihilate the once accumulated energy. Such a field balance is desirable to minimize dynamic RF losses, but not necessarily achievable in reality depending on individual cavity performance, such as early Q.sub.0-drop or quench field. The method enables a significant energy reduction for upstream-directed electrons within a relatively short distance. As a result of the suppression of upstream-directed field emission, electrons will impact surfaces at rathermore » low energies leading to reduction of dark current and less issues with heating and damage of accelerator components as well as radiation levels including neutron generation and thus radio-activation.« less

Protective coatings of metal surfaces by cold plasma treatment

NASA Technical Reports Server (NTRS)

Manory, R.; Grill, A.

1985-01-01

The cold plasma techniques for deposition of various types of protective coatings are reviewed. The main advantage of these techniques for deposition of ceramic films is the lower process temperature, which enables heat treating of the metal prior to deposition. In the field of surface hardening of steel, significant reduction of treatment time and energy consumption were obtained. A simple model for the plasma - surface reactions in a cold plasma system is presented, and the plasma deposition techniques are discussed in view of this model.

Enhanced thermoelectric performance in three-dimensional superlattice of topological insulator thin films

PubMed Central

2012-01-01

We show that certain three-dimensional (3D) superlattice nanostructure based on Bi2Te3 topological insulator thin films has better thermoelectric performance than two-dimensional (2D) thin films. The 3D superlattice shows a predicted peak value of ZT of approximately 6 for gapped surface states at room temperature and retains a high figure of merit ZT of approximately 2.5 for gapless surface states. In contrast, 2D thin films with gapless surface states show no advantage over bulk Bi2Te3. The enhancement of the thermoelectric performance originates from a combination of the reduction of lattice thermal conductivity by phonon-interface scattering, the high mobility of the topologically protected surface states, the enhancement of Seebeck coefficient, and the reduction of electron thermal conductivity by energy filtering. Our study shows that the nanostructure design of topological insulators provides a possible new way of ZT enhancement. PMID:23072433

Enhanced thermoelectric performance in three-dimensional superlattice of topological insulator thin films.

PubMed

Fan, Zheyong; Zheng, Jiansen; Wang, Hui-Qiong; Zheng, Jin-Cheng

2012-10-16

We show that certain three-dimensional (3D) superlattice nanostructure based on Bi2Te3 topological insulator thin films has better thermoelectric performance than two-dimensional (2D) thin films. The 3D superlattice shows a predicted peak value of ZT of approximately 6 for gapped surface states at room temperature and retains a high figure of merit ZT of approximately 2.5 for gapless surface states. In contrast, 2D thin films with gapless surface states show no advantage over bulk Bi2Te3. The enhancement of the thermoelectric performance originates from a combination of the reduction of lattice thermal conductivity by phonon-interface scattering, the high mobility of the topologically protected surface states, the enhancement of Seebeck coefficient, and the reduction of electron thermal conductivity by energy filtering. Our study shows that the nanostructure design of topological insulators provides a possible new way of ZT enhancement.

Thermal effects of laser marking on microstructure and corrosion properties of stainless steel.

PubMed

Švantner, M; Kučera, M; Smazalová, E; Houdková, Š; Čerstvý, R

2016-12-01

Laser marking is an advanced technique used for modification of surface optical properties. This paper presents research on the influence of laser marking on the corrosion properties of stainless steel. Processes during the laser beam-surface interaction cause structure and color changes and can also be responsible for reduction of corrosion resistance of the surface. Corrosion tests, roughness, microscopic, energy dispersive x-ray, grazing incidence x-ray diffraction, and ferrite content analyses were carried out. It was found that increasing heat input is the most crucial parameter regarding the degradation of corrosion resistance of stainless steel. Other relevant parameters include the pulse length and pulse frequency. The authors found a correlation between laser processing parameters, grazing incidence x-ray measurement, ferrite content, and corrosion resistance of the affected surface. Possibilities and limitations of laser marking of stainless steel in the context of the reduction of its corrosion resistance are discussed.

Dry fractionation process as an important step in current and future lignocellulose biorefineries: a review.

PubMed

Barakat, Abdellatif; de Vries, Hugo; Rouau, Xavier

2013-04-01

The use of lignocellulosic biomass is promising for biofuels and materials and new technologies for the conversion need to be developed. However, the inherent properties of native lignocellulosic materials make them resistant to enzymatic and chemical degradation. Lignocellulosic biomass requires being pretreated to change the physical and chemical properties of lignocellulosic matrix in order to increase cell wall polymers accessibility and bioavailability. Mechanical size reduction may be chemical free intensive operation thanks to decreasing particles size and cellulose crystallinity, and increasing accessible surface area. Changes in these parameters improve the digestibility and the bioconversion of lignocellulosic biomass. However, mechanical size reduction requires cost-effective approaches from an energy input point of view. Therefore, the energy consumption in relation to physicochemical properties of lignocellulosic biomass was discussed. Even more, chemical treatments combined with physicochemical size reduction approaches are proposed to reduce energy consumption in this review. Copyright © 2013 Elsevier Ltd. All rights reserved.

A method for the reduction of aerodynamic drag of road vehicles

NASA Technical Reports Server (NTRS)

Pamadi, Bandu N.; Taylor, Larry W.; Leary, Terrance O.

1990-01-01

A method is proposed for the reduction of the aerodynamic drag of bluff bodies, particularly for application to road transport vehicles. This technique consists of installation of panels on the forward surface of the vehicle facing the airstream. With the help of road tests, it was demonstrated that the attachment of proposed panels can reduce aerodynamic drag of road vehicles and result in significant fuel cost savings and conservation of energy resources.

The structure of reconstructed chalcopyrite surfaces

NASA Astrophysics Data System (ADS)

Thinius, Sascha; Islam, Mazharul M.; Bredow, Thomas

2018-03-01

Chalcopyrite (CuFeS2) surfaces are of major interest for copper exploitation in aqueous solution, called leaching. Since leaching is a surface process knowledge of the surface structure, bonding pattern and oxidation states is important for improving the efficiency. At present such information is not available from experimental studies. Therefore a detailed computational study of chalcopyrite surfaces is performed. The structures of low-index stoichiometric chalcopyrite surfaces {hkl} h, k, l ∈ {0, 1, 2} have been studied with density functional theory (DFT) and global optimization strategies. We have applied ab initio molecular dynamics (MD) in combination with simulated annealing (SA) in order to explore possible reconstructions via a minima hopping (MH) algorithm. In almost all cases reconstruction involving substantial rearrangement has occurred accompanied by reduction of the surface energy. The analysis of the change in the coordination sphere and migration during reconstruction reveals that S-S dimers are formed on the surface. Further it was observed that metal atoms near the surface move toward the bulk forming metal alloys passivated by sulfur. The obtained surface energies of reconstructed surfaces are in the range of 0.53-0.95 J/m2.

Surface properties of poly(acrylonitrile) (PAN) precipitation polymerized in supercritical CO2 and the influence of the molecular weight.

PubMed

Shen, Qing; Gu, Qing-Feng; Hu, Jian-Feng; Teng, Xin-Rong; Zhu, Yun-Feng

2003-11-15

In this paper, the surface properties, e.g., the total surface free energy and the related Lifshitz-van der Waals and Lewis acid-base components, of polyacrylonitrile (PAN) precipitation polymerized in supercritical CO(2) have been characterized. Moreover, the influence of molecular weight varying has been also investigated. Results show that the surface properties of PAN resulting from supercritical CO(2) are different from those obtained by the conventional method. Of these data, one important finding is that the supercritical CO(2) PAN seems to decrease the surface free energy with the increased molecular weight. Based on previous recorded NMR spectra of this PAN and especially compared to commercial PAN, such phenomena are discussed and ascribed to an increase of the H-bonds and a reduction of the isotacticity in the supercritical CO(2) condition for PAN.

Documenting helicopter operations from an energy standpoint

NASA Technical Reports Server (NTRS)

Davis, S. J.; Stepniewski, W. Z.

1974-01-01

Results are presented of a study of the relative and absolute energy consumption of helicopters, including limited comparisons with fixed-wing aircraft, and selected surface transportation vehicles. Additional comparisons were made to determine the level of reduction in energy consumption expected from the application of advanced technologies to the helicopter design and sizing process. It was found that improvements in helicopter consumption characteristics can be accomplished through the utilization of advanced technology to reduce drag, structures weight, and powerplant fuel consumption.

Carbonaceous thin film coating with Fe-N4 site for enhancement of dioxovanadium ion reduction

NASA Astrophysics Data System (ADS)

Maruyama, Jun; Hasegawa, Takahiro; Iwasaki, Satoshi; Fukuhara, Tomoko; Orikasa, Yuki; Uchimoto, Yoshiharu

2016-08-01

It has been found that carbonaceous materials containing a transition metal coordinated by 4 nitrogens in the square-planar configuration (metal-N4 site) on the surface possessed a catalytic activity for various electrochemical reactions related to energy conversion and storage; i.e., oxygen reduction, hydrogen evolution, and quite recently, the electrode reactions in vanadium redox flow batteries (VRFB). The catalyst for the VRFB positive electrode discharge reaction, i.e., the dioxovanadium ion reduction, was formed by coating the surface of cup-stack carbon nanotubes with a carbonaceous thin film with the Fe-N4 site generated by the sublimation, deposition, and pyrolysis of iron phthalocyanine. In this study, the influence of the physical properties of the catalyst on the electrochemical reactions was investigated to optimize the coating. With an increase in the coating, the specific surface area increased, whereas the pore size decreased. The surface Fe concentration was increased in spite of the Fe aggregation inside the carbon matrix. The catalytic activity enhancement was achieved due to the increase in the specific surface area and the surface Fe concentration, but was lowered due to the decrease in the pore size, which was disadvantageous for the penetration of the electrolyte and the mass transfer.

Imaging Catalytic Activation of CO 2 on Cu 2O (110): A First-Principles Study

DOE PAGES

Li, Liang; Zhang, Rui; Vinson, John; ...

2018-03-05

Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO 2 reduction. While photoreduction of CO 2 is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu 2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO 2 and the Cu 2O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu 2O (110) surface stoichiometry that favors CO 2 reduction. To facilitate interpretation ofmore » scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO 2 reduction reaction on, and rational surface engineering of, Cu 2O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.« less

Imaging Catalytic Activation of CO 2 on Cu 2O (110): A First-Principles Study

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

Li, Liang; Zhang, Rui; Vinson, John

Balancing global energy needs against increasing greenhouse gas emissions requires new methods for efficient CO 2 reduction. While photoreduction of CO 2 is a viable approach for fuel generation, the rational design of photocatalysts hinges on precise characterization of the surface catalytic reactions. Cu 2O is a promising next-generation photocatalyst, but the atomic-scale description of the interaction between CO 2 and the Cu 2O surface is largely unknown, and detailed experimental measurements are lacking. In this study, density-functional-theory (DFT) calculations have been performed to identify the Cu 2O (110) surface stoichiometry that favors CO 2 reduction. To facilitate interpretation ofmore » scanning tunneling microscopy (STM) and X-ray absorption near-edge structures (XANES) measurements, which are useful for characterizing catalytic reactions, we present simulations based on DFT-derived surface morphologies with various adsorbate types. STM and XANES simulations were performed using the Tersoff Hamann approximation and Bethe-Salpeter equation (BSE) approach, respectively. The results provide guidance for observation of CO 2 reduction reaction on, and rational surface engineering of, Cu 2O (110). In conclusion, they also demonstrate the effectiveness of computational image and spectroscopy modeling as a predictive tool for surface catalysis characterization.« less

Communication: Hot-atom abstraction dynamics of hydrogen from tungsten surfaces: The role of surface structure

NASA Astrophysics Data System (ADS)

Galparsoro, Oihana; Busnengo, Heriberto Fabio; Juaristi, Joseba Iñaki; Crespos, Cédric; Alducin, Maite; Larregaray, Pascal

2017-09-01

Adiabatic and non-adiabatic quasiclassical molecular dynamics simulations are performed to investigate the role of the crystal face on hot-atom abstraction of H adsorbates by H scattering from covered W(100) and W(110). On both cases, hyperthermal diffusion is strongly affected by the energy dissipated into electron-hole pair excitations. As a result, the hot-atom abstraction is highly reduced in favor of adsorption at low incidence energy and low coverages, i.e., when the mean free path of the hyperthermal H is typically larger. Qualitatively, this reduction is rather similar on both surfaces, despite at such initial conditions, the abstraction process involves more subsurface penetration on W(100) than on W(110).

Energy Saving Melting and Revert Reduction Technology: Improved Die Casting Process to Preserve the Life of the Inserts

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

David Schwam, PI; Xuejun Zhu, Sr. Research Associate

2012-09-30

The goal of this project was to study the combined effects of die design, proper internal cooling and efficient die lubricants on die life. The project targeted improvements in die casting insert life by: Optomized Die Design for Reduced Surface Temperature: The life of die casting dies is significantly shorter when the die is exposed to elevated temperature for significant periods of time. Any die operated under conditions leading to surface temperature in excess of 1050oF undergoes structural changes that reduce its strength. Optimized die design can improve die life significantly. This improvement can be accomplished by means of coolingmore » lines, baffles and bubblers in the die. A key objective of the project was to establish criteria for the minimal distance of the cooling lines from the surface. This effort was supported with alloys and machining by BohlerUddeholm, Dunn Steel, HH Stark and Rex Buckeye. In plant testing and evaluation was conducted as in-kind cost share at St. Clair Die Casting. The Uddeholm Dievar steel evaluated in this program showed superior resistance to thermal fatigue resistance. Based on the experimental evidence, cooling lines could be placed as close as 0.5" from the surface. Die Life Extension by Optimized Die Lubrication: The life of die casting dies is affected by additions made to its surface with the proper lubricants. These lubricants will protect the surface from the considerable temperature peaks that occur when the molten melt enters the die. Dies will reach a significantly higher temperature without this lubricant being applied. The amount and type of the lubricant are critical variables in the die casting process. However, these lubricants must not corrode the die surface. This effort was supported with alloys and machining by BohlerUddeholm, Dunn Steel, HH Stark and Rex Buckeye. In plant testing and evaluation was conducted as in-kind cost share at St. Clair Die Casting. Chem- Trend participated in the program with die lubricants and technical support. Experiments conducted with these lubricants demonstrated good protection of the substrate steel. Graphite and boron nitride used as benchmarks are capable of completely eliminating soldering and washout. However, because of cost and environmental considerations these materials are not widely used in industry. The best water-based die lubricants evaluated in this program were capable of providing similar protection from soldering and washout. In addition to improved part quality and higher production rates, improving die casting processes to preserve the life of the inserts will result in energy savings and a reduction in environmental wastes. Improving die life by means of optimized cooling line placement, baffles and bubblers in the die will allow for reduced die temperatures during processing, saving energy associated with production. The utilization of optimized die lubricants will also reduce heat requirements in addition to reducing waste associated with soldering and washout. This new technology was predicted to result in an average energy savings of 1.1 trillion BTU's/year over a 10 year period. Current (2012) annual energy saving estimates, based on commercial introduction in 2010, a market penetration of 70% by 2020 is 1.26 trillion BTU's/year. Along with these energy savings, reduction of scrap and improvement in casting yield will result in a reduction of the environmental emissions associated with the melting and pouring of the metal which will be saved as a result of this technology. The average annual estimate of CO2 reduction per year through 2020 is 0.025 Million Metric Tons of Carbon Equivalent (MM TCE).« less

Surface Chemistry of Perovskite-Type Electrodes During High Temperature CO2 Electrolysis Investigated by Operando Photoelectron Spectroscopy.

PubMed

Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Kubicek, Markus; Götsch, Thomas; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Klötzer, Bernhard; Fleig, Jürgen

2017-10-18

Any substantial move of energy sources from fossil fuels to renewable resources requires large scale storage of excess energy, for example, via power to fuel processes. In this respect electrochemical reduction of CO 2 may become very important, since it offers a method of sustainable CO production, which is a crucial prerequisite for synthesis of sustainable fuels. Carbon dioxide reduction in solid oxide electrolysis cells (SOECs) is particularly promising owing to the high operating temperature, which leads to both improved thermodynamics and fast kinetics. Additionally, compared to purely chemical CO formation on oxide catalysts, SOECs have the outstanding advantage that the catalytically active oxygen vacancies are continuously formed at the counter electrode, and move to the working electrode where they reactivate the oxide surface without the need of a preceding chemical (e.g., by H 2 ) or thermal reduction step. In the present work, the surface chemistry of (La,Sr)FeO 3-δ and (La,Sr)CrO 3-δ based perovskite-type electrodes was studied during electrochemical CO 2 reduction by means of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) at SOEC operating temperatures. These measurements revealed the formation of a carbonate intermediate, which develops on the oxide surface only upon cathodic polarization (i.e., under sufficiently reducing conditions). The amount of this adsorbate increases with increasing oxygen vacancy concentration of the electrode material, thus suggesting vacant oxygen lattice sites as the predominant adsorption sites for carbon dioxide. The correlation of carbonate coverage and cathodic polarization indicates that an electron transfer is required to form the carbonate and thus to activate CO 2 on the oxide surface. The results also suggest that acceptor doped oxides with high electron concentration and high oxygen vacancy concentration may be particularly suited for CO 2 reduction. In contrast to water splitting, the CO 2 electrolysis reaction was not significantly affected by metallic particles, which were exsolved from the perovskite electrodes upon cathodic polarization. Carbon formation on the electrode surface was only observed under very strong cathodic conditions, and the carbon could be easily removed by retracting the applied voltage without damaging the electrode, which is particularly promising from an application point of view.

Surface Chemistry of Perovskite-Type Electrodes During High Temperature CO2 Electrolysis Investigated by Operando Photoelectron Spectroscopy

PubMed Central

2017-01-01

Any substantial move of energy sources from fossil fuels to renewable resources requires large scale storage of excess energy, for example, via power to fuel processes. In this respect electrochemical reduction of CO2 may become very important, since it offers a method of sustainable CO production, which is a crucial prerequisite for synthesis of sustainable fuels. Carbon dioxide reduction in solid oxide electrolysis cells (SOECs) is particularly promising owing to the high operating temperature, which leads to both improved thermodynamics and fast kinetics. Additionally, compared to purely chemical CO formation on oxide catalysts, SOECs have the outstanding advantage that the catalytically active oxygen vacancies are continuously formed at the counter electrode, and move to the working electrode where they reactivate the oxide surface without the need of a preceding chemical (e.g., by H2) or thermal reduction step. In the present work, the surface chemistry of (La,Sr)FeO3−δ and (La,Sr)CrO3−δ based perovskite-type electrodes was studied during electrochemical CO2 reduction by means of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) at SOEC operating temperatures. These measurements revealed the formation of a carbonate intermediate, which develops on the oxide surface only upon cathodic polarization (i.e., under sufficiently reducing conditions). The amount of this adsorbate increases with increasing oxygen vacancy concentration of the electrode material, thus suggesting vacant oxygen lattice sites as the predominant adsorption sites for carbon dioxide. The correlation of carbonate coverage and cathodic polarization indicates that an electron transfer is required to form the carbonate and thus to activate CO2 on the oxide surface. The results also suggest that acceptor doped oxides with high electron concentration and high oxygen vacancy concentration may be particularly suited for CO2 reduction. In contrast to water splitting, the CO2 electrolysis reaction was not significantly affected by metallic particles, which were exsolved from the perovskite electrodes upon cathodic polarization. Carbon formation on the electrode surface was only observed under very strong cathodic conditions, and the carbon could be easily removed by retracting the applied voltage without damaging the electrode, which is particularly promising from an application point of view. PMID:28933825

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

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

Taylor, S. D.; Becker, U.; Rosso, K. M.

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed,more » such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis for experimental interrogation of this important process at mineral-water interfaces.« less

Reduced chemical warfare agent sorption in polyurethane-painted surfaces via plasma-enhanced chemical vapor deposition of perfluoroalkanes.

PubMed

Gordon, Wesley O; Peterson, Gregory W; Durke, Erin M

2015-04-01

Perfluoralkalation via plasma chemical vapor deposition has been used to improve hydrophobicity of surfaces. We have investigated this technique to improve the resistance of commercial polyurethane coatings to chemicals, such as chemical warfare agents. The reported results indicate the surface treatment minimizes the spread of agent droplets and the sorption of agent into the coating. The improvement in resistance is likely due to reduction of the coating's surface free energy via fluorine incorporation, but may also have contributing effects from surface morphology changes. The data indicates that plasma-based surface modifications may have utility in improving chemical resistance of commercial coatings.

Synthesis and photocatalytic CO2 reduction performance of Cu2O/Coal-based carbon nanoparticle composites

NASA Astrophysics Data System (ADS)

Dedong, Zhang; Maimaiti, Halidan; Awati, Abuduheiremu; Yisilamu, Gunisakezi; Fengchang, Sun; Ming, Wei

2018-05-01

The photocatalytic reduction of CO2 into hydrocarbons provides a promising approach to overcome the challenges of environmental crisis and energy shortage. Here we fabricated a cuprous oxide (Cu2O) based composite photocatalyst consisting of Cu2O/carbon nanoparticles (CNPs). To prepare the CNPs, coal samples from Wucaiwan, Xinjiang, China, were first treated with HNO3, followed by hydrogen peroxide (H2O2) oxidation to strip nanocrystalline carbon from coal. After linking with oxygen-containing group such as hydroxyl, coal-based CNPs with sp2 carbon structure and multilayer graphene lattice structure were synthesized. Subsequently, the CNPs were loaded onto the surface of Cu2O nanoparticles prepared by in-situ reduction of copper chloride (CuCl2·2H2O). The physical properties and chemical structure of the Cu2O/CNPs as well as photocatalytic activity of CO2/H2O reduction into CH3OH were measured. The results demonstrate that the Cu2O/CNPs are composed of spherical particles with diameter of 50 nm and mesoporous structure, which are suitable for CO2 adsorption. Under illumination of visible light, electron-hole pairs are generated in Cu2O. Thanks to the CNPs, the fast recombination of electron-hole pairs is suppressed. The energy gradient formed on the surface of Cu2O/CNPs facilitates the efficient separation of electron-hole pairs for CO2 reduction and H2O oxidation, leading to enhanced photocatalytic activity.

Efficient and Selective Electrochemical and Photoelectrochemical Reduction of 5-Hydroxymethylfurfural to 2,5-Bis(hydroxymethyl)furan using Water as the Hydrogen Source

DOE PAGES

Roylance, John J.; Kim, Tae Woo; Choi, Kyoung-Shin

2016-02-17

Reductive biomass conversion has been conventionally conducted using H 2 gas under high-temperature and-pressure conditions. Here, efficient electrochemical reduction of 5-hydroxymethylfurfural (HMF), a key intermediate for biomass conversion, to 2,5-bis(hydroxymethyl)furan (BHMF), an important monomer for industrial processes, was demonstrated using Ag catalytic electrodes. This process uses water as the hydrogen source under ambient conditions and eliminates the need to generate and consume H 2 for hydrogenation, providing a practical and efficient route for BHMF production. By systematic investigation of HMF reduction on the Ag electrode surface, BHMF production was achieved with the Faradaic efficiency and selectivity nearing 100%, and plausiblemore » reduction mechanisms were also elucidated. Furthermore, construction of a photoelectrochemical cell (PEC) composed of an n-type BiVO 4 semiconductor anode, which uses photogenerated holes for water oxidation, and a catalytic Ag cathode, which uses photoexcited electrons from BiVO 4 for the reduction of HMF to BHMF, was demonstrated to utilize solar energy to significantly decrease the external voltage necessary for HMF reduction. This shows the possibility of coupling electrochemical HMF reduction and solar energy conversion, which can provide more efficient and environmentally benign routes for reductive biomass conversion.« less

Charge transfer and symmetry reduction at the CuPc/Ag(110) interface studied by photoemission tomography

NASA Astrophysics Data System (ADS)

Schönauer, K.; Weiss, S.; Feyer, V.; Lüftner, D.; Stadtmüller, B.; Schwarz, D.; Sueyoshi, T.; Kumpf, C.; Puschnig, P.; Ramsey, M. G.; Tautz, F. S.; Soubatch, S.

2016-11-01

On the Ag(110) surface copper phthalocyanine (CuPc) orders in two structurally similar superstructures, as revealed by low-energy electron diffraction. Scanning tunneling microscopy (STM) shows that in both superstructures the molecular planes are oriented parallel to the surface and the long molecular axes, defined as diagonals of the square molecule, are rotated by ≃±32∘ away from the high-symmetry directions [1 1 ¯0 ] and [001] of the silver surface. Similarly to many other adsorbed metal phthalocyanines, the CuPc molecules on Ag(110) appear in STM as crosslike features with twofold symmetry. Photoemission tomography based on angle-resolved photoemission spectroscopy reveals a charge transfer from the substrate into the molecule. A symmetry analysis of experimental and theoretical constant binding energy maps of the photoemission intensity in the kx,ky -plane points to a preferential occupation of one of the two initially degenerate lowest unoccupied molecular orbitals (LUMOs) of eg symmetry. The occupied eg orbital is rotated by 32∘ against the [001] direction of the substrate. The lifting of the degeneracy of the LUMOs and the related reduction of the symmetry of the adsorbed CuPc molecule are attributed to an anisotropy in the chemical reactivity of the Ag(110) surface.

Molten-salt treatment of waste biomass for preparation of carbon with enhanced capacitive properties and electrocatalytic activity towards oxygen reduction.

PubMed

Lu, Beihu; Zhou, Jing; Song, Yuqiao; Wang, Hailong; Xiao, Wei; Wang, Dihua

2016-08-15

Carbon powders are building blocks for electrochemical energy storage/conversion devices. Green, cost-affordable and facile preparation of carbon with applicable electrochemical properties is therefore essential for effective utilization of fluctuating renewable energy. Herein, the preparation of carbon nanoflakes via impregnation of waste biomass i.e. boiled coffee beans in molten Na2CO3-K2CO3 (with equal mass) at 800 °C and molten CaCl2 at 850 °C is reported. The microstructure and surface chemistry of the obtained carbons are specified. The correlations between synthetic conditions and microstructure/surface chemistry of the obtained carbons are rationalized. The derived carbon nanosheets are tested and compared as active materials for supercapacitors in a configuration of symmetric full cells in 1 M MeEt3NBF4 in acetonitrile and electrocatalysts towards the oxygen reduction reaction (ORR) in O2-saturated 0.1 M aqueous KOH. Despite the lower surface area, the carbon nanosheets derived in molten Na2CO3-K2CO3 exhibit enhanced capacitive properties and electrocatalytic ORR activity. The present study highlights the importance of thermal media on the microstructure, surface chemistry and electrochemistry of carbon from biomass.

Towards spin-polarized two-dimensional electron gas at a surface of an antiferromagnetic insulating oxide

DOE PAGES

Mishra, Rohan; Kim, Young -Min; He, Qian; ...

2016-07-18

Here, the surfaces of transition-metal oxides with the perovskite structure are fertile grounds for the discovery of novel electronic and magnetic phenomena. In this article, we combine scanning transmission electron microscopy (STEM) with density functional theory (DFT) calculations to obtain the electronic and magnetic properties of the (001) surface of a (LaFeO 3) 8/(SrFeO 3) 1 superlattice film capped with four layers of LaFeO 3. Simultaneously acquired STEM images and electron-energy-loss spectra reveal the surface structure and a reduction in the oxidation state of iron from Fe 3+ in the bulk to Fe 2+ at the surface, extending over severalmore » atomic layers, which signals the presence of oxygen vacancies. The DFT calculations confirm the reduction in terms of oxygen vacancies and further demonstrate the stabilization of an exotic phase in which the surface layer is half metallic and ferromagnetic, while the bulk remains antiferromagnetic and insulating. Based on the calculations, we predict that the surface magnetism and conductivity can be controlled by tuning the partial pressure of oxygen.« less

Fiscal Year 2012 Operational Energy Budget Certification Report

DTIC Science & Technology

2011-01-01

superconducting  degaussing systems  • Advanced material, energy efficient propellers and waterjets  • Ship drag reduction and corrosion resistant surface...significant savings include: optimizing aircraft centers of  gravity , diplomatic cleared  routing, European routing, aircraft crew ratios, and departure

Effects of rare earth oxide additive on surface and tribological properties of polyimide composites

NASA Astrophysics Data System (ADS)

Pan, Zihe; Wang, Tianchang; Chen, Li; Idziak, Stefan; Huang, Zhaohui; Zhao, Boxin

2017-09-01

Rare earth oxide La2O3 microparticles-reinforced polyimide (PI) composites (La-PI-Cs) were fabricated, aiming to improve the tribological property of PI. Surface roughness, surface composition, bulk structure, friction force (Ff) and coefficient of friction (COF) at macro/micro preload, and anti-wear performances of La-PI-Cs were studied and compared with neat PI. With La2O3 microparticles, La-PI-Cs showed larger surface roughness, lower surface energy, and higher hydrophobicity than neat PI, and displayed beneficial layered structure different from the compact structure of PI. Owing to these advantages, La-PI-Cs were found to show a 70% reduction in Ff and COF, and a 30% reduction in wear rate, indicating significantly lowered friction and enhanced anti-wear properties after adding La2O3 microparticles. Our research findings demonstrated an easy and low cost method to fabricate polymer composites with low friction and high wear resistance, and help meet the demanding of polymer composites with high tribological performances in broaden applications.

A theoretical analysis of the current-voltage characteristics of solar cells. [and their energy conversion efficiency

NASA Technical Reports Server (NTRS)

Dunbar, P. M.; Hauser, J. R.

1976-01-01

Various mechanisms which limit the conversion efficiency of silicon solar cells were studied. The effects of changes in solar cell geometry such as layer thickness on performance were examined. The effects of various antireflecting layers were also examined. It was found that any single film antireflecting layer results in a significant surface loss of photons. The use of surface texturing techniques or low loss antireflecting layers can enhance by several percentage points the conversion efficiency of silicon cells. The basic differences between n(+)-p-p(+) and p(+)-n-n(+) cells are treated. A significant part of the study was devoted to the importance of surface region lifetime and heavy doping effects on efficiency. Heavy doping bandgap reduction effects are enhanced by low surface layer lifetimes, and conversely, the reduction in solar cell efficiency due to low surface layer lifetime is further enhanced by heavy doping effects. A series of computer studies is reported which seeks to determine the best cell structure and doping levels for maximum efficiency.

Charge Retention by Monodisperse Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

NASA Astrophysics Data System (ADS)

Johnson, Grant; Priest, Thomas; Laskin, Julia

2012-02-01

Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Gold clusters were synthesized in methanol solution by reduction of a gold precursor with a weak reducing agent in the presence of a diphosphine capping ligand. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (SIMS) it is demonstrated that the cluster retains its 3+ charge state when soft landed onto the surface of a fluorinated self assembled monolayer on gold. In contrast, when deposited onto carboxylic acid terminated and conventional alkyl thiol surfaces on gold the clusters exhibit larger relative abundances of the 2+ and 1+ charge states, respectively. The kinetics of charge reduction on the surface have been investigated using in-situ Fourier Transform Ion Cyclotron Resonance SIMS. It is shown that an extremely slow interfacial charge reduction occurs on the fluorinated monolayer surface while an almost instantaneous neutralization takes place on the surface of the alkyl thiol monolayer. Our results demonstrate that the size and charge state of small gold clusters on surfaces, both of which exert a dramatic influence on their chemical and physical properties, may be tuned through soft landing of mass-selected ions onto selected substrates.

Reduction mechanism of surface oxide films and characterization of formations on pulse electric-current sintered Al Mg alloy powders

NASA Astrophysics Data System (ADS)

Xie, Guoqiang; Ohashi, Osamu; Song, Minghui; Mitsuishi, Kazutaka; Furuya, Kazuo

2005-02-01

The microstructure of interfaces between powder particles in Al-Mg alloy specimens sintered by pulse electric-current sintering (PECS) process was characterized using high resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDS). The crystalline precipitates with nano-size in the interface were observed in all of Al-Mg alloy specimens. The composition was determined to be MgAl 2O 4 or MgO, or both of them, which depended on Mg content in alloy powder and sintering temperature. The precipitates were suggested to contribute to reduction reaction of Mg with oxide films originally covered at powder particles surface.

The Role of Subsurface Oxygen on Cu Surfaces for CO 2 Electrochemical Reduction

DOE PAGES

Fields, Meredith; Hong, Xin; Norskov, Jens K.; ...

2018-06-12

Under ambient conditions, copper with oxygen near the surface displays strengthened CO 2 and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO 2 reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity ofmore » crystalline Cu.« less

The Role of Subsurface Oxygen on Cu Surfaces for CO 2 Electrochemical Reduction

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

Fields, Meredith; Hong, Xin; Norskov, Jens K.

Under ambient conditions, copper with oxygen near the surface displays strengthened CO 2 and CO adsorption energies. This finding is often used to rationalize differences seen in product distributions between Cu-oxide and pure Cu electrodes during electrochemical CO 2 reduction. However, little evidence exists to confirm the presence of oxygen within first few layers of the Cu matrix under relevant experimental reducing conditions. As a result, using density functional theory calculations, we discuss the stability of subsurface oxygen from thermodynamic and kinetic perspectives, and show that under reducing potentials, subsurface oxygen alone should have negligible effects on the activity ofmore » crystalline Cu.« less

Self-spinning nanoparticle laden microdroplets for sensing and energy harvesting.

PubMed

Bhattacharjee, Mitradip; Pasumarthi, Viswanath; Chaudhuri, Joydip; Singh, Amit Kumar; Nemade, Harshal; Bandyopadhyay, Dipankar

2016-03-21

Exposure of a volatile organic vapour could set in powerful rotational motion a microdroplet composed of an aqueous salt solution loaded with metal nanoparticles. The solutal Marangoni motion on the surface originating from the sharp difference in the surface tension of water and organic vapour stimulated the strong vortices inside the droplet. The vapour sources of methanol, ethanol, diethyl ether, toluene, and chloroform stimulated motions of different magnitudes could easily be correlated to the surface tension gradient on the drop surface. Interestingly, when the nanoparticle laden droplet of aqueous salt solution was connected to an external electric circuit through a pair of electrodes, an ∼85-95% reduction in the electrical resistance was observed across the spinning droplet. The extent of reduction in the resistance was found to have a correlation with the difference in the surface tension of the vapour source and the water droplet, which could be employed to distinguish the vapour sources. Remarkably, the power density of the same prototype was estimated to be around 7 μW cm(-2), which indicated the potential of the phenomenon in converting surface energy into electrical in a non-destructive manner and under ambient conditions. Theoretical analysis uncovered that the difference in the ζ-potential near the electrodes was the major reason for the voltage generation. The prototype could also detect the repeated exposure and withdrawal of vapour sources, which helped in the development of a proof-of-concept detector to sense alcohol issuing out of the human breathing system.

Rolling viscous drops on a non-wettable surface containing both micro- and macro-scale roughness

NASA Astrophysics Data System (ADS)

Abolghasemibizaki, Mehran; Robertson, Connor J.; Fergusson, Christian P.; McMasters, Robert L.; Mohammadi, Reza

2018-02-01

It has previously been shown that when a liquid drop of high viscosity is placed on a non-wettable inclined surface, it rolls down at a constant descent velocity determined by the balance between viscous dissipation and the reduction rate of its gravitational potential energy. Since increasing the roughness of the surface boosts its non-wetting property, the drop should move faster on a surface structured with macrotextures (ribbed surface). Such a surface was obtained from a superhydrophobic soot coating on a solid specimen printed with an extruder-type 3D printer. The sample became superoleophobic after a functionalization process. The descent velocity of glycerol drops of different radii was then measured on the prepared surface for varied tilting angles. Our data show that the drops roll down on the ribbed surface approximately 27% faster (along the ridges) than on the macroscopically smooth counterpart. This faster velocity demonstrates that ribbed surfaces can be promising candidates for drag-reduction and self-cleaning applications. Moreover, we came up with a modified scaling model to predict the descent velocity of viscous rolling drops more accurately than what has previously been reported in the literature.

Experimental assessment of the performance of ablative heat shield materials from plasma wind tunnel testing

NASA Astrophysics Data System (ADS)

Löhle, S.; Hermann, T.; Zander, F.

2018-06-01

A method for assessing the performance of typical heat shield materials is presented in this paper. Three different material samples, the DLR material Zuram, the Airbus material Asterm and the carbon preform Calcarb were tested in the IRS plasma wind tunnel PWK1 at the same nominal condition. State of the art diagnostic tools, i.e., surface temperature with pyrometry and thermography and boundary layer optical emission spectroscopy were completed by photogrammetric surface recession measurements. These data allow the assessment of the net heat flux for each material. The analysis shows that the three materials each have a different effect on heat flux mitigation with ASTERM showing the largest reduction in surface heat flux. The effect of pyrolysis and blowing is clearly observed and the heat flux reduction can be determined from an energy balance.

Paradigm shift in lead design.

PubMed

Irnich, W

1999-09-01

During the past 30 years there has been a tremendous development in electrode technology from bulky (90 mm2) to pin-sized (1.0 mm2) electrodes. Simultaneously, impedance has increased from 110 Ohms to >1 kOhms, which has been termed a "paradigm shift" in lead design. If current is responsible for stimulation, why is its impedance a key factor in saving energy? Further, what mechanism is behind this development based on experimental findings and what conclusion can be drawn from it to optimize electrode size? If it is assumed that there is always a layer of nonexcitable tissue between the electrode surface and excitable myocardium and that the electric field (potential gradient) produced by the electrode at this boundary is reaching threshold level, then a formula can be derived for the voltage threshold that completely describes the electrophysiology and electrophysics of a hemispherical electrode. Assuming that the mean chronic threshold for porous steroid-eluting electrodes is 0.6 V with 0.5-ms pulse duration, thickness of nonexcitable tissue can be estimated to be 1.5 mm. Taking into account this measure and the relationship between chronaxie and electrode area, voltage threshold, impedance, and energy as a function of surface area can be calculated. The lowest voltage for 0.5-ms pulse duration is reached with r(o) = 0.5 d, yielding a surface area of 4 mm2 and a voltage threshold of 0.62 V, an impedance of 1 kOhms, and an energy level of 197 nJ. It can be deduced from our findings that a further reduction of surface areas below 1.6 mm2 will not diminish energy threshold substantially, if pulse duration remains at 0.5 ms. Lowest energy is reached with t = chronaxie, yielding an energy level <100 nJ with surface areas < or =1.5 mm2. It is striking to see how well the theoretically derived results correspond to the experimental findings. It is also surprising that the hemispheric model so accurately approximates experimental results with differently shaped electrodes that it can be concluded that electrode shape seems to play a minor role in electrode efficiency. Further energy reduction can only be achieved by reducing the pulse duration to chronaxie. A real paradigm shift will occur only if the fundamentals of electrostimulation in combination with electrophysics are accepted by the pacing community.

Periodic density functional theory calculations of bulk and the (010) surface of goethite

PubMed Central

Kubicki, James D; Paul, Kristian W; Sparks, Donald L

2008-01-01

Background Goethite is a common and reactive mineral in the environment. The transport of contaminants and anaerobic respiration of microbes are significantly affected by adsorption and reduction reactions involving goethite. An understanding of the mineral-water interface of goethite is critical for determining the molecular-scale mechanisms of adsorption and reduction reactions. In this study, periodic density functional theory (DFT) calculations were performed on the mineral goethite and its (010) surface, using the Vienna Ab Initio Simulation Package (VASP). Results Calculations of the bulk mineral structure accurately reproduced the observed crystal structure and vibrational frequencies, suggesting that this computational methodology was suitable for modeling the goethite-water interface. Energy-minimized structures of bare, hydrated (one H2O layer) and solvated (three H2O layers) (010) surfaces were calculated for 1 × 1 and 3 × 3 unit cell slabs. A good correlation between the calculated and observed vibrational frequencies was found for the 1 × 1 solvated surface. However, differences between the 1 × 1 and 3 × 3 slab calculations indicated that larger models may be necessary to simulate the relaxation of water at the interface. Comparison of two hydrated surfaces with molecularly and dissociatively adsorbed H2O showed a significantly lower potential energy for the former. Conclusion Surface Fe-O and (Fe)O-H bond lengths are reported that may be useful in surface complexation models (SCM) of the goethite (010) surface. These bond lengths were found to change significantly as a function of solvation (i.e., addition of two extra H2O layers above the surface), indicating that this parameter should be carefully considered in future SCM studies of metal oxide-water interfaces. PMID:18477389

Tensile and fracture properties of type 316 stainless steel after creep

NASA Astrophysics Data System (ADS)

Gan, D.

1982-12-01

The effects of creep on the mechanical properties of type 316 stainless steel were studied. Tensile and Charpy specimens were machined from the oversize specimens crept at 750 °C and 103 MPa. The ambient fracture energy was found to deteriorate rapidly after creep. The ambient yield stress was increased moderately, but the tensile ductility was severely reduced. The effects of intergranular carbides alone on mechanical properties were studied with specimens thermal aged without load. These carbides were shown to cause a moderate reduction in fracture energy and tensile ductility but had little effect on yield stress. Extensive grain boundary separations were observed on the fracture surfaces. SEM studies showed that these grain boundaries were covered with micro voids initiated by the dense intergranular carbides. Frequently, large dimples on grain boundary joined up and initiated shear fracture into the grain. In the crept specimens additional microstructural changes in the form of intragranular carbides and subgrain boundaries were observed. Both are responsible for the increase in yield stress and the further reduction in tensile ductility and fracture energy. The intragranular carbides also modified the size and density of the dimples on the fracture surfaces.

Stellar fibril magnetic systems. I - Reduced energy state

NASA Technical Reports Server (NTRS)

Parker, E. N.

1984-01-01

The remarkable fibril structure of the magnetic fields at the surface of the sun (with fibrils compressed to 1,000-2,000 gauss) lies outside existing statistical theories of magnetohydrodynamic turbulence. The total energy of the fibril field is enhanced by a factor of more than 100 above the energy for the mean field in a continuum state. The magnetic energy density within a fibril is of the order of 100 times the local kinetic energy density, so that no simple application of equipartition principles is possible. It is pointed out that the total energy of the atmosphere (thermal + gravitational + magnetic) is reduced by the fibril state of the field by avoiding the magnetic inhibition of the convective overturning, suggesting that the formation of the observed intense fibril state may be in response to the associated energy reduction. Calculation of the minimum total energy of a polytropic atmosphere permeated by magnetic fibrils yields theoretical fibril fields of the order of 1-5 kilogauss when characteristics appropriate to the solar convective zone are introduced, in rough agreement with the actual fields of 1-2 kilogauss. The polytrope model, although crude, establishes that a large reduction in total energy is made possible by the fibril state.

Plasma-assisted reduction of silver ions impregnated into a natural zeolite framework

NASA Astrophysics Data System (ADS)

Osonio, Airah P.; Vasquez, Magdaleno R.

2018-02-01

A green, dry, and energy-efficient method for the fabrication of silver-zeolite (AgZ) composite via 13.56 MHz radio-frequency plasma reduction is demonstrated. Impregnation by soaking and ion-exchange deposition were performed to load the silver ions (Ag+) into the sodium-zeolite samples. Characterization was performed by optical emission spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller analyses. Results indicate the successful reduction of Ag+ to its metallic state on the surface of the zeolite with a mean diameter of 165 nm. This plasma-induced reduction technique opens possibilities in several areas including catalysis, adsorption, water treatment, and medicine.

Electrochemical oxygen reduction behavior of selectively deposited platinum atoms on gold nanoparticles.

PubMed

Sarkar, A; Kerr, J B; Cairns, E J

2013-07-22

Carbon-supported Pt@Au "core-shell" nanoparticles with varying surface concentration of platinum atoms have been synthesized using a novel redox-mediated synthesis approach. The synthesis technique allows for a selective deposition of platinum atoms on the surface of prefabricated gold nanoparticles. Energy dispersive spectroscopic analyses in a scanning electron microscope reveal that the platinum to gold atomic ratios are close to the nominal values, validating the synthesis scheme. X-ray diffraction data indicate an un-alloyed structure. The platinum to gold surface atomic ratio determined from cyclic voltammetry and copper under-potential deposition experiments reveal good agreement with the calculated values at low platinum concentration. However, there is an increase in non-uniformity in the deposition process upon increasing the platinum concentration. Koutecky-Levich analysis of the samples indicates a transition of the total number of electrons transferred (n) in the electrochemical oxygen reduction reaction from two to four electrons upon increasing the surface concentration of platinum atoms. Furthermore, the data indicate that isolated platinum atoms can reduce molecular oxygen but via a two-electron route. Moreover, successful four-electron reduction of molecular oxygen requires clusters of platinum atoms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mitigating Climate Change with Ocean Pipes: Influencing Land Temperature and Hydrology and Termination Overshoot Risk

NASA Astrophysics Data System (ADS)

Kwiatkowski, L.; Caldeira, K.; Ricke, K.

2014-12-01

With increasing risk of dangerous climate change geoengineering solutions to Earth's climate problems have attracted much attention. One proposed geoengineering approach considers the use of ocean pipes as a means to increase ocean carbon uptake and the storage of thermal energy in the deep ocean. We use a latest generation Earth System Model (ESM) to perform simulations of idealised extreme implementations of ocean pipes. In our simulations, downward transport of thermal energy by ocean pipes strongly cools the near surface atmosphere - by up to 11°C on a global mean. The ocean pipes cause net thermal energy to be transported from the terrestrial environment to the deep ocean while increasing the global net transport of water to land. By cooling the ocean surface more than the land, ocean pipes tend to promote a monsoonal-type circulation, resulting in increased water vapour transport to land. Throughout their implementation, ocean pipes prevent energy from escaping to space, increasing the amount of energy stored in Earth's climate system despite reductions in surface temperature. As a consequence, our results indicate that an abrupt termination of ocean pipes could cause dramatic increases in surface temperatures beyond that which would have been obtained had ocean pipes not been implemented.

Light Reflector

NASA Astrophysics Data System (ADS)

1988-01-01

Ultra Sales, Inc.'s fluorescent lighting fixture gets a boost in reflectivity through installation of Lightdriver, a thin tough thermoplastic film plated with aluminum, capable of reflecting 95 percent of visible light striking it. Lightdriver increases brightness without adding bulbs, and allows energy savings by removing some bulbs because the mirrorlike surface cuts light loss generally occasioned by conventional low reflectivity white painted surface above the bulbs in many fluorescent fixtures. Forty-five percent reduction in lighting electricity is attainable.

Monte Carlo investigation of backscatter factors for skin dose determination in interventional neuroradiology procedures

NASA Astrophysics Data System (ADS)

Omar, Artur; Benmakhlouf, Hamza; Marteinsdottir, Maria; Bujila, Robert; Nowik, Patrik; Andreo, Pedro

2014-03-01

Complex interventional and diagnostic x-ray angiographic (XA) procedures may yield patient skin doses exceeding the threshold for radiation induced skin injuries. Skin dose is conventionally determined by converting the incident air kerma free-in-air into entrance surface air kerma, a process that requires the use of backscatter factors. Subsequently, the entrance surface air kerma is converted into skin kerma using mass energy-absorption coefficient ratios tissue-to-air, which for the photon energies used in XA is identical to the skin dose. The purpose of this work was to investigate how the cranial bone affects backscatter factors for the dosimetry of interventional neuroradiology procedures. The PENELOPE Monte Carlo system was used to calculate backscatter factors at the entrance surface of a spherical and a cubic water phantom that includes a cranial bone layer. The simulations were performed for different clinical x-ray spectra, field sizes, and thicknesses of the bone layer. The results show a reduction of up to 15% when a cranial bone layer is included in the simulations, compared with conventional backscatter factors calculated for a homogeneous water phantom. The reduction increases for thicker bone layers, softer incident beam qualities, and larger field sizes, indicating that, due to the increased photoelectric crosssection of cranial bone compared to water, the bone layer acts primarily as an absorber of low-energy photons. For neurointerventional radiology procedures, backscatter factors calculated at the entrance surface of a water phantom containing a cranial bone layer increase the accuracy of the skin dose determination.

Electro-Reduction of Nitrogen on Molybdenum Nitride: Structure, Energetics, and Vibrational Spectra from DFT

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

Matanovic, Ivana; Garzon, Fernando; Henson, Neil J.

2014-02-21

We used density functional theory to study the electrochemical conversion of nitrogen to ammonia on the (001), (100/010), (101), and (111) surfaces of g-Mo2N. Based on the calculated free energy profiles for the reduction of nitrogen by the associative and dissociative mechanisms, reactivity was found to decrease in the order (111) > (101) > (100/010) E (001). Namely, the cell potentials needed to drive the reduction to ammonia increase in the following order: *0.7 V on (111), *1.2 V on (101), and *1.4 V on (100/010) and (001) surfaces. The (111) surface was found to be the most reactive formore » nitrogen due to (i) its ability to adsorb the N2 in the side-on position which activates N–N bonding and (ii) its high affinity for N-adatoms which also prevents accumulation of H-adatoms on the catalytic surface at low cell potentials. We have also calculated vibrational frequencies of different NxHy species adsorbed on various g-Mo2N surfaces. The frequencies are found to depend strongly on the type of the binding sites available on the crystal facets. A comparison of the calculated frequencies with the frequencies of the corresponding species in transition metal complexes and other metal surfaces shows that the frequencies of several signature modes fall in a similar region and might be used to assign the spectra of hydrogen and nitrogen containing surface species on different metal surfaces.« less

Suppressing breakers with polar oil films: Using an epic sea rescue to model wave energy budgets

NASA Astrophysics Data System (ADS)

Cox, Charles S.; Zhang, Xin; Duda, Timothy F.

2017-02-01

Oil has been used to still stormy seas for centuries, but the mechanisms are poorly understood. Here we examine the processes by using quantitative information from a remarkable 1883 sea rescue where oil was used to reduce large breakers during a storm. Modeling of the oil film's extent and waves under the film suggests that large breakers were suppressed by a reduction of wind energy input. Modification of surface roughness by the film is hypothesized to alter the wind profile above the sea and the energy flow. The results are central to understanding air-sea momentum exchange, including its role in such processes as cyclone growth and storm surge, although they address only one aspect of the complex problem of wind interaction with the ocean surface.

Ocean Warming, More than Acidification, Reduces Shell Strength in a Commercial Shellfish Species during Food Limitation

PubMed Central

Mackenzie, Clara L.; Ormondroyd, Graham A.; Curling, Simon F.; Ball, Richard J.; Whiteley, Nia M.; Malham, Shelagh K.

2014-01-01

Ocean surface pH levels are predicted to fall by 0.3–0.4 pH units by the end of the century and are likely to coincide with an increase in sea surface temperature of 2–4°C. The combined effect of ocean acidification and warming on the functional properties of bivalve shells is largely unknown and of growing concern as the shell provides protection from mechanical and environmental challenges. We examined the effects of near-future pH (ambient pH –0.4 pH units) and warming (ambient temperature +4°C) on the shells of the commercially important bivalve, Mytilus edulis when fed for a limited period (4–6 h day−1). After six months exposure, warming, but not acidification, significantly reduced shell strength determined as reductions in the maximum load endured by the shells. However, acidification resulted in a reduction in shell flex before failure. Reductions in shell strength with warming could not be explained by alterations in morphology, or shell composition but were accompanied by reductions in shell surface area, and by a fall in whole-body condition index. It appears that warming has an indirect effect on shell strength by re-allocating energy from shell formation to support temperature-related increases in maintenance costs, especially as food supply was limited and the mussels were probably relying on internal energy reserves. The maintenance of shell strength despite seawater acidification suggests that biomineralisation processes are unaffected by the associated changes in CaCO3 saturation levels. We conclude that under near-future climate change conditions, ocean warming will pose a greater risk to shell integrity in M. edulis than ocean acidification when food availability is limited. PMID:24489785

Ocean warming, more than acidification, reduces shell strength in a commercial shellfish species during food limitation.

PubMed

Mackenzie, Clara L; Ormondroyd, Graham A; Curling, Simon F; Ball, Richard J; Whiteley, Nia M; Malham, Shelagh K

2014-01-01

Ocean surface pH levels are predicted to fall by 0.3-0.4 pH units by the end of the century and are likely to coincide with an increase in sea surface temperature of 2-4 °C. The combined effect of ocean acidification and warming on the functional properties of bivalve shells is largely unknown and of growing concern as the shell provides protection from mechanical and environmental challenges. We examined the effects of near-future pH (ambient pH -0.4 pH units) and warming (ambient temperature +4 °C) on the shells of the commercially important bivalve, Mytilus edulis when fed for a limited period (4-6 h day(-1)). After six months exposure, warming, but not acidification, significantly reduced shell strength determined as reductions in the maximum load endured by the shells. However, acidification resulted in a reduction in shell flex before failure. Reductions in shell strength with warming could not be explained by alterations in morphology, or shell composition but were accompanied by reductions in shell surface area, and by a fall in whole-body condition index. It appears that warming has an indirect effect on shell strength by re-allocating energy from shell formation to support temperature-related increases in maintenance costs, especially as food supply was limited and the mussels were probably relying on internal energy reserves. The maintenance of shell strength despite seawater acidification suggests that biomineralisation processes are unaffected by the associated changes in CaCO3 saturation levels. We conclude that under near-future climate change conditions, ocean warming will pose a greater risk to shell integrity in M. edulis than ocean acidification when food availability is limited.

Designed Proteins as Optimized Oxygen Carriers for Artificial Blood

DTIC Science & Technology

2013-02-01

to the lower energy for electron transfer when coupled to a proton transfer from water (3). Thus we set out to compare the rate of solvent...binding affinities and reduction potentials are the sole result of differences in internal electric fields in these proteins wrought by the surface...serving as the source of potential energy for the hexa- to penta-coordinate conformational change, and one in which the b-position glutamates from

Can regional climate engineering save the summer Arctic sea ice?

NASA Astrophysics Data System (ADS)

Tilmes, S.; Jahn, Alexandra; Kay, Jennifer E.; Holland, Marika; Lamarque, Jean-Francois

2014-02-01

Rapid declines in summer Arctic sea ice extent are projected under high-forcing future climate scenarios. Regional Arctic climate engineering has been suggested as an emergency strategy to save the sea ice. Model simulations of idealized regional dimming experiments compared to a business-as-usual greenhouse gas emission simulation demonstrate the importance of both local and remote feedback mechanisms to the surface energy budget in high latitudes. With increasing artificial reduction in incoming shortwave radiation, the positive surface albedo feedback from Arctic sea ice loss is reduced. However, changes in Arctic clouds and the strongly increasing northward heat transport both counteract the direct dimming effects. A 4 times stronger local reduction in solar radiation compared to a global experiment is required to preserve summer Arctic sea ice area. Even with regional Arctic dimming, a reduction in the strength of the oceanic meridional overturning circulation and a shut down of Labrador Sea deep convection are possible.

The effects of drought-induced mortality on the response of surviving trees in piñon-juniper woodlands

NASA Astrophysics Data System (ADS)

Huang, C. W.; Pockman, W.; Litvak, M. E.

2017-12-01

lthough it is well-established that land cover change influences water and carbon cycles across different spatiotemporal scales, the impact of climate-driven mortality events on site energy and water balance and subsequently on vegetation dynamics is more variable among studies. In semi-arid ecosystems globally, mortality events following severe drought are increasingly common. We used long-term observations (i.e., from 2009 to present) in two piñon-juniper (i.e., Pinus edulis and Juniperus monosperma) woodlands located at central New Mexico USA to explore the consequence of mortality events in such water-stressed environments. We compared a pinon-juniper woodland site where girdling was used to mimic mortality of adult pinon (PJG) with a nearby untreated woodland site (PJC). Our primary goal is to disentangle the reduction in water loss via biological pathway (i.e., leaf and sapwood area) introduced by girdling manipulation from other effects contributing to the response of surviving trees such as modifications in surface reflectivity (i.e., albedo and emissivity) and surface roughness impacting the partitioning between components in both energy and water balance at canopy level. To achieve this goal, we directly measured sap flux, environmental factors and ecosystem-atmosphere exchange of carbon, water and energy fluxes using eddy-covariance systems at both sites. We found that 1) for each component of the energy balance the difference between PJC and PJG was surprisingly negligible such that the canopy-level surface temperature (i.e., both radiometric and aerodynamic temperature) remains nearly identical for the two sites; 2) the surface reflectivity and roughness are mainly dominated by the soil surface especially when the foliage coverage in semi-arid regions is small; 3) the increase in soil evaporation after girdling manipulation outcompetes the surviving trees for the use of water in the soil. These results suggest that the so-called `water release hypothesis' may not occur in such water-stressed environments and the surviving trees may become less resilient to further drought conditions mainly due to the reduction in the soil water availability. Keywords: drought resilience, tree mortality, partitioning in energy and water balance, water release hypothesis

Effects of surface motion and electron-hole pair excitations in CO2 dissociation and scattering on Ni(100)

NASA Astrophysics Data System (ADS)

Luo, Xuan; Zhou, Xueyao; Jiang, Bin

2018-05-01

The energy transfer between different channels is an important aspect in chemical reactions at surfaces. We investigate here in detail the energy transfer dynamics in a prototypical system, i.e., reactive and nonreactive scattering of CO2 on Ni(100), which is related to heterogeneous catalytic processes with Ni-based catalysts for CO2 reduction. On the basis of our earlier nine-dimensional potential energy surface for CO2/Ni(100), dynamical calculations have been done using the generalized Langevin oscillator (GLO) model combined with local density friction approximation (LDFA), in which the former accounts for the surface motion and the latter accounts for the low-energy electron-hole pair (EHP) excitation. In spite of its simplicity, it is found that the GLO model yields quite satisfactory results, including the significant energy loss and product energy disposal, trapping, and steering dynamics, all of which agree well with the ab initio molecular dynamics ones where many surface atoms are explicitly involved with high computational cost. However, the GLO model fails to describe the reactivity enhancement due to the lattice motion because it intrinsically does not incorporate the variance of barrier height on the surface atom displacement. On the other hand, in LDFA, the energy transferred to EHPs is found to play a minor role and barely alter the dynamics, except for slightly reducing the dissociation probabilities. In addition, vibrational state-selected dissociative sticking probabilities are calculated and previously observed strong mode specificity is confirmed. Our work suggests that further improvement of the GLO model is needed to consider the lattice-induced barrier lowering.

Optical design of tunnel lighting with white light-emitting diodes.

PubMed

Tsai, Ming-Shiou; Lee, Xuan-Hao; Lo, Yi-Chien; Sun, Ching-Cherng

2014-10-10

This paper presents a tunnel lighting design consisting of a cluster light-emitting diode and a free-form lens. Most of the energy emitted from the proposed luminaire is transmitted onto the surface of the road in front of drivers, and the probability that that energy is emitted directly into drivers' eyes is low. Compared with traditional fluorescent lamps, the proposed luminaire, of which the optical utilization factor, optical efficiency, and uniformity are, respectively, 44%, 92.5%, and 0.72, exhibits favorable performance in energy saving, glare reduction, and traffic safety.

Characterization of p-Type CdTe Electrodes in Acetonitrile/Electrolyte Solutions. Nearly Ideal Behavior from Reductive Surface Pretreatments.

DTIC Science & Technology

1983-06-30

using Ag conductive palnt and the entire assembly was mounted in glass tubing with ordinary epoxy leaving only the front crystal face, ...energy set, several eV higher than either Te2- or Teo (as measured for sputtered CdTe and Te, respectively) is assigned to TeO2 , the lowest stable...binding energy reported for TeO2 (575.9 eV). 33 The lower binding energy set of bands, lying midway between Teo and Te2 - , results from both Teo and

Improving density functional tight binding predictions of free energy surfaces for peptide condensation reactions in solution

NASA Astrophysics Data System (ADS)

Kroonblawd, Matthew; Goldman, Nir

First principles molecular dynamics using highly accurate density functional theory (DFT) is a common tool for predicting chemistry, but the accessible time and space scales are often orders of magnitude beyond the resolution of experiments. Semi-empirical methods such as density functional tight binding (DFTB) offer up to a thousand-fold reduction in required CPU hours and can approach experimental scales. However, standard DFTB parameter sets lack good transferability and calibration for a particular system is usually necessary. Force matching the pairwise repulsive energy term in DFTB to short DFT trajectories can improve the former's accuracy for chemistry that is fast relative to DFT simulation times (<10 ps), but the effects on slow chemistry and the free energy surface are not well-known. We present a force matching approach to increase the accuracy of DFTB predictions for free energy surfaces. Accelerated sampling techniques are combined with path collective variables to generate the reference DFT data set and validate fitted DFTB potentials without a priori knowledge of transition states. Accuracy of force-matched DFTB free energy surfaces is assessed for slow peptide-forming reactions by direct comparison to DFT results for particular paths. Extensions to model prebiotic chemistry under shock conditions are discussed. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Solar energy utilization in the direct photocarboxylation of 2,3-dihydrofuran using CO2.

PubMed

Aresta, Michele; Dibenedetto, Angela; Baran, Tomasz; Wojtyła, Szymon; Macyk, Wojciech

2015-01-01

The conversion of CO2 into high energy products (fuels) and the direct carboxylation of C-H bonds require a high energy input. Energy cannot be derived from fossil carbon, in this case. Solar energy can be used instead, with a low environmental impact and good profit. We have studied the use of white light or solar energy in the photoreduction of CO2 and in photocarboxylation reactions, using different semiconductors modified at their surface. Two examples of reduction of CO2 to methanol and CO will be shortly discussed, and two cases of carboxylation of organic substrates. The case of carboxylation of 2,3-dihydrofuran will be discussed in detail.

A strategy for analysis of (molecular) equilibrium simulations: Configuration space density estimation, clustering, and visualization

NASA Astrophysics Data System (ADS)

Hamprecht, Fred A.; Peter, Christine; Daura, Xavier; Thiel, Walter; van Gunsteren, Wilfred F.

2001-02-01

We propose an approach for summarizing the output of long simulations of complex systems, affording a rapid overview and interpretation. First, multidimensional scaling techniques are used in conjunction with dimension reduction methods to obtain a low-dimensional representation of the configuration space explored by the system. A nonparametric estimate of the density of states in this subspace is then obtained using kernel methods. The free energy surface is calculated from that density, and the configurations produced in the simulation are then clustered according to the topography of that surface, such that all configurations belonging to one local free energy minimum form one class. This topographical cluster analysis is performed using basin spanning trees which we introduce as subgraphs of Delaunay triangulations. Free energy surfaces obtained in dimensions lower than four can be visualized directly using iso-contours and -surfaces. Basin spanning trees also afford a glimpse of higher-dimensional topographies. The procedure is illustrated using molecular dynamics simulations on the reversible folding of peptide analoga. Finally, we emphasize the intimate relation of density estimation techniques to modern enhanced sampling algorithms.

Skin Temperature Analysis and Bias Correction in a Coupled Land-Atmosphere Data Assimilation System

NASA Technical Reports Server (NTRS)

Bosilovich, Michael G.; Radakovich, Jon D.; daSilva, Arlindo; Todling, Ricardo; Verter, Frances

2006-01-01

In an initial investigation, remotely sensed surface temperature is assimilated into a coupled atmosphere/land global data assimilation system, with explicit accounting for biases in the model state. In this scheme, an incremental bias correction term is introduced in the model's surface energy budget. In its simplest form, the algorithm estimates and corrects a constant time mean bias for each gridpoint; additional benefits are attained with a refined version of the algorithm which allows for a correction of the mean diurnal cycle. The method is validated against the assimilated observations, as well as independent near-surface air temperature observations. In many regions, not accounting for the diurnal cycle of bias caused degradation of the diurnal amplitude of background model air temperature. Energy fluxes collected through the Coordinated Enhanced Observing Period (CEOP) are used to more closely inspect the surface energy budget. In general, sensible heat flux is improved with the surface temperature assimilation, and two stations show a reduction of bias by as much as 30 Wm(sup -2) Rondonia station in Amazonia, the Bowen ratio changes direction in an improvement related to the temperature assimilation. However, at many stations the monthly latent heat flux bias is slightly increased. These results show the impact of univariate assimilation of surface temperature observations on the surface energy budget, and suggest the need for multivariate land data assimilation. The results also show the need for independent validation data, especially flux stations in varied climate regimes.

Wind reduction by aerosol particles

NASA Astrophysics Data System (ADS)

Jacobson, Mark Z.; Kaufman, Yoram J.

2006-12-01

Aerosol particles are known to affect radiation, temperatures, stability, clouds, and precipitation, but their effects on spatially-distributed wind speed have not been examined to date. Here, it is found that aerosol particles, directly and through their enhancement of clouds, may reduce near-surface wind speeds below them by up to 8% locally. This reduction may explain a portion of observed ``disappearing winds'' in China, and it decreases the energy available for wind-turbine electricity. In California, slower winds reduce emissions of wind-driven soil dust and sea spray. Slower winds and cooler surface temperatures also reduce moisture advection and evaporation. These factors, along with the second indirect aerosol effect, may reduce California precipitation by 2-5%, contributing to a strain on water supply.

Analysis of the interactions between He + ions and transition metal surfaces using co-axial impact collision ion scattering spectroscopy

NASA Astrophysics Data System (ADS)

Walker, M.; Brown, M. G.; Draxler, M.; Fishwick, L.; Dowsett, M. G.; McConville, C. F.

2011-01-01

The interactions between low energy He + ions and a series of transition metal surfaces have been studied using co-axial impact collision ion scattering spectroscopy (CAICISS). Experimental data were collected from the Ni(110), Cu(100), Pd(111), Pt(111) and Au(111) surfaces using ion beams with primary energies between 1.5 keV and 4.0 keV. The shadow cone radii deduced from the experimental surface peak positions were found to closely match theoretical predictions. Data analysis was performed using both the FAN and Kalypso simulation codes, revealing a consistent requirement for a reduction of 0.252 in the screening length correction in the Molière approximation within the Thomas-Fermi (TFM) interaction potential. The adjustments of the screening length in the TFM potential, predicted by O'Connor, and the uncorrected Ziegler-Biersack-Littmark (ZBL) potential both yielded inaccurate results for all of the surfaces and incident energies studied. We also provide evidence that, despite their different computational methodologies, the FAN and Kalypso simulation codes generate similar results given identical input parameters for the analysis of 180° backscattering spectra.

Chemical grafting of the superhydrophobic surface on copper with hierarchical microstructure and its formation mechanism

NASA Astrophysics Data System (ADS)

Cai, Junyan; Wang, Shuhui; Zhang, Junhong; Liu, Yang; Hang, Tao; Ling, Huiqin; Li, Ming

2018-04-01

In this paper, a superhydrophobic surface with hierarchical structure was fabricated by chemical deposition of Cu micro-cones array, followed by chemical grafting of poly(methyl methacrylate) (PMMA). Water contact measurements give contact angle of 131.0° on these surfaces after PMMA grafting of 2 min and 165.2° after 6 min. The superhydrophobicity results from two factors: (1) the hierarchical structure due to Cu micro-cones array and the second level structure caused by intergranular corrosion during grafting of PMMA (confirmed by the scanning electron microscopy) and (2) the chemical modification of a low surface energy PMMA layer (confirmed by Fourier transform infrared spectrometer and X-ray photoelectron spectroscopy). In the chemical grafting process, the spontaneous reduction of nitrobenzene diazonium (NBD) tetrafluoroborate not only causes the corrosion of the Cu surface that leads to a hierarchical structure, but also initiates the polymerization of methyl methacrylate (MMA) monomers and thus the low free energy surface. Such a robust approach to fabricate the hierarchical structured surface with superhydrophobicity is expected to have practical application in anti-corrosion industry.

Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

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

Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P.

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction onmore » Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.« less

Sensitivity of surface temperature and atmospheric temperature to perturbations in the stratospheric concentration of ozone and nitrogen dioxide

NASA Technical Reports Server (NTRS)

Ramanathan, V.; Callis, L. B.; Boughner, R. E.

1976-01-01

A radiative-convective model is proposed for estimating the sensitivity of the atmospheric radiative heating rates and atmospheric and surface temperatures to perturbations in the concentration of O3 and NO2 in the stratosphere. Contribution to radiative energy transfer within the atmosphere from H2O, CO2, O3, and NO2 is considered. It is found that the net solar radiation absorbed by the earth-atmosphere system decreases with a reduction in O3; if the reduction of O3 is accompanied by an increase in NO2, there is a compensating effect due to solar absorption by NO2. The surface temperature and atmospheric temperature decrease with decreasing stratospheric O3. Another major conclusion is the strong sensitivity of surface temperature to the vertical distribution of O3 within the atmosphere. The results should be considered as reflecting the sensitivity of the proposed model rather than the sensitivity of the actual earth-atmosphere system.

Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

DOE PAGES

Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P.; ...

2017-01-06

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction onmore » Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.« less

Role of LiCoO 2 Surface Terminations in Oxygen Reduction and Evolution Kinetics

DOE PAGES

Han, Binghong; Qian, Danna; Risch, Marcel; ...

2015-03-22

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO 2 nanorods with sizes in the range from 9 to 40 nm were studied in alkaline solution. The sides of these nanorods were terminated with low-index surfaces such as (003) while the tips were terminated largely with high-index surfaces such as (104) as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co 3+ prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co 3+. We correlated the electronic and atomic structure to higher specific ORR and OER activities at themore » tips as compared to the sides, which was accompanied by more facile redox of Co 2+/3+ and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition metal oxides on the ORR and OER activity.« less

Communication: Visualization and spectroscopy of defects induced by dehydrogenation in individual silicon nanocrystals

NASA Astrophysics Data System (ADS)

Kislitsyn, Dmitry A.; Mills, Jon M.; Kocevski, Vancho; Chiu, Sheng-Kuei; DeBenedetti, William J. I.; Gervasi, Christian F.; Taber, Benjamen N.; Rosenfield, Ariel E.; Eriksson, Olle; Rusz, Ján; Goforth, Andrea M.; Nazin, George V.

2016-06-01

We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

Mesoporous metallic rhodium nanoparticles

NASA Astrophysics Data System (ADS)

Jiang, Bo; Li, Cuiling; Dag, Ömer; Abe, Hideki; Takei, Toshiaki; Imai, Tsubasa; Hossain, Md. Shahriar A.; Islam, Md. Tofazzal; Wood, Kathleen; Henzie, Joel; Yamauchi, Yusuke

2017-05-01

Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ~2.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O2.

Surface hardness of different restorative materials after long-term immersion in sports and energy drinks.

PubMed

Erdemir, Ugur; Yildiz, Esra; Eren, Meltem Mert; Ozel, Sevda

2012-01-01

The purpose of this study was to evaluate the effect of sports and energy drinks on the surface hardness of different restorative materials over a 6-month period. Forty-two disk-shaped specimens were prepared for each of the four restorative materials tested: Compoglass F, Filtek Z250, Filtek Supreme, and Premise. Specimens were immersed for 2 min daily, up to 6 months, in six storage solutions (n=7 per material for each solution): distilled water, Powerade, Gatorade, X-IR, Burn, and Red Bull. Surface hardness was measured at baseline, after 1 week, 1 month, and 6 months. Data were analyzed statistically using repeated measures ANOVA followed by the Bonferroni test for multiple comparisons (α=0.05). Surface hardness of the restorative materials was significantly affected by both immersion solution and immersion period (p<0.001). All tested solutions induced significant reduction in surface hardness of the restorative materials over a 6-month immersion period.

Slow-muon study of quaternary solar-cell materials: Single layers and p -n junctions

NASA Astrophysics Data System (ADS)

Alberto, H. V.; Vilão, R. C.; Vieira, R. B. L.; Gil, J. M.; Weidinger, A.; Sousa, M. G.; Teixeira, J. P.; da Cunha, A. F.; Leitão, J. P.; Salomé, P. M. P.; Fernandes, P. A.; Törndahl, T.; Prokscha, T.; Suter, A.; Salman, Z.

2018-02-01

Thin films and p -n junctions for solar cells based on the absorber materials Cu (In ,G a ) Se2 and Cu2ZnSnS4 were investigated as a function of depth using implanted low energy muons. The most significant result is a clear decrease of the formation probability of the Mu+ state at the heterojunction interface as well as at the surface of the Cu (In ,G a ) Se2 film. This reduction is attributed to a reduced bonding reaction of the muon in the absorber defect layer at its surface. In addition, the activation energies for the conversion from a muon in an atomiclike configuration to a anion-bound position are determined from temperature-dependence measurements. It is concluded that the muon probe provides a measurement of the effective surface defect layer width, both at the heterojunctions and at the films. The CIGS surface defect layer is crucial for solar-cell electrical performance and additional information can be used for further optimizations of the surface.

Modification of polyvinyl alcohol surface properties by ion implantation

NASA Astrophysics Data System (ADS)

Pukhova, I. V.; Kurzina, I. A.; Savkin, K. P.; Laput, O. A.; Oks, E. M.

2017-05-01

We describe our investigations of the surface physicochemical properties of polyvinyl alcohol modified by silver, argon and carbon ion implantation to doses of 1 × 1014, 1 × 1015 and 1 × 1016 ion/cm2 and energies of 20 keV (for C and Ar) and 40 keV (for Ag). Infrared spectroscopy (IRS) indicates that destructive processes accompanied by chemical bond (sbnd Cdbnd O) generation are induced by implantation, and X-ray photoelectron spectroscopy (XPS) analysis indicates that the implanted silver is in a metallic Ag3d state without stable chemical bond formation with polymer chains. Ion implantation is found to affect the surface energy: the polar component increases while the dispersion part decreases with increasing implantation dose. Surface roughness is greater after ion implantation and the hydrophobicity increases with increasing dose, for all ion species. We find that ion implantation of Ag, Ar and C leads to a reduction in the polymer microhardness by a factor of five, while the surface electrical resistivity declines modestly.

Can Aerosol Offset Urban Heat Island Effect?

NASA Astrophysics Data System (ADS)

Jin, M. S.; Shepherd, J. M.

2009-12-01

The Urban Heat Island effect (UHI) refers to urban skin or air temperature exceeding the temperatures in surrounding non-urban regions. In a warming climate, the UHI may intensify extreme heat waves and consequently cause significant health and energy problems. Aerosols reduce surface insolation via the direct effect, namely, scattering and absorbing sunlight in the atmosphere. Combining the National Aeronautics and Space Administration (NASA) AERONET (AErosol RObotic NETwork) observations over large cities together with Weather Research and Forecasting Model (WRF) simulations, we find that the aerosol direct reduction of surface insolation range from 40-100 Wm-2, depending on seasonality and aerosol loads. As a result, surface skin temperature can be reduced by 1-2C while 2-m surface air temperature by 0.5-1C. This study suggests that the aerosol direct effect is a competing mechanism for the urban heat island effect (UHI). More importantly, both aerosol and urban land cover effects must be adequately represented in meteorological and climate modeling systems in order to properly characterize urban surface energy budgets and UHI.

Enhanced mechanical, thermal, and electric properties of graphene aerogels via supercritical ethanol drying and high-temperature thermal reduction.

PubMed

Cheng, Yehong; Zhou, Shanbao; Hu, Ping; Zhao, Guangdong; Li, Yongxia; Zhang, Xinghong; Han, Wenbo

2017-05-03

Graphene aerogels with high surface areas, ultra-low densities and thermal conductivities have been prepared to exploit their wide applications from pollution adsorption to energy storage, supercapacitor, and thermal insulation. However, the low mechanical properties, poor thermal stability and electric conductivity restrict these aerogels' applications. In this paper, we prepared mechanically strong graphene aerogels with large BET surface areas, low thermal conductivities, high thermal stability and electric conductivities via hydrothermal reduction and supercritical ethanol drying. Annealing at 1500 °C resulted in slightly increased thermal conductivity and further improvement in mechanical properties, oxidation temperature and electric conductivity of the graphene aerogel. The large BET surface areas, together with strong mechanical properties, low thermal conductivities, high thermal stability and electrical conductivities made these graphene aerogels feasible candidates for use in a number of fields covering from batteries to sensors, electrodes, lightweight conductor and insulation materials.

Surface spectators and their role in relationships between activity and selectivity of the oxygen reduction reaction in acid environments.

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

Ciapina, Eduardo G.; Lopes, Pietro P.; Subbaraman, Ram

2015-11-01

We use the rotating ring disk (RRDE) method to study activity-selectivity relationships for the oxygen reduction reaction (ORR) on Pt(111) modified by various surface coverages of adsorbed CNad (ΘCNad). The results demonstrate that small variations in ΘCNad have dramatic effect on the ORR activity and peroxide production, resulting in “volcano-like” dependence with an optimal surface coverage of ΘCNad = 0.3 ML. These relationships can be simply explained by balancing electronic and ensemble effects of co-adsorbed CNad and adsorbed spectator species from the supporting electrolytes, without the need for intermediate adsorption energy arguments. Although this study has focused on the Pt(111)-CNad/H2SO4more » interface, the results and insight gained here are invaluable for controlling another dimension in the properties of electrochemical interfaces.« less

Synthesis, Characterization, Topographical Modification, and Surface Properties of Copoly(Imide Siloxane)s

NASA Technical Reports Server (NTRS)

Wohl, Christopher J.; Atkins, Brad M.; Belcher, Marcus A.; Connell, John W.

2012-01-01

Novel copoly(imide siloxane)s were synthesized from commercially available aminopropyl terminated siloxane oligomers, aromatic dianhydrides, and diamines. This synthetic approach produced copolymers with well-defined siloxane blocks linked with imide units in a random fashion. The copoly(amide acid)s were characterized by solution viscosity and subsequently used to cast thin films followed by thermal imidization in an inert atmosphere. Thin films were characterized using contact angle goniometry, attenuated total reflection Fourier transform infrared spectroscopy, confocal and optical microscopy, and tensile testing. Adhesion of micronsized particles was determined quantitatively using a sonication device. The polydimethylsiloxane (PDMS) moieties lowered the copolymer surface energy due to migration of siloxane moieties to the film s surface, resulting in a notable reduction in particle adhesion. A further reduction in particle adhesion was achieved by introducing topographical features on a scale of several to tens of microns by a laser ablation technique.

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

Favaro, Marco; Xiao, Hai; Cheng, Tao

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide ismore » essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.« less

Experimental assessment of the performance of ablative heat shield materials from plasma wind tunnel testing

NASA Astrophysics Data System (ADS)

Löhle, S.; Hermann, T.; Zander, F.

2017-12-01

A method for assessing the performance of typical heat shield materials is presented in this paper. Three different material samples, the DLR material uc(Zuram), the Airbus material uc(Asterm) and the carbon preform uc(Calcarb) were tested in the IRS plasma wind tunnel PWK1 at the same nominal condition. State of the art diagnostic tools, i.e., surface temperature with pyrometry and thermography and boundary layer optical emission spectroscopy were completed by photogrammetric surface recession measurements. These data allow the assessment of the net heat flux for each material. The analysis shows that the three materials each have a different effect on heat flux mitigation with ASTERM showing the largest reduction in surface heat flux. The effect of pyrolysis and blowing is clearly observed and the heat flux reduction can be determined from an energy balance.

Enhanced Hydrogen Transport over Palladium Ultrathin Films through Surface Nanostructure Engineering.

PubMed

Abate, Salvatore; Giorgianni, Gianfranco; Gentiluomo, Serena; Centi, Gabriele; Perathoner, Siglinda

2015-11-01

Palladium ultrathin films (around 2 μm) with different surface nanostructures are characterized by TEM, SEM, AFM, and temperature programmed reduction (TPR), and evaluated in terms of H2 permeability and H2-N2 separation. A change in the characteristics of Pd seeds by controlled oxidation-reduction treatments produces films with the same thickness, but different surface and bulk nanostructure. In particular, the films have finer and more homogeneous Pd grains, which results in lower surface roughness. Although all samples show high permeo-selectivity to H2 , the samples with finer grains exhibit enhanced permeance and lower activation energy for H2 transport. The analysis of the data suggests that grain boundaries between the Pd grains at the surface favor H2 transfer from surface to subsurface. Thus, the surface nanostructure plays a relevant role in enhancing the transport of H2 over the Pd ultrathin film, which is an important aspect to develop improved membranes that function at low temperatures and toward new integrated process architectures in H2 and syngas production with enhanced sustainability. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bifunctional Nitrogen-Doped Microporous Carbon Microspheres Derived from Poly(o-methylaniline) for Oxygen Reduction and Supercapacitors.

PubMed

He, Yanzhen; Han, Xijiang; Du, Yunchen; Song, Bo; Xu, Ping; Zhang, Bin

2016-02-17

Heteroatom-doped carbon materials have attracted significant attention because of their applications in oxygen reduction reaction (ORR) and supercapacitors. Here we demonstrate a facile poly(o-methylaniline)-derived fabrication of bifunctional microporous nitrogen-doped carbon microspheres (NCMSs) with high electrocatalytic activity and stability for ORR and energy storage in supercapacitors. At a pyrolysis temperature of 900 °C, the highly dispersed NCMSs present a high surface area (727.1 m(2) g(-1)), proper total content of doping N, and high concentration of quaternary N, which exhibit superior electrocatalytic activities for ORR to the commercial Pt/C catalysts, high specific capacitance (414 F g(-1)), and excellent durability, making them very promising for advanced energy conversion and storage. The presented conducting polymer-derived strategy may provide a new way for the fabrication of heteroatom-doped carbon materials for energy device applications.

Modeling of the oxygen reduction reaction for dense LSM thin films

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

Yang, Tao; Liu, Jian; Yu, Yang

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Modeling of the oxygen reduction reaction for dense LSM thin films

DOE PAGES

Yang, Tao; Liu, Jian; Yu, Yang; ...

2017-10-17

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Lateral engineering of surface states - towards surface-state nanoelectronics.

PubMed

García de Abajo, F J; Cordón, J; Corso, M; Schiller, F; Ortega, J E

2010-05-01

Patterned metal surfaces can host electron quantum waves that display interference phenomena over distances of a few nanometres, thus providing excellent information carriers for future atomic-scale devices. Here we demonstrate that collimation and waveguiding of surface electrons can be realized in silver-induced strain dislocation networks on Cu(111) surfaces, as a conceptual proof-of-principle of surface-state nanoelectronics (SSNE). The Ag/Cu(111) system exhibits featured surface bands with gaps at the Fermi energy, which are basic requirements for a potential SSNE material. We establish a solid analogy between the behavior of surface-state electrons and surface plasmons in patterned metal surfaces, thus facilitating the transfer of existing knowledge on plasmonic structures to the new scenario presented by engineered electronic surface-state nanostructures, with the advantage of a 1000-fold reduction in wavelength and geometrical parameters.

A significant reduction of ice adhesion on nanostructured surfaces that consist of an array of single-walled carbon nanotubes: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Bao, Luyao; Huang, Zhaoyuan; Priezjev, Nikolai V.; Chen, Shaoqiang; Luo, Kai; Hu, Haibao

2018-04-01

It is well recognized that excessive ice accumulation at low-temperature conditions can cause significant damage to civil infrastructure. The passive anti-icing surfaces provide a promising solution to suppress ice nucleation and enhance ice removal. However, despite extensive efforts, it remains a challenge to design anti-icing surfaces with low ice adhesion. Using all-atom molecular dynamics (MD) simulations, we show that surfaces with single-walled carbon nanotube array (CNTA) significantly reduce ice adhesion due to the extremely low solid areal fraction. It was found that the CNTA surface exhibits up to a 45% decrease in the ice adhesion strength in comparison with the atomically smooth graphene surface. The details of the ice detachment from the CNTA surface were examined for different water-carbon interaction energies and temperatures of the ice cube. Remarkably, the results of MD simulations demonstrate that the ice detaching strength depends linearly on the ratio of the ice-surface interaction energy and the ice temperature. These results open the possibility for designing novel robust surfaces with low ice adhesion for passive anti-icing applications.

Nanocrystalline copper films are never flat.

PubMed

Zhang, Xiaopu; Han, Jian; Plombon, John J; Sutton, Adrian P; Srolovitz, David J; Boland, John J

2017-07-28

We used scanning tunneling microscopy to study low-angle grain boundaries at the surface of nearly planar copper nanocrystalline (111) films. The presence of grain boundaries and their emergence at the film surface create valleys composed of dissociated edge dislocations and ridges where partial dislocations have recombined. Geometric analysis and simulations indicated that valleys and ridges were created by an out-of-plane grain rotation driven by reduction of grain boundary energy. These results suggest that in general, it is impossible to form flat two-dimensional nanocrystalline films of copper and other metals exhibiting small stacking fault energies and/or large elastic anisotropy, which induce a large anisotropy in the dislocation-line energy. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Vegetation controls on the biophysical surface properties at global scale

NASA Astrophysics Data System (ADS)

Forzieri, Giovanni; Cescatti, Alessandro

2016-04-01

Leaf area index (LAI) plays an important role in determining resistances to heat, moisture and momentum exchanges between the land surface and atmosphere. Exploring how variations in LAI may induce changes in the surface energy balance is a key to understanding vegetation-climate interactions and for predicting biophysical climate impacts associated to changes in land cover. To this end, we analyzed remote sensing-observed dynamics in LAI, surface energy fluxes and climate drivers at global scale. We investigated the link between interannual variability of LAI and the components of the surface energy budget under diverse climate gradients. Results show that a 25% increase in annual LAI may induce up to 2% increase in available surface energy, as consequence of higher short wave absorption due to reduced albedos, up to 20% increase and 10% decrease in latent and sensible heat, respectively, leading to a decrease of the Bowen ratio in densely vegetated canopies. Opposite patterns are found for a reduction in LAI of similar magnitude. Such changes are strongly modulated by concurrent year-to-year variations and climatological means of air temperature, precipitation and snow cover as well as by land cover-specific physiological processes. Boreal and semi-arid regions appear to be mostly exposed to large changes in biophysical surface processes induced by interannual fluctuations in LAI. The combination of the emergent patters translates into variations in the long-wave outgoing radiation that reflect the surface warming/cooling associated to LAI changes. These findings provide a deeper understanding of the vegetation control on biophysical surface properties and define a set of observational-based diagnostics of LAI-dependent land surface-atmosphere interactions.

Self-spinning nanoparticle laden microdroplets for sensing and energy harvesting

NASA Astrophysics Data System (ADS)

Bhattacharjee, Mitradip; Pasumarthi, Viswanath; Chaudhuri, Joydip; Singh, Amit Kumar; Nemade, Harshal; Bandyopadhyay, Dipankar

2016-03-01

Exposure of a volatile organic vapour could set in powerful rotational motion a microdroplet composed of an aqueous salt solution loaded with metal nanoparticles. The solutal Marangoni motion on the surface originating from the sharp difference in the surface tension of water and organic vapour stimulated the strong vortices inside the droplet. The vapour sources of methanol, ethanol, diethyl ether, toluene, and chloroform stimulated motions of different magnitudes could easily be correlated to the surface tension gradient on the drop surface. Interestingly, when the nanoparticle laden droplet of aqueous salt solution was connected to an external electric circuit through a pair of electrodes, an ~85-95% reduction in the electrical resistance was observed across the spinning droplet. The extent of reduction in the resistance was found to have a correlation with the difference in the surface tension of the vapour source and the water droplet, which could be employed to distinguish the vapour sources. Remarkably, the power density of the same prototype was estimated to be around 7 μW cm-2, which indicated the potential of the phenomenon in converting surface energy into electrical in a non-destructive manner and under ambient conditions. Theoretical analysis uncovered that the difference in the ζ-potential near the electrodes was the major reason for the voltage generation. The prototype could also detect the repeated exposure and withdrawal of vapour sources, which helped in the development of a proof-of-concept detector to sense alcohol issuing out of the human breathing system.Exposure of a volatile organic vapour could set in powerful rotational motion a microdroplet composed of an aqueous salt solution loaded with metal nanoparticles. The solutal Marangoni motion on the surface originating from the sharp difference in the surface tension of water and organic vapour stimulated the strong vortices inside the droplet. The vapour sources of methanol, ethanol, diethyl ether, toluene, and chloroform stimulated motions of different magnitudes could easily be correlated to the surface tension gradient on the drop surface. Interestingly, when the nanoparticle laden droplet of aqueous salt solution was connected to an external electric circuit through a pair of electrodes, an ~85-95% reduction in the electrical resistance was observed across the spinning droplet. The extent of reduction in the resistance was found to have a correlation with the difference in the surface tension of the vapour source and the water droplet, which could be employed to distinguish the vapour sources. Remarkably, the power density of the same prototype was estimated to be around 7 μW cm-2, which indicated the potential of the phenomenon in converting surface energy into electrical in a non-destructive manner and under ambient conditions. Theoretical analysis uncovered that the difference in the ζ-potential near the electrodes was the major reason for the voltage generation. The prototype could also detect the repeated exposure and withdrawal of vapour sources, which helped in the development of a proof-of-concept detector to sense alcohol issuing out of the human breathing system. Electronic supplementary information (ESI) available: Discussion of simulation with results, characterization and movies of particle motion inside droplets along with detailed explanation. See DOI: 10.1039/c6nr00217j

Size Reduction Techniques for Large Scale Permanent Magnet Generators in Wind Turbines

NASA Astrophysics Data System (ADS)

Khazdozian, Helena; Hadimani, Ravi; Jiles, David

2015-03-01

Increased wind penetration is necessary to reduce U.S. dependence on fossil fuels, combat climate change and increase national energy security. The U.S Department of Energy has recommended large scale and offshore wind turbines to achieve 20% wind electricity generation by 2030. Currently, geared doubly-fed induction generators (DFIGs) are typically employed in the drivetrain for conversion of mechanical to electrical energy. Yet, gearboxes account for the greatest downtime of wind turbines, decreasing reliability and contributing to loss of profit. Direct drive permanent magnet generators (PMGs) offer a reliable alternative to DFIGs by eliminating the gearbox. However, PMGs scale up in size and weight much more rapidly than DFIGs as rated power is increased, presenting significant challenges for large scale wind turbine application. Thus, size reduction techniques are needed for viability of PMGs in large scale wind turbines. Two size reduction techniques are presented. It is demonstrated that 25% size reduction of a 10MW PMG is possible with a high remanence theoretical permanent magnet. Additionally, the use of a Halbach cylinder in an outer rotor PMG is investigated to focus magnetic flux over the rotor surface in order to increase torque. This work was supported by the National Science Foundation under Grant No. 1069283 and a Barbara and James Palmer Endowment at Iowa State University.

Tuning Product Selectivity for Aqueous CO2 Reduction with a Mn(bipyridine)-pyrene Catalyst Immobilized on a Carbon Nanotube Electrode

PubMed Central

2017-01-01

The development of high-performance electrocatalytic systems for the controlled reduction of CO2 to value-added chemicals is a key goal in emerging renewable energy technologies. The lack of selective and scalable catalysts in aqueous solution currently hampers the implementation of such a process. Here, the assembly of a [MnBr(2,2′-bipyridine)(CO)3] complex anchored to a carbon nanotube electrode via a pyrene unit is reported. Immobilization of the molecular catalyst allows electrocatalytic reduction of CO2 under fully aqueous conditions with a catalytic onset overpotential of η = 360 mV, and controlled potential electrolysis generated more than 1000 turnovers at η = 550 mV. The product selectivity can be tuned by alteration of the catalyst loading on the nanotube surface. CO was observed as the main product at high catalyst loadings, whereas formate was the dominant CO2 reduction product at low catalyst loadings. Using UV–vis and surface-sensitive IR spectroelectrochemical techniques, two different intermediates were identified as responsible for the change in selectivity of the heterogenized Mn catalyst. The formation of a dimeric Mn0 species at higher surface loading was shown to preferentially lead to CO formation, whereas at lower surface loading the electrochemical generation of a monomeric Mn-hydride is suggested to greatly enhance the production of formate. These results emphasize the advantages of integrating molecular catalysts onto electrode surfaces for enhancing catalytic activity while allowing excellent control and a deeper understanding of the catalytic mechanisms. PMID:28885841

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

China's air pollution reduction efforts may result in an increase in surface ozone levels in highly polluted areas.

PubMed

Anger, Annela; Dessens, Olivier; Xi, Fengming; Barker, Terry; Wu, Rui

2016-03-01

China, as a fast growing fossil-fuel-based economy, experiences increasing levels of air pollution. To tackle air pollution, China has taken the first steps by setting emission-reduction targets for nitrogen oxides (NO x ) and sulphur dioxide (SO2) in the 11th and 12th Five Year Plans. This paper uses two models-the Energy-Environment-Economy Model at the Global level (E3MG) and the global Chemistry Transport Model pTOMCAT-to test the effects of these policies. If the policy targets are met, then the maximum values of 32 % and 45 % reductions below 'business as usual' in the monthly mean NO x and SO2 concentrations, respectively, will be achieved in 2015. However, a decrease in NO x concentrations in some highly polluted areas of East, North-East and South-East China can lead to up to a 10% increase in the monthly mean concentrations in surface ozone in 2015. Our study demonstrates an urgent need for the more detailed analysis of the impacts and designs of air pollution reduction guidelines for China.

Oxidation of aromatic contaminants coupled to microbial iron reduction

USGS Publications Warehouse

Lovley, D.R.; Baedecker, M.J.; Lonergan, D.J.; Cozzarelli, I.M.; Phillips, E.J.P.; Siegel, D.I.

1989-01-01

THE contamination of sub-surface water supplies with aromatic compounds is a significant environmental concern1,2. As these contaminated sub-surface environments are generally anaerobic, the microbial oxidation of aromatic compounds coupled to nitrate reduction, sulphate reduction and methane production has been studied intensively1-7. In addition, geochemical evidence suggests that Fe(III) can be an important electron acceptor for the oxidation of aromatic compounds in anaerobic groundwater. Until now, only abiological mechanisms for the oxidation of aromatic compounds with Fe(III) have been reported8-12. Here we show that in aquatic sediments, microbial activity is necessary for the oxidation of model aromatic compounds coupled to Fe(III) reduction. Furthermore, a pure culture of the Fe(III)-reducing bacterium GS-15 can obtain energy for growth by oxidizing benzoate, toluene, phenol or p-cresol with Fe(III) as the sole electron acceptor. These results extend the known physiological capabilities of Fe(III)-reducing organisms and provide the first example of an organism of any type which can oxidize an aromatic hydrocarbon anaerobically. ?? 1989 Nature Publishing Group.

Improving wind energy forecasts using an Ensemble Kalman Filter data assimilation technique in a fully coupled hydrologic and atmospheric model

NASA Astrophysics Data System (ADS)

Williams, J. L.; Maxwell, R. M.; Delle Monache, L.

2012-12-01

Wind power is rapidly gaining prominence as a major source of renewable energy. Harnessing this promising energy source is challenging because of the chaotic nature of wind and its propensity to change speed and direction over short time scales. Accurate forecasting tools are critical to support the integration of wind energy into power grids and to maximize its impact on renewable energy portfolios. Numerous studies have shown that soil moisture distribution and land surface vegetative processes profoundly influence atmospheric boundary layer development and weather processes on local and regional scales. Using the PF.WRF model, a fully-coupled hydrologic and atmospheric model employing the ParFlow hydrologic model with the Weather Research and Forecasting model coupled via mass and energy fluxes across the land surface, we have explored the connections between the land surface and the atmosphere in terms of land surface energy flux partitioning and coupled variable fields including hydraulic conductivity, soil moisture and wind speed, and demonstrated that reductions in uncertainty in these coupled fields propagate through the hydrologic and atmospheric system. We have adapted the Data Assimilation Research Testbed (DART), an implementation of the robust Ensemble Kalman Filter data assimilation algorithm, to expand our capability to nudge forecasts produced with the PF.WRF model using observational data. Using a semi-idealized simulation domain, we examine the effects of assimilating observations of variables such as wind speed and temperature collected in the atmosphere, and land surface and subsurface observations such as soil moisture on the quality of forecast outputs. The sensitivities we find in this study will enable further studies to optimize observation collection to maximize the utility of the PF.WRF-DART forecasting system.

Quadratic String Method for Locating Instantons in Tunneling Splitting Calculations.

PubMed

Cvitaš, Marko T

2018-03-13

The ring-polymer instanton (RPI) method is an efficient technique for calculating approximate tunneling splittings in high-dimensional molecular systems. In the RPI method, tunneling splitting is evaluated from the properties of the minimum action path (MAP) connecting the symmetric wells, whereby the extensive sampling of the full potential energy surface of the exact quantum-dynamics methods is avoided. Nevertheless, the search for the MAP is usually the most time-consuming step in the standard numerical procedures. Recently, nudged elastic band (NEB) and string methods, originaly developed for locating minimum energy paths (MEPs), were adapted for the purpose of MAP finding with great efficiency gains [ J. Chem. Theory Comput. 2016 , 12 , 787 ]. In this work, we develop a new quadratic string method for locating instantons. The Euclidean action is minimized by propagating the initial guess (a path connecting two wells) over the quadratic potential energy surface approximated by means of updated Hessians. This allows the algorithm to take many minimization steps between the potential/gradient calls with further reductions in the computational effort, exploiting the smoothness of potential energy surface. The approach is general, as it uses Cartesian coordinates, and widely applicable, with computational effort of finding the instanton usually lower than that of determining the MEP. It can be combined with expensive potential energy surfaces or on-the-fly electronic-structure methods to explore a wide variety of molecular systems.

KF post-deposition treatment of industrial Cu(In, Ga)(S, Se) 2 thin-film surfaces: Modifying the chemical and electronic structure

DOE PAGES

Mezher, Michelle; Mansfield, Lorelle M.; Horsley, Kimberly; ...

2017-08-14

The chemical and electronic structures of industrial chalcopyrite photovoltaic absorbers after KF post-deposition treatment (KF-PDT) are investigated using electron spectroscopies to probe the occupied and unoccupied electronic states. In contrast to a variety of recent publications on the impact of KF-PDT, this study focuses on industrial Cu(In,Ga)(S,Se) 2 absorbers that also contain sulfur at the surface. We find that the KF-PDT removes surface adsorbates and oxides and also observe a change in the S/Se ratio. Furthermore, the KF-PDT leads to a Cu reduction at the surface but to a much lower degree than the strongly Cu-depleted or even Cu-free surfacesmore » reported for (non-industrial) sulfur-free Cu(In,Ga)Se 2 absorbers. Furthermore, the valence band maximum at the surface is found at a lower energy compared to the untreated absorber, and the conduction band minimum is found at a higher energy, overall revealing a widening of the bandgap in the surface region.« less

KF post-deposition treatment of industrial Cu(In, Ga)(S, Se) 2 thin-film surfaces: Modifying the chemical and electronic structure

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

Mezher, Michelle; Mansfield, Lorelle M.; Horsley, Kimberly

The chemical and electronic structures of industrial chalcopyrite photovoltaic absorbers after KF post-deposition treatment (KF-PDT) are investigated using electron spectroscopies to probe the occupied and unoccupied electronic states. In contrast to a variety of recent publications on the impact of KF-PDT, this study focuses on industrial Cu(In,Ga)(S,Se) 2 absorbers that also contain sulfur at the surface. We find that the KF-PDT removes surface adsorbates and oxides and also observe a change in the S/Se ratio. Furthermore, the KF-PDT leads to a Cu reduction at the surface but to a much lower degree than the strongly Cu-depleted or even Cu-free surfacesmore » reported for (non-industrial) sulfur-free Cu(In,Ga)Se 2 absorbers. Furthermore, the valence band maximum at the surface is found at a lower energy compared to the untreated absorber, and the conduction band minimum is found at a higher energy, overall revealing a widening of the bandgap in the surface region.« less

Real-time first-principles simulations of thermionic emission from N-doped diamond surfaces

NASA Astrophysics Data System (ADS)

Shinozaki, Tomoki; Hagiwara, Satoshi; Morioka, Naoya; Kimura, Yuji; Watanabe, Kazuyuki

2018-06-01

We investigate thermionic emission from N-doped C(100) surfaces terminated with H or Li atoms using finite-temperature real-time density functional theory simulations. The current–temperature characteristics are found to follow the Richardson–Dushman (RD) equation, which was derived from a semiclassical theory. However, the Richardson constants are two orders of magnitude smaller than the ideal values from the RD theory. This considerable reduction is attributed primarily to the extremely low transmission probability of electrons from the surfaces toward the vacuum. The present method enables straightforward evaluation of the ideal efficiency of a thermionic energy converter.

A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles

PubMed Central

2016-01-01

Copper catalyzes the electrochemical reduction of CO to valuable C2+ products including ethanol, acetate, propanol, and ethylene. These reactions could be very useful for converting renewable energy into fuels and chemicals, but conventional Cu electrodes are energetically inefficient and have poor selectivity for CO vs H2O reduction. Efforts to design improved catalysts have been impeded by the lack of experimentally validated, quantitative structure–activity relationships. Here we show that CO reduction activity is directly correlated to the density of grain boundaries (GBs) in Cu nanoparticles (NPs). We prepared electrodes of Cu NPs on carbon nanotubes (Cu/CNT) with different average GB densities quantified by transmission electron microscopy. At potentials ranging from −0.3 V to −0.5 V vs the reversible hydrogen electrode, the specific activity for CO reduction to ethanol and acetate was linearly proportional to the fraction of NP surfaces comprised of GB surface terminations. Our results provide a design principle for CO reduction to ethanol and acetate on Cu. GB-rich Cu/CNT electrodes are the first NP catalysts with significant CO reduction activity at moderate overpotential, reaching a mass activity of up to ∼1.5 A per gram of Cu and a Faradaic efficiency >70% at −0.3 V. PMID:27163043

A Direct Grain-Boundary-Activity Correlation for CO Electroreduction on Cu Nanoparticles.

PubMed

Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan; Kanan, Matthew W

2016-03-23

Copper catalyzes the electrochemical reduction of CO to valuable C2+ products including ethanol, acetate, propanol, and ethylene. These reactions could be very useful for converting renewable energy into fuels and chemicals, but conventional Cu electrodes are energetically inefficient and have poor selectivity for CO vs H2O reduction. Efforts to design improved catalysts have been impeded by the lack of experimentally validated, quantitative structure-activity relationships. Here we show that CO reduction activity is directly correlated to the density of grain boundaries (GBs) in Cu nanoparticles (NPs). We prepared electrodes of Cu NPs on carbon nanotubes (Cu/CNT) with different average GB densities quantified by transmission electron microscopy. At potentials ranging from -0.3 V to -0.5 V vs the reversible hydrogen electrode, the specific activity for CO reduction to ethanol and acetate was linearly proportional to the fraction of NP surfaces comprised of GB surface terminations. Our results provide a design principle for CO reduction to ethanol and acetate on Cu. GB-rich Cu/CNT electrodes are the first NP catalysts with significant CO reduction activity at moderate overpotential, reaching a mass activity of up to ∼1.5 A per gram of Cu and a Faradaic efficiency >70% at -0.3 V.

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.

Graphene-Based Photocatalysts for CO2 Reduction to Solar Fuel.

PubMed

Low, Jingxiang; Yu, Jiaguo; Ho, Wingkei

2015-11-05

Recently, photocatalytic CO2 reduction for solar fuel production has attracted much attention because of its potential for simultaneously solving energy and global warming problems. Many studies have been conducted to prepare novel and efficient photocatalysts for CO2 reduction. Graphene, a two-dimensional material, has been increasingly used in photocatalytic CO2 reduction. In theory, graphene shows several remarkable properties, including excellent electronic conductivity, good optical transmittance, large specific surface area, and superior chemical stability. Attributing to these advantages, fabrication of graphene-based materials has been known as one of the most feasible strategies to improve the CO2 reduction performance of photocatalysts. This Perspective mainly focuses on the recent important advances in the fabrication and application of graphene-based photocatalysts for CO2 reduction to solar fuels. The existing challenges and difficulties of graphene-based photocatalysts are also discussed for future application.

Electrodeposition of nano-sized bismuth on copper foil as electrocatalyst for reduction of CO2 to formate

NASA Astrophysics Data System (ADS)

Lv, Weixin; Zhou, Jing; Bei, Jingjing; Zhang, Rui; Wang, Lei; Xu, Qi; Wang, Wei

2017-01-01

Electrochemical reduction of carbon dioxide (CO2) to formate is energetically inefficient because high overpotential is required for reduction of CO2 to formate on most traditional catalysts. In this paper, a novel nano-sized Bi-based electrocatalyst deposited on a Cu foil has been synthesized, which can be used as a cathode for electrochemical reduction of CO2 to formate with a low overpotential (0.69 V) and a high selectivity (91.3%). The electrocatalyst can show excellent catalytic performance toward reduction of CO2 which can probably be attributed to the nano-sized structure and the surface oxide layer. The energy efficiency for reduction of CO2 to formate can reach to 50% when an IrxSnyRuzO2/Ti electrode is used as anode, it is one of the highest values found in the literatures and very practicable for sustainable fuel synthesis.

Quantum chemical investigation on the role of Li adsorbed on anatase (101) surface nano-materials on the storage of molecular hydrogen.

PubMed

Srinivasadesikan, V; Raghunath, P; Lin, M C

2015-06-01

Lithiation of TiO2 has been shown to enhance the storage of hydrogen up to 5.6 wt% (Hu et al. J Am Chem Soc 128:11740-11741, 2006). The mechanism for the process is still unknown. In this work we have carried out a study on the adsorption and diffusion of Li atoms on the surface and migration into subsurface layers of anatase (101) by periodic density functional theory calculations implementing on-site Coulomb interactions (DFT+U). The model consists of 24 [TiO2] units with 11.097 × 7.655 Å(2) surface area. Adsorption energies have been calculated for different Li atoms (1-14) on the surface. A maximum of 13 Li atoms can be accommodated on the surface at two bridged O, Ti-O, and Ti atom adsorption sites, with 83 kcal mol(-1) adsorption energy for a single Li atom adsorbed between two bridged O atoms from where it can migrate into the subsurface layer with 27 kcal mol(-1) energy barrier. The predicted adsorption energies for H2 on the lithiated TiO2 (101) surface with 1-10 Li atoms revealed that the highest adsorption energies occurred on 1-Li, 5-Li, and 9-Li surfaces with 3.5, 4.4, and 7.6 kcal mol(-1), respectively. The values decrease rapidly with additional H2 co-adsorbed on the lithiated surfaces; the maximum H2 adsorption on the 9Li-TiO2(a) surface was estimated to be only 0.32 wt% under 100 atm H2 pressure at 77 K. The result of Bader charge analysis indicated that the reduction of Ti occurred depending on the Li atoms covered on the TiO2 surface.

InN/GaN quantum dot superlattices: Charge-carrier states and surface electronic structure

NASA Astrophysics Data System (ADS)

Kanouni, F.; Brezini, A.; Djenane, M.; Zou, Q.

2018-03-01

We have theoretically investigated the electron energy spectra and surface states energy in the three dimensionally ordered quantum dot superlattices (QDSLs) made of InN and GaN semiconductors. The QDSL is assumed in this model to be a matrix of GaN containing cubic dots of InN of the same size and uniformly distributed. For the miniband’s structure calculation, the resolution of the effective mass Schrödinger equation is done by decoupling it in the three directions within the framework of Kronig-Penney model. We found that the electrons minibands in infinite ODSLs are clearly different from those in the conventional quantum-well superlattices. The electrons localization and charge-carrier states are very dependent on the quasicrystallographic directions, the size and the shape of the dots which play a role of the artificial atoms in such QD supracrystal. The energy spectrum of the electron states localized at the surface of InN/GaN QDSL is represented by Kronig-Penney like-model, calculated via direct matching procedure. The calculation results show that the substrate breaks symmetrical shape of QDSL on which some localized electronic surface states can be produced in minigap regions. Furthermore, we have noticed that the surface states degeneracy is achieved in like very thin bands located in the minigaps, identified by different quantum numbers nx, ny, nz. Moreover, the surface energy bands split due to the reduction of the symmetry of the QDSL in z-direction.

Rapid sampling of local minima in protein energy surface and effective reduction through a multi-objective filter

PubMed Central

2013-01-01

Background Many problems in protein modeling require obtaining a discrete representation of the protein conformational space as an ensemble of conformations. In ab-initio structure prediction, in particular, where the goal is to predict the native structure of a protein chain given its amino-acid sequence, the ensemble needs to satisfy energetic constraints. Given the thermodynamic hypothesis, an effective ensemble contains low-energy conformations which are similar to the native structure. The high-dimensionality of the conformational space and the ruggedness of the underlying energy surface currently make it very difficult to obtain such an ensemble. Recent studies have proposed that Basin Hopping is a promising probabilistic search framework to obtain a discrete representation of the protein energy surface in terms of local minima. Basin Hopping performs a series of structural perturbations followed by energy minimizations with the goal of hopping between nearby energy minima. This approach has been shown to be effective in obtaining conformations near the native structure for small systems. Recent work by us has extended this framework to larger systems through employment of the molecular fragment replacement technique, resulting in rapid sampling of large ensembles. Methods This paper investigates the algorithmic components in Basin Hopping to both understand and control their effect on the sampling of near-native minima. Realizing that such an ensemble is reduced before further refinement in full ab-initio protocols, we take an additional step and analyze the quality of the ensemble retained by ensemble reduction techniques. We propose a novel multi-objective technique based on the Pareto front to filter the ensemble of sampled local minima. Results and conclusions We show that controlling the magnitude of the perturbation allows directly controlling the distance between consecutively-sampled local minima and, in turn, steering the exploration towards conformations near the native structure. For the minimization step, we show that the addition of Metropolis Monte Carlo-based minimization is no more effective than a simple greedy search. Finally, we show that the size of the ensemble of sampled local minima can be effectively and efficiently reduced by a multi-objective filter to obtain a simpler representation of the probed energy surface. PMID:24564970

Laser processing of metallic biomaterials: An approach for surface patterning and wettability control

NASA Astrophysics Data System (ADS)

Razi, Sepehr; Mollabashi, Mahmoud; Madanipour, Khosro

2015-12-01

Q -switched Nd:YAG laser is used to manipulate the surface morphology and wettability characteristic of 316L stainless steel (SS) and titanium biomaterials. Water and glycerol are selected as wettability testing liquids and the sessile drop method is used for the contact angle measurements. Results indicate that on both of the metals, wettability toward water improves significantly after the laser treatment. Different analyses including the study of the surface morphology, free energy and oxidation are assessed in correlation with wettability. Beside the important role of the laser-induced surface patterns, the increase in the surface roughness, oxygen content and the polar component of the surface energy, are detected as the most important physical and chemical phenomena controlling the improvement in the wettability. However, all the processed hydrophilic surfaces that are exposed to air become hydrophobic over time. The time dependency of the surface wettability is related to the chemical activities on the treated surfaces and the reduction of oxygen/carbon (O/C) ratio on them. The behavior is further studied with investigating the effect of the keeping environment and changes of the components of the surface tension. Results show that the pulsed laser treatment is a versatile approach to create either hydrophobic or super hydrophilic surfaces for industrial and medical applications.

Activity of N-coordinated multi-metal-atom active site structures for Pt-free oxygen reduction reaction catalysis: Role of *OH ligands

DOE PAGES

Holby, Edward F.; Taylor, Christopher D.

2015-03-19

We report calculated oxygen reduction reaction energy pathways on multi-metal-atom structures that have previously been shown to be thermodynamically favorable. We predict that such sites have the ability to spontaneously cleave the O₂ bond and then will proceed to over-bind reaction intermediates. In particular, the *OH bound state has lower energy than the final 2 H₂O state at positive potentials. Contrary to traditional surface catalysts, this *OH binding does not poison the multi-metal-atom site but acts as a modifying ligand that will spontaneously form in aqueous environments leading to new active sites that have higher catalytic activities. These *OH boundmore » structures have the highest calculated activity to date.« less

Self-organization, preferential flow and rainfall runoff behavior - is there a connection?

NASA Astrophysics Data System (ADS)

Zehe, Erwin; Blume, Theresa; Kleidon, Axel; Ehret, Uwe; Scherer, Ulrike; Westhoff, Martijn

2013-04-01

In line with the studies of Kleidon et al. (2012) and Zehe et al. (2010) the proposed study analyzes mass flow related flows of free energy in open hydrological systems - hillslopes and small catchments - using thermodynamics methods. Why a thermodynamic treatment? A small part of the kinetic energy input from incoming rainfall is dissipated into heat and to break up soil aggregates. Depending on the partitioning of the incoming rainfall into overland flow and soil water, the remaining part of the incoming kinetic energy is partly transformed into potential energy of surface water and subsequently partly exported as kinetic energy of overland flow from the system; the rest is dissipated by frictional losses. The other part of rainfall infiltrates thereby increasing potential energy of soil water but depleting at the same time (gradients in) capillary binding energy of soil water, which again comprises energy dissipation into heat of immersion. Although, these mass fluxes are not associated with large heat fluxes, they reflect the overall conservation of energy as well as the second law of thermodynamics. They require thus a thermodynamic treatment, because tiny amounts of kinetic energy, surface energy and potential energy are dissipated into heat: this implies irreversibility and explains why water does not flow uphill. Soil hydraulic equilibrium (HE), arising from a balance in potential and capillary binding energy in soil, can be interpreted as a state of maximum entropy in soil. Soil water potential, defined as sum of matric potential and gravity potential, is in HE equal to zero along the soil profile. This corresponds to a state of maximum entropy due to a zero potential gradient, which implies due to Zehe et al. (2010) a state of minimum (Helmholtz) free energy. Our first main objective is to quantify to which extent connected preferential flow path, in our case vertical macropores and the river network enhance flow velocities at a given driving gradient and thus power in the associated mass fluxes. This implies either an enhanced export of free energy in form of kinetic energy in case of the river net, or an accelerated reduction of potential energy of infiltrating surface water which implies a reduction free energy in form of capillary binding energy of soil water. We hypothesize (H1) that network like structures act as dissipative structures "serving the purpose" of reducing the relaxation time to a state of lower "free" energy in the entire system. This is because they minimize dissipative losses of kinetic energy along their extent. This faster relaxation towards a state of smaller free energy is deemed to be favorable for mechanic stability of the entire hydrological system because a) mass flows perform due to the enhanced export of kinetic energy less work on the system itself and b) mechanical stress from ponded surface water is quickly reduced by fast infiltration and preferential flow. Our second main objective is, in line with the study of Zehe et al. (2010), the search for thermodynamic optimal hillslope architectures both with respect to the surface density of vertical macropores in soil and with respect to the spatial arrangement of soil types and macropores at the hillslope scale. In line with H1 we suggest (H2) that a hydro-geo-ecosystem is closer to a functional optimum than other possible configurations if it dissipates and exports more of the kinetic energy input from incoming rainfall by redistributing water against internal gradients and exporting water against macroscale geo-potential gradients. Note that H2 does not postulate that functionally optimal hillslope architectures necessarily exist, if they exist H2 implies however that they maximize entropy production and thus reduction of total free energy of the system at a "wisely" selected time scale. The surface density of apparent macropores does for instance control the tradeoff between Hortonian overland flow formation and infiltration, which implies a tradeoff between the amount of kinetic energy input from rainfall that is converted in to power associated with overland flow and power associated with soil water flows depleting gradients in soil water potential. Does this tradeoff imply an optimum surface density of macropores at the hillslope scale in the sense that power in soil water flow is maximized or reduction of free energy is maximized? In case such an optimum hillslope architecture existed, and in case that the evolution of the hydrological systems of interested was indeed in accordance with hypothesis H2, this optimal architecture should allow an acceptable uncalibrated simulation of the systems rainfall -runoff behavior (if the selected model structure can properly represent this architecture). We will address these questions and test the main implications of our hypotheses by means of numerical experiments with the physically based hydrological model CATFLOW. We use behavioral model structures as basic model setup, which have been shown to closely portray system behavior and its architecture in a sense that they reproduce distributed observations of soil moisture and catchment scale discharge and represent the observed structural and textural signatures of soils, flow networks and vegetation. Our test areas are the Weiherbach (Germany) and the Malalcahuello research headwaters (Chile), which are located in distinctly different hydro-climatic and hydro-pedological settings. Within the numerical experiments we will simulate the full concert of hydrological processes at the hillslope and headwater scales for meaningful perturbations of the behavioral model structure and compare them with respect to dynamics of free energy and production of power. These perturbations affect a) the river network and the geomorphology of the Weiherbach catchment, b) surface density of macropores in both catchments c) the spatial arrangement of soils and preferential pathways at the hillslope scale in the Weiherbach catchment. References: Kleidon, A., Zehe, E., Ehret, U., and Scherer, U.: Thermodynamics, maximum power, and the dynamics of preferential river flow structures on continents, Hydrol. Earth Syst. Sci. Discuss., 9, 7317-7378, 10.5194/hessd-9-7317-2012, 2012. Zehe, E., Blume, T., and Blöschl, G.: The principle of 'maximum energy dissipation': a novel thermodynamic perspective on rapid water flow in connected soil structures, Phil. Trans. R. Soc. B, 1-10, doi:10.1098/rstb.2009.0308, 2010.

Dosimetric effects of polyethylene glycol surface coatings on gold nanoparticle radiosensitization

NASA Astrophysics Data System (ADS)

Koger, B.; Kirkby, C.

2017-11-01

One of the main appeals of using gold nanoparticles (GNPs) as radiosensitizers is that their surface coatings can be altered to manipulate their pharmacokinetic properties. However, Monte Carlo studies of GNP dosimetry tend to neglect these coatings, potentially changing the dosimetric results. This study quantifies the dosimetric effects of including a polyethylene glycol (PEG) surface coating on GNPs over both nanoscopic and microscopic ranges. Two dosimetric scales were explored using PENELOPE Monte Carlo simulations. In microscopic simulations, 500-1000 GNPs, with and without coatings, were placed in cavities of side lengths 0.8-4 µm, and the reduction of dose deposited to surrounding medium within these volumes due to the coating was quantified. Including PEG surface coatings of up to 20 nm thickness resulted in reductions of up to 7.5%, 4.0%, and 2.0% for GNP diameters of 10, 20, and 50 nm, respectively. Nanoscopic simulations observed the dose falloff in the first 500 nm surrounding a single GNP both with and without surface coatings of various thicknesses. Over the first 500 nm surrounding a single GNP, the presence of a PEG surface coating reduced dose by 5-26%, 8-28%, 8-30%, and 8-34% for 2, 10, 20, and 50 nm diameter GNPs, respectively, for various energies and coating thicknesses. Reductions in dose enhancement due to the inclusion of a GNP surface coating are non-negligible and should be taken into consideration when investigating GNP dose enhancement. Further studies should be carried out to investigate the biological effects of these coatings.

Enhanced photocatalytic CO₂-reduction activity of electrospun mesoporous TiO₂ nanofibers by solvothermal treatment.

PubMed

Fu, Junwei; Cao, Shaowen; Yu, Jiaguo; Low, Jingxiang; Lei, Yongpeng

2014-06-28

Photocatalytic reduction of CO2 into renewable hydrocarbon fuels using semiconductor photocatalysts is considered as a potential solution to the energy deficiency and greenhouse effect. In this work, mesoporous TiO2 nanofibers with high specific surface areas and abundant surface hydroxyl groups are prepared using an electrospinning strategy combined with a subsequent calcination process, followed by a solvothermal treatment. The solvothermally treated mesoporous TiO2 nanofibers exhibit excellent photocatalytic performance on CO2 reduction into hydrocarbon fuels. The significantly improved photocatalytic activity can be attributed to the enhanced CO2 adsorption capacity and the improved charge separation after solvothermal treatment. The highest activity is achieved for the sample with a 2-h solvothermal treatment, showing 6- and 25-fold higher CH4 production rate than those of TiO2 nanofibers without solvothermal treatment and P25, respectively. This work may also provide a prototype for studying the effect of solvothermal treatment on the structure and photocatalytic activity of semiconductor photocatalysts.

Active and stable Ir@Pt core–shell catalysts for electrochemical oxygen reduction

DOE PAGES

Strickler, Alaina L.; Jackson, Ariel; Jaramillo, Thomas F.

2016-12-28

Electrochemical oxygen reduction is an important reaction for many sustainable energy technologies, such as fuel cells and metal–air batteries. Kinetic limitations of this reaction, expensive electrocatalysts, and catalyst instability, however, limit the commercial viability of such devices. Herein, we report an active Ir@Pt core–shell catalyst that combines platinum overlayers with nanostructure effects to tune the oxygen binding to the Pt surface, thereby achieving enhanced activity and stability for the oxygen reduction reaction. Ir@Pt nanoparticles with several shell thicknesses were synthesized in a scalable, inexpensive, one-pot polyol method. Electrochemical analysis demonstrates the activity and stability of the Ir@Pt catalyst, with specificmore » and mass activities increasing to 2.6 and 1.8 times that of commercial Pt/C (TKK), respectively, after 10 000 stability cycles. Furthermore, activity enhancement of the Ir@Pt catalyst is attributed to weakening of the oxygen binding to the Pt surface induced by the Ir core.« less

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

Yadav, Praveen Kumar, E-mail: praveenyadav@rrcat.gov.in; Nayak, Maheswar; Rai, Sanjay Kumar

The authors report the effect of argon ion to molybdenum atom ratio (r) on the microstructure of low energy (70 eV) argon ion assisted electron beam evaporated Mo thin films. Surface roughness, morphology, and crystallinity of Mo films are found to strongly depend on “r.” Increase of “r” from 0 to 100 induces gradual loss in crystallinity, reduction in surface roughness and systematic increase in density of the film. For “r” ∼ 100, average atomic density of the film approaches the bulk value (97%) with lowest surface roughness. Further, increasing “r” up to 170 reduces the atomic density, increases roughness, and increase inmore » crystallinity induced by low energy Ar ion beam. The observed surface roughness and grain size determined by x-ray reflectivity and glancing incidence x-ray diffraction correlate well with atomic force microscopy measurements. This study demonstrates that for r = 100 one gets lowest roughness Mo film with highest density and nearly amorphous microstructure. The growth model is discussed by structural zone model.« less

Nature of the Active Sites for CO Reduction on Copper Nanoparticles; Suggestions for Optimizing Performance.

PubMed

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

2017-08-30

Recent experiments show that the grain boundaries (GBs) of copper nanoparticles (NPs) lead to an outstanding performance in reducing CO 2 and CO to alcohol products. We report here multiscale simulations that simulate experimental synthesis conditions to predict the structure of a 10 nm Cu NP (158 555 atoms). To identify active sites, we first predict the CO binding at a large number of sites and select four exhibiting CO binding stronger than the (211) step surface. Then, we predict the formation energy of the *OCCOH intermediate as a descriptor for C-C coupling, identifying two active sites, both of which have an under-coordinated surface square site adjacent to a subsurface stacking fault. We then propose a periodic Cu surface (4 by 4 supercell) with a similar site that substantially decreases the formation energy of *OCCOH, by 0.14 eV.

Surfactant effects on alpha-factors in aeration systems.

PubMed

Rosso, Diego; Stenstrom, Michael K

2006-04-01

Aeration in wastewater treatment processes accounts for the largest fraction of plant energy costs. Aeration systems function by shearing the surface (surface aerators) or releasing bubbles at the bottom of the tank (coarse- or fine-bubble aerators). Surfactant accumulation on gas-liquid interfaces reduces mass transfer rates, and this reduction in general is larger for fine-bubble aerators. This study evaluates mass transfer effects on the characterization and specification of aeration systems in clean and process water conditions. Tests at different interfacial turbulence regimes show higher gas transfer depression for lower turbulence regimes. Contamination effects can be offset at the expense of operating efficiency, which is characteristic of surface aerators and coarse-bubble diffusers. Results describe the variability of alpha-factors measured at small scale, due to uncontrolled energy density. Results are also reported in dimensionless empirical correlations describing mass transfer as a function of physiochemical and geometrical characteristics of the aeration process.

a Photoemission Study of the Electronic Structure Induced by Potassium Adsorption on TiO2(110)

NASA Astrophysics Data System (ADS)

Heise, Rainer; Courths, Ralf

Electronic structure effects induced by potassium adsorption up to one monolayer (ML) on a nearly stoichiometric TiO2(110) surface has been studied by means of angle-resolved photoemission spectroscopy (ARUPS and ARXPS) from valence states and core levels. In agreement with the observations on K/TiO2(100) [P.J. Hardman et al., Surf. Sci. 269/270, 677 (1992)], potassium adsorption at room temperature leads—due to K-to-substrate charge transfer—to the reduction of surface Ti ions (to nominally Ti3+ ions), evidenced by lowered Ti 2p core-level binding energy (ΔBE=-1.6 eV) and occupation of Ti 3d-like band-gap states centered at 0.9 eV BE. The gap-state intensity exhibits a pronounced maximum at 0.37 ML coverage, where the work function has a weak minimum. This behavior is in agreement with a ionic-to-neutral transition of the K-substrate bonding with increasing K coverage, as suggested recently [Souda et al., Surf. Sci. 285, 265 (1993)]. Annealing of a surface precovered with 0.27 ML potassium up to 1000 K results in metallization of the surface, evidenced by (i) the occupation of a second gap-state centered at 0.4 BE and with a considerable state-density at the Fermi energy, and (ii) Ti 2p core-levels lowered by 3.2 eV in BE (nominally “Ti2+” ions). This dramatic reduction of the surface is healed out with complete desorption of potassium. A discussion in terms of desorption of KOx species and oxygen diffusion from the bulk to the surface is given.

Decreasing the Hydroxylation Affinity of La 1–x Sr x MnO 3 Perovskites To Promote Oxygen Reduction Electrocatalysis

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

Stoerzinger, Kelsey A.; Hong, Wesley T.; Wang, Xiao Renshaw

Understanding the interaction between oxides and water is critical to design many of their functionalities, including the electrocatalysis of molecular oxygen reduction. In this study, we probed the hydroxylation of model (001)-oriented La(1-x)SrxMnO3 (LSMO) perovskite surfaces, where the electronic structure and manganese valence was controlled by five substitution levels of lanthanum with strontium, using ambient pressure X-ray photoelectron spectroscopy in a humid environment. The degree of hydroxyl formation on the oxide surface correlated with the proximity of the valence band center relative to the Fermi level. LSMO perovskites with a valence band center closer to the Fermi level were moremore » reactive toward water, forming more hydroxyl species at a given relative humidity. More hydroxyl species correlate with greater electron-donating character to the surface free energy in wetting, and reduce the activity to catalyze oxygen reduction reaction (ORR) kinetics in basic solution. New strategies to design more active catalysts should include design of electronically conducting oxides with lower valence band centers relative to the Fermi level at ORR-relevant potentials.« less

Singular reduction of resonant Hamiltonians

NASA Astrophysics Data System (ADS)

Meyer, Kenneth R.; Palacián, Jesús F.; Yanguas, Patricia

2018-06-01

We investigate the dynamics of resonant Hamiltonians with n degrees of freedom to which we attach a small perturbation. Our study is based on the geometric interpretation of singular reduction theory. The flow of the Hamiltonian vector field is reconstructed from the cross sections corresponding to an approximation of this vector field in an energy surface. This approximate system is also built using normal forms and applying reduction theory obtaining the reduced Hamiltonian that is defined on the orbit space. Generically, the reduction is of singular character and we classify the singularities in the orbit space, getting three different types of singular points. A critical point of the reduced Hamiltonian corresponds to a family of periodic solutions in the full system whose characteristic multipliers are approximated accordingly to the nature of the critical point.

Riblets for aircraft skin-friction reduction

NASA Technical Reports Server (NTRS)

Walsh, Michael J.

1986-01-01

Energy conservation and aerodynamic efficiency are the driving forces behind research into methods to reduce turbulent skin friction drag on aircraft fuselages. Fuselage skin friction reductions as small as 10 percent provide the potential for a 250 million dollar per year fuel savings for the commercial airline fleet. One passive drag reduction concept which is relatively simple to implement and retrofit is that of longitudinally grooved surfaces aligned with the stream velocity. These grooves (riblets) have heights and spacings on the order of the turbulent wall streak and burst dimensions. The riblet performance (8 percent net drag reduction thus far), sensitivity to operational/application considerations such as yaw and Reynolds number variation, an alternative fabrication technique, results of extensive parametric experiments for geometrical optimization, and flight test applications are summarized.

Evapotranspiration and surface energy balance across an agricultural-urban landscape gradient in Southern California, USA.

NASA Astrophysics Data System (ADS)

Shiflett, S. A.; Anderson, R. G.; Jenerette, D.

2014-12-01

Urbanization substantially affects energy, surface and air temperature, and hydrology due to extensive modifications in land surface properties such as vegetation, albedo, thermal capacity and soil moisture. The magnitude and direction of these alterations depends heavily on the type of urbanization that occurs. We investigated energy balance variation in a local network of agricultural and urban ecosystems using the eddy covariance method to better understand how vegetation fraction and degree of urbanization affects energy exchanges between the land surface and the atmosphere. We deployed eddy flux systems within a well-irrigated, agricultural citrus orchard, a moderately developed urban zone with a substantial amount of local vegetative cover, and an intensely developed urban zone with minimal vegetative cover and increased impervious surfaces relative to the other two sites. Latent energy (LE) fluxes in the agricultural area ranged from 7.9 ± 1.4 W m-2 (nighttime) to 168.7 ± 6.2 W m-2 (daytime) compared to 10.2 ± 3.5 W m-2 and 40.6 ± 4.1 W m-2, respectively, for the moderately developed urban area. Sensible energy (H) fluxes ranged from -9.1 ± 1.0 W m-2 (nighttime) to 119 ± 7.0 W m-2 (daytime) in the agricultural area compared to 9.6 ± 2.6 W m-2 and 134 ± 6.0 W m-2, respectively, for the moderately developed urban zone. Daytime LE is reduced with increasing urbanization; however, daily cycles of LE are less recognizable in urban areas compared to distinct daily cycles obtained above a mature citrus crop. In contrast, both daytime and nighttime H increases with increasing degree of urbanization. Reduction in vegetation and increases in impervious surfaces along an urbanization gradient leads to alterations in energy balance, which are associated with microclimate and water use changes.

Impact of Dust Radiative Forcing upon Climate. Chapter 13

NASA Technical Reports Server (NTRS)

Miller, Ronald L.; Knippertz, Peter; Perez Garcia-Pando, Carlos; Perlwitz, Jan P.; Tegan, Ina

2014-01-01

Dust aerosols perturb the atmospheric radiative flux at both solar and thermal wavelengths, altering the energy and water cycles. The climate adjusts by redistributing energy and moisture, so that local temperature perturbations, for example, depend upon the forcing over the entire extent of the perturbed circulation. Within regions frequently mixed by deep convection, including the deep tropics, dust particles perturb the surface air temperature primarily through radiative forcing at the top of the atmosphere (TOA). Many models predict that dust reduces global precipitation. This reduction is typically attributed to the decrease of surface evaporation in response to dimming of the surface. A counterexample is presented, where greater shortwave absorption by dust increases evaporation and precipitation despite greater dimming of the surface. This is attributed to the dependence of surface evaporation upon TOA forcing through its influence upon surface temperature and humidity. Perturbations by dust to the surface wind speed and vegetation (through precipitation anomalies) feed back upon the dust aerosol concentration. The current uncertainty of radiative forcing attributed to dust and the resulting range of climate perturbations calculated by models remain a useful test of our understanding of the mechanisms relating dust radiative forcing to the climate response.

Promoted Fixation of Molecular Nitrogen with Surface Oxygen Vacancies on Plasmon-Enhanced TiO2 Photoelectrodes.

PubMed

Li, Chengcheng; Wang, Tuo; Zhao, Zhi-Jian; Yang, Weimin; Li, Jian-Feng; Li, Ang; Yang, Zhilin; Ozin, Geoffrey A; Gong, Jinlong

2018-05-04

A hundred years on, the energy-intensive Haber-Bosch process continues to turn the N 2 in air into fertilizer, nourishing billions of people while causing pollution and greenhouse gas emissions. The urgency of mitigating climate change motivates society to progress toward a more sustainable method for fixing N 2 that is based on clean energy. Surface oxygen vacancies (surface O vac ) hold great potential for N 2 adsorption and activation, but introducing O vac on the very surface without affecting bulk properties remains a great challenge. Fine tuning of the surface O vac by atomic layer deposition is described, forming a thin amorphous TiO 2 layer on plasmon-enhanced rutile TiO 2 /Au nanorods. Surface O vac in the outer amorphous TiO 2 thin layer promote the adsorption and activation of N 2 , which facilitates N 2 reduction to ammonia by excited electrons from ultraviolet-light-driven TiO 2 and visible-light-driven Au surface plasmons. The findings offer a new approach to N 2 photofixation under ambient conditions (that is, room temperature and atmospheric pressure). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of Paint Color on Rest Period Climate Control Loads in Long-Haul Trucks: Preprint

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

Lustbader, J.; Kreutzer, C.; Jeffers, M.

Cab climate conditioning is one of the primary reasons for operating the main engine in a long-haul truck during driver rest periods. In the United States, sleeper cab trucks use approximately 667 million gallons of fuel annually for rest period idling. The U.S. Department of Energy's National Renewable Energy Laboratory's (NREL) CoolCab Project works closely with industry to design efficient thermal management systems for long-haul trucks that minimize engine idling and fuel use while maintaining occupant comfort. Heat transfer to the vehicle interior from opaque exterior surfaces is one of the major heat pathways that contribute to air conditioning loadsmore » during long-haul truck daytime rest period idling. To quantify the impact of paint color and the opportunity for advanced paints, NREL collaborated with Volvo Group North America, PPG Industries, and Dometic Environmental Corporation. Initial screening simulations using CoolCalc, NREL's rapid HVAC load estimation tool, showed promising air-conditioning load reductions due to paint color selection. Tests conducted at NREL's Vehicle Testing and Integration Facility using long-haul truck cab sections, 'test bucks,' showed a 31.1% of maximum possible reduction in rise over ambient temperature and a 20.8% reduction in daily electric air conditioning energy use by switching from black to white paint. Additionally, changing from blue to an advanced color-matched solar reflective blue paint resulted in a 7.3% reduction in daily electric air conditioning energy use for weather conditions tested in Colorado. National-level modeling results using weather data from major U.S. cities indicated that the increase in heating loads due to lighter paint colors is much smaller than the reduction in cooling loads.« less

SPM observation of slow highly charged ion induced nanodots on highly orientated pyrolytic graphite

NASA Astrophysics Data System (ADS)

Mitsuda, Y.; Nakamura, B. E. O'Rourke1 N.; Kanai, Y.; Ohtani, S.; Yamazaki, Y.

2007-03-01

We have observed nanodots on a highly orientated pyrolytic graphite (HOPG) surface produced by highly charged ion impacts using a scanning tunneling microscope. Previous measurements have con.rmed the dominant role of the potential energy or the incident ion charge state on the size and height of the observed nanodots. The present results extend these previous measurements to much lower kinetic energy. It appears that there is no observable influence on the lateral size of the nanodots due to the incident ion kinetic energy down to approximately 200 eV. In contrast some slight reduction in the nanodot height was observed as the kinetic energy was reduced.

Mechanism of H adatoms improving the O2 reduction reaction on the Zn-modified anatase TiO2 (101) surface studied by first principles calculation.

PubMed

Liu, Liangliang; Li, Chongyang; Jiang, Man; Li, Xiaodong; Huang, Xiaowei; Wang, Zhu; Jia, Yu

2018-06-05

First principles calculations were performed to cast insight into the mechanism of the improvement of O2 reduction reaction (ORR) activity by Zn and H interstitials on the anatase TiO2 (101) surface. For the Zn-modified anatase TiO2 (101) surface, both surface and subsurface Zn interstitials could contribute to O2 adsorption and dissociation, but the dissociation barriers of O2 molecules are still too high, which limits the ORR activity. After a H adatom is introduced onto the Zn-modified anatase TiO2 (101) surface, the highest energy barriers are greatly reduced compared with those of the Zn-modified surface. Meanwhile, it is observed that the dissociation barriers decrease almost linearly with the increase of the charge difference of adsorption O2 between initial and transition state configurations. Specifically, subsurface Zn and surface H interstitials facilitate O2 dissociation and subsequent oxidation reactions, and further frequency analysis shows that these dissociation processes are frequent even at the room temperature of 300 K. In a word, this work provides a theoretical support to design a high ORR activity catalyst of the TiO2 nanocrystal comparable to precious Pt catalysts.

Influence of urban resilience measures in the magnitude and behaviour of energy fluxes in the city of Porto (Portugal) under a climate change scenario.

PubMed

Rafael, S; Martins, H; Sá, E; Carvalho, D; Borrego, C; Lopes, M

2016-10-01

Different urban resilience measures, such as the increase of urban green areas and the application of white roofs, were evaluated with the WRF-SUEWS modelling system. The case study consists of five heat waves occurring in Porto (Portugal) urban area in a future climate scenario. Meteorological forcing and boundary data were downscaled for Porto urban area from the CMIP5 earth system model MPI-ESM, for the Representative Concentration Pathway RCP8.5 scenario. The influence of different resilience measures on the energy balance components was quantified and compared between each other. Results show that the inclusion of green urban areas increases the evaporation and the availability of surface moisture, redirecting the energy to the form of latent heat flux (maximum increase of +200Wm(-2)) rather than to sensible heat. The application of white roofs increases the solar radiation reflection, due to the higher albedo of such surfaces, reducing both sensible and storage heat flux (maximum reductions of -62.8 and -35Wm(-2), respectively). The conjugations of the individual benefits related to each resilience measure shows that this measure is the most effective one in terms of improving the thermal comfort of the urban population, particularly due to the reduction of both sensible and storage heat flux. The obtained results contribute to the knowledge of the surface-atmosphere exchanges and can be of great importance for stakeholders and decision-makers. Copyright © 2016 Elsevier B.V. All rights reserved.

Dynamic processes occurring at the Cr IIIaq-manganite (γ-MnOOH) interface: simultaneous adsorption, microprecipitation, oxidation/reduction, and dissolution

NASA Astrophysics Data System (ADS)

Weaver, Robert M.; Hochella, Michael F.; Ilton, Eugene S.

2002-12-01

The complex interaction between Cr IIIaq and manganite (γ-MnOOH) was systematically studied at room temperature over a pH range of 3 to 6, and within a concentration range of 10 -4 to 10 -2 M CrOH 2+aq. Solution compositional changes during batch reactions were characterized by inductively coupled plasma spectroscopy and ultraviolet-visible spectrophotometry. The manganites were characterized before and after reaction with X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), high-resolution field-emission SEM, and energy-dispersive spectroscopy analysis. Fluid-cell atomic force microscopy was used to follow these metal-mineral interactions in situ. The reactions are characterized by (1) sorption of Cr III and the surface-catalyzed microprecipitation of Cr III-hydroxy hydrate on manganite surfaces, (2) the acidic dissolution of the manganite, and (3) the simultaneous reductive dissolution of manganite coupled with the oxidation of Cr IIIaq to highly toxic Cr VIaq. Cr III-hydroxy hydrate was shown to precipitate on the manganite surface while still undersaturated in bulk solution. The rate of manganite dissolution increased with decreasing pH due both to acid-promoted and Mn-reduction-promoted dissolution. Cr oxidation also increased in the lower pH range, this as a result of its direct redox coupling with Mn reduction. Neither Mn II nor Cr VI were ever detected on manganite surfaces, even at the maximum rate of their generation. At the highest pHs of this study, Cr IIIaq was effectively removed from solution to form Cr III-hydroxy hydrate on manganite surfaces and in the bulk solution, and manganite dissolution and Cr VIaq generation were minimized. All interface reactions described above were heterogeneous across the manganite surfaces. This heterogeneity is a direct result of the heterogeneous semiconducting nature of natural manganite crystals and is also an expression of the proximity effect, whereby redox processes on semiconducting surfaces are not limited to next nearest neighbor sites.

Relationships between PEMFC Cathode Kinetic Losses and Contaminants’ Dipole Moment and Adsorption Energy on Pt

DOE PAGES

St-Pierre, Jean; Zhai, Yunfeng; Ge, Junjie

2016-01-05

A database summarizing the effects of 21 contaminants on the performance of proton exchange membrane fuel cells (PEMFCs) was used to examine relationships between cathode kinetic losses and contaminant physicochemical parameters. Impedance spectroscopy data were employed to obtain oxygen reduction kinetic resistances by fitting data in the 10-158 Hz range to a simplified equivalent circuit. The contaminant dipole moment and the adsorption energy of the contaminant on a Pt surface were chosen as parameters. Dipole moments did not correlate with dimensionless cathode kinetic resistances. In contrast, adsorption energies were quantitatively and linearly correlated with minimum dimensionless cathode kinetic resistances. Contaminantsmore » influence the oxygen reduction for contaminant adsorption energies smaller than -24.5 kJ mol -1, a value near the high limit of the adsorption energy of O 2 on Pt. Dimensionless cathode kinetic resistances linearly increase with decreasing O 2 adsorption energies below -24.5 kJ mol -1. Measured total cell voltage losses are mostly larger than the cathode kinetic losses calculated from kinetic resistance changes, which indicates the existence of other sources of performance degradation. Modifications to the experimental procedure are proposed to ensure that data are comparable on a similar basis and improve the correlation between contaminant adsorption energy and kinetic cell voltage losses.« less

Relationships between PEMFC Cathode Kinetic Losses and Contaminants’ Dipole Moment and Adsorption Energy on Pt

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

St-Pierre, Jean; Zhai, Yunfeng; Ge, Junjie

A database summarizing the effects of 21 contaminants on the performance of proton exchange membrane fuel cells (PEMFCs) was used to examine relationships between cathode kinetic losses and contaminant physicochemical parameters. Impedance spectroscopy data were employed to obtain oxygen reduction kinetic resistances by fitting data in the 10-158 Hz range to a simplified equivalent circuit. The contaminant dipole moment and the adsorption energy of the contaminant on a Pt surface were chosen as parameters. Dipole moments did not correlate with dimensionless cathode kinetic resistances. In contrast, adsorption energies were quantitatively and linearly correlated with minimum dimensionless cathode kinetic resistances. Contaminantsmore » influence the oxygen reduction for contaminant adsorption energies smaller than -24.5 kJ mol -1, a value near the high limit of the adsorption energy of O 2 on Pt. Dimensionless cathode kinetic resistances linearly increase with decreasing O 2 adsorption energies below -24.5 kJ mol -1. Measured total cell voltage losses are mostly larger than the cathode kinetic losses calculated from kinetic resistance changes, which indicates the existence of other sources of performance degradation. Modifications to the experimental procedure are proposed to ensure that data are comparable on a similar basis and improve the correlation between contaminant adsorption energy and kinetic cell voltage losses.« less

Dark matter sterile neutrinos in stellar collapse: Alteration of energy/lepton number transport, and a mechanism for supernova explosion enhancement

NASA Astrophysics Data System (ADS)

Hidaka, Jun; Fuller, George M.

2006-12-01

We investigate matter-enhanced Mikheyev-Smirnov-Wolfenstein (MSW) active-sterile neutrino conversion in the νe⇌νs channel in the collapse of the iron core of a presupernova star. For values of sterile neutrino rest mass ms and vacuum mixing angle θ (specifically, 0.5keV5×10-12) which include those required for viable sterile neutrino dark matter, our one-zone in-fall phase collapse calculations show a significant reduction in core lepton fraction. This would result in a smaller homologous core and therefore a smaller initial shock energy, disfavoring successful shock reheating and the prospects for an explosion. However, these calculations also suggest that the MSW resonance energy can exhibit a minimum located between the center and surface of the core. In turn, this suggests a post-core-bounce mechanism to enhance neutrino transport and neutrino luminosities at the core surface and thereby augment shock reheating: (1) scattering-induced or coherent MSW νe→νs conversion occurs deep in the core, at the first MSW resonance, where νe energies are large (˜150MeV); (2) the high energy νs stream outward at near light speed; (3) they deposit their energy when they encounter the second MSW resonance νs→νe just below the proto-neutron star surface.

A Measurement and Analysis of Buildup Region Dose for Open Field Photon Beams (Cobalt-60 through 24 MV)

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

McCullough, Edwin C.

2015-01-15

The central axis depth dose in the build-up region (surface to d{sub max}) of single open field photon beams (cobalt-60 through 24 MV) has been measured utilizing parallel plate and extrapolation chamber methodology. These data were used to derive, for a prescription dose of 100 cGy, values of surface dose, the maximum value of dose along the central axis (D{sub max}) and the depth (nearest the surface) at which 90% of the prescription dose occurs (d{sub 90}). For both single and parallel opposed pair (POP) open field configurations, data are presented at field sizes of 5 × 5, 15 ×more » 15 and 25 × 25 cm{sup 2} for prescription depths of 10, 15 and 20 cm (midplane for POP). For the treatment machines, field sizes, and prescription depths studied, it is possible to conclude that: for single open field irradiation, surface dose values (as a percentage of the prescription dose) can be either low (<10%) or comparable to the prescription dose itself; for POP open fields, surface dose values are relatively independent of photon energy and midplane depth, and range between 30% and 70% of prescription dose, being principally dependent on field size; the depth of the initial 90 cGy point for a prescription dose of 100 cGy, d{sub 90}, was larger for POP fields. For either single or POP open field treatments, d{sub 90} was always less than 22 mm, while for 6 MV or less, values of d{sub 90} were less than 4 mm; D{sub max} values can be very large (e.g., above 300 cGy) for certain treatment situations and are reduced significantly for POP treatments; for open field POP treatments, the percent reduction in D{sub max} with each increment in beam energy above 10 MV is reduced over that seen at 10 MV or less and, possibly, this further reduction may be clinically insignificant; for open field POP treatments, changes in surface dose, d{sub 90} and D{sub max} with beam energy above 10 MV do not suggest, with regard to these specific build-up curve parameters, any obvious advantage for treatment with beam energies greater than 10 MV for the specific machines and situations studied.« less

The Effect of Host Star Spectral Energy Distribution and Ice-Albedo Feedback on the Climate of Extrasolar Planets

PubMed Central

Meadows, Victoria S.; Bitz, Cecilia M.; Pierrehumbert, Raymond T.; Joshi, Manoj M.; Robinson, Tyler D.

2013-01-01

Abstract Planetary climate can be affected by the interaction of the host star spectral energy distribution with the wavelength-dependent reflectivity of ice and snow. In this study, we explored this effect with a one-dimensional (1-D), line-by-line, radiative transfer model to calculate broadband planetary albedos as input to a seasonally varying, 1-D energy balance climate model. A three-dimensional (3-D) general circulation model was also used to explore the atmosphere's response to changes in incoming stellar radiation, or instellation, and surface albedo. Using this hierarchy of models, we simulated planets covered by ocean, land, and water-ice of varying grain size, with incident radiation from stars of different spectral types. Terrestrial planets orbiting stars with higher near-UV radiation exhibited a stronger ice-albedo feedback. We found that ice extent was much greater on a planet orbiting an F-dwarf star than on a planet orbiting a G-dwarf star at an equivalent flux distance, and that ice-covered conditions occurred on an F-dwarf planet with only a 2% reduction in instellation relative to the present instellation on Earth, assuming fixed CO2 (present atmospheric level on Earth). A similar planet orbiting the Sun at an equivalent flux distance required an 8% reduction in instellation, while a planet orbiting an M-dwarf star required an additional 19% reduction in instellation to become ice-covered, equivalent to 73% of the modern solar constant. The reduction in instellation must be larger for planets orbiting cooler stars due in large part to the stronger absorption of longer-wavelength radiation by icy surfaces on these planets in addition to stronger absorption by water vapor and CO2 in their atmospheres, which provides increased downwelling longwave radiation. Lowering the IR and visible-band surface ice and snow albedos for an M-dwarf planet increased the planet's climate stability against changes in instellation and slowed the descent into global ice coverage. The surface ice-albedo feedback effect becomes less important at the outer edge of the habitable zone, where atmospheric CO2 could be expected to be high such that it maintains clement conditions for surface liquid water. We showed that ∼3–10 bar of CO2 will entirely mask the climatic effect of ice and snow, leaving the outer limits of the habitable zone unaffected by the spectral dependence of water ice and snow albedo. However, less CO2 is needed to maintain open water for a planet orbiting an M-dwarf star than would be the case for hotter main-sequence stars. Key Words: Extrasolar planets—M stars—Habitable zone—Snowball Earth. Astrobiology 13, 715–739. PMID:23855332

The effect of host star spectral energy distribution and ice-albedo feedback on the climate of extrasolar planets.

PubMed

Shields, Aomawa L; Meadows, Victoria S; Bitz, Cecilia M; Pierrehumbert, Raymond T; Joshi, Manoj M; Robinson, Tyler D

2013-08-01

Planetary climate can be affected by the interaction of the host star spectral energy distribution with the wavelength-dependent reflectivity of ice and snow. In this study, we explored this effect with a one-dimensional (1-D), line-by-line, radiative transfer model to calculate broadband planetary albedos as input to a seasonally varying, 1-D energy balance climate model. A three-dimensional (3-D) general circulation model was also used to explore the atmosphere's response to changes in incoming stellar radiation, or instellation, and surface albedo. Using this hierarchy of models, we simulated planets covered by ocean, land, and water-ice of varying grain size, with incident radiation from stars of different spectral types. Terrestrial planets orbiting stars with higher near-UV radiation exhibited a stronger ice-albedo feedback. We found that ice extent was much greater on a planet orbiting an F-dwarf star than on a planet orbiting a G-dwarf star at an equivalent flux distance, and that ice-covered conditions occurred on an F-dwarf planet with only a 2% reduction in instellation relative to the present instellation on Earth, assuming fixed CO(2) (present atmospheric level on Earth). A similar planet orbiting the Sun at an equivalent flux distance required an 8% reduction in instellation, while a planet orbiting an M-dwarf star required an additional 19% reduction in instellation to become ice-covered, equivalent to 73% of the modern solar constant. The reduction in instellation must be larger for planets orbiting cooler stars due in large part to the stronger absorption of longer-wavelength radiation by icy surfaces on these planets in addition to stronger absorption by water vapor and CO(2) in their atmospheres, which provides increased downwelling longwave radiation. Lowering the IR and visible-band surface ice and snow albedos for an M-dwarf planet increased the planet's climate stability against changes in instellation and slowed the descent into global ice coverage. The surface ice-albedo feedback effect becomes less important at the outer edge of the habitable zone, where atmospheric CO(2) could be expected to be high such that it maintains clement conditions for surface liquid water. We showed that ∼3-10 bar of CO(2) will entirely mask the climatic effect of ice and snow, leaving the outer limits of the habitable zone unaffected by the spectral dependence of water ice and snow albedo. However, less CO(2) is needed to maintain open water for a planet orbiting an M-dwarf star than would be the case for hotter main-sequence stars.

Growth and Surface Modification of LaFeO3 Thin Films Induced By Reductive Annealing

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

Flynn, Brendan T.; Zhang, Hongliang; Shutthanandan, V.

2015-03-01

The electronic and ionic conductivity of perovskite oxides has enabled their use in diverse applications such as automotive exhaust catalysts, solid oxide fuel cell cathodes, and visible light photocatalysts. The redox chemistry at the surface of perovskite oxides is largely dependent on the oxidation state of the metal cations as well as the oxide surface stoichiometry. In this study, LaFeO3 (LFO) thin films grown on yttria-stabilized zirconia (YSZ) was characterized using both bulk and surface sensitive techniques. A combination of in situ reflection high energy electron diffraction (RHEED), x-ray diffraction (XRD), transmission electron microscopy (TEM) and Rutherford backscattering spectrometry (RBS)more » demonstrated that the film is highly oriented and stoichiometric. The film was annealed in an ultra-high vacuum chamber to simulate reducing conditions and studied by angle-resolved x-ray photoelectron spectroscopy (XPS). Iron was found to exist as Fe(0), Fe(II), and Fe(III) depending on the annealing conditions and the depth within the film. A decrease in the concentration of surface oxygen species was correlated with iron reduction. These results should help guide and enhance the design of perovskite materials for catalysts.« less

Improving the degradation behavior and in vitro biological property of nano-hydroxyapatite surface- grafted with the assist of citric acid.

PubMed

Jiang, Liuyun; Jiang, Lixin; Xiong, Chengdong; Su, Shengpei

2016-10-01

To obtain ideal nano-hydroxyapatite(n-HA) filler for poly(lactide-co-glycolide) (PLGA), a new surface-grafting with the assist of citric acid for nano-hydroxyapatite (n-HA) was designed, and the effect of n-HA surface-grafted with or without citric acid on in vitro degradation behavior and cells viability was studied by the experiments of soaking in simulated body fluid (SBF) and incubating with human osteoblast-like cells (MG-63). The change of pH value, tensile strength reduction, the surface deposits, cells attachment and proliferation of samples during the soaking and incubation were investigated by means of pH meter, electromechanical universal tester, scanning electron microscope (SEM) coupled with energy-dispersive spectro-scopy (EDS), fluorescence microscope and MTT method. The results showed that the introduction of citric acid not only delayed the strength reduction during the degradation by inhibiting the detachment of n-HA from PLGA, but also endowed it better cell attachment and proliferation, suggesting that the n-HA surface-grafted with the assist of citric acid was an important bioactive ceramic fillers for PLGA used as bone materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Flows, strains, and the formation of joints in oblique collision of metal plates

NASA Astrophysics Data System (ADS)

Shtertser, A. A.; Zlobin, B. S.

2015-09-01

The processes of high-velocity oblique collision of metal plates which lead to the formation of their joints (seizure) are considered. It is found that the cleaning of the plate surface necessary for seizure results from a jet flow (particle stream), whose source is at least one of the welded materials or an interlayer of ductile material located in the initial region of collision. It is shown that additional cleaning may occur due to the emergence of rotating microregions in intense gradient flows localized in the joint area; seizure on cleaned surfaces is due to reduction of the surface energy of the system.

Electrohydrodynamic behavior of water droplets on a horizontal super hydrophobic surface and its self-cleaning application

NASA Astrophysics Data System (ADS)

Li, Jian; Wei, Yuan; Huang, Zhengyong; Wang, Feipeng; Yan, Xinzhu; Wu, Zhuolin

2017-05-01

Moisture is a significant factor that affects the insulation performance of outdoor high-voltage insulators in power systems. Accumulation of water droplets on insulators causes severe problems such as flashover of insulators and power outage. In this study, we develop a method to fabricate a micro/nano hierarchical super hydrophobic surface. The as-prepared super hydrophobic surface exhibits a water contact angle (WCA) of 160.4 ± 2°, slide angle (SA) less than 1° and surface free energy (SFE) of 5.99 mJ/m2. We investigated the electrohydropdynamic behavior of water droplet on a horizontal super hydrophobic surface compared with hydrophobic RTV silicone rubber surface which was widely used as anti-pollution coating or shed material of composite insulator. Results show that water droplet tended to a self-propelled motion on the super hydrophobic surface while it tended to elongate and break up on the RTV surface. The micro/nano hierarchical surface structure and chemical components with low surface free energy of the super hydrophobic surface jointly contributed to the reduction of skin fraction drag and subsequently made it possible for the motion of water droplet driven by electric field. Furthermore, the self-propelled motion of water droplets could also sweep away contaminations along its moving trace, which provides super hydrophobic surface a promising anti-pollution prospect in power systems.

Development and verification of a new wind speed forecasting system using an ensemble Kalman filter data assimilation technique in a fully coupled hydrologic and atmospheric model

NASA Astrophysics Data System (ADS)

Williams, John L.; Maxwell, Reed M.; Monache, Luca Delle

2013-12-01

Wind power is rapidly gaining prominence as a major source of renewable energy. Harnessing this promising energy source is challenging because of the chaotic nature of wind and its inherently intermittent nature. Accurate forecasting tools are critical to support the integration of wind energy into power grids and to maximize its impact on renewable energy portfolios. We have adapted the Data Assimilation Research Testbed (DART), a community software facility which includes the ensemble Kalman filter (EnKF) algorithm, to expand our capability to use observational data to improve forecasts produced with a fully coupled hydrologic and atmospheric modeling system, the ParFlow (PF) hydrologic model and the Weather Research and Forecasting (WRF) mesoscale atmospheric model, coupled via mass and energy fluxes across the land surface, and resulting in the PF.WRF model. Numerous studies have shown that soil moisture distribution and land surface vegetative processes profoundly influence atmospheric boundary layer development and weather processes on local and regional scales. We have used the PF.WRF model to explore the connections between the land surface and the atmosphere in terms of land surface energy flux partitioning and coupled variable fields including hydraulic conductivity, soil moisture, and wind speed and demonstrated that reductions in uncertainty in these coupled fields realized through assimilation of soil moisture observations propagate through the hydrologic and atmospheric system. The sensitivities found in this study will enable further studies to optimize observation strategies to maximize the utility of the PF.WRF-DART forecasting system.

The influence of Ag content and annealing time on structural and optical properties of SGS antimony-germanate glass doped with Er3+ ions

NASA Astrophysics Data System (ADS)

Zmojda, J.; Kochanowicz, M.; Miluski, P.; Baranowska, A.; Basa, A.; Jadach, R.; Sitarz, M.; Dorosz, D.

2018-05-01

A series of erbium doped SGS antimony-germanate glass embedding silver (Ag0) nanoparticles have been synthesized by a one-step melt-quench thermochemical reduction technique. The effect of NPs concentration and annealing time on the structural and photoluminescent (PL) properties were investigated. The Raman spectra as a function of temperature measured in-situ allow to determine the structural changes in vicinity of Ag+ ions and confirmed thermochemical reduction of Ag+ ions by Sb3+ ions. The surface plasmon resonance absorption band was evidenced near 450 nm. The impact of local field effect generated by Ag0 nanoparticles (NPs) and energy transfer from surface of silver NPs to trivalent erbium ions on near-infrared and up-conversion luminescence was described in terms of enhancement and quench phenomena.

Carbon-doped boron nitride nanosheet as a promising catalyst for N2O reduction by CO or SO2 molecule: A comparative DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Saeidi, Nasibeh

2018-06-01

We report for the first time, the catalytic activity of the experimentally available carbon-doped boron nitride nanosheet (C-BNNS) towards the reduction of N2O in the presence of CO or SO2 molecule. According to our density functional theory calculations, C-doping can introduce high spin density into BN monolayer which is mainly localized over the C and its neighboring N atoms. The Hirshfeld charge density analysis reveals that the electron-rich C-BNNS acts as an electron donating support to activate N2O molecule which is an important step in the reduction of N2O. The N2O reduction reaction starts with the dissociative adsorption of N2O over the C-BNNS surface, yielding the N2 molecule and an activated oxygen moiety (Oads) adsorbed over the C atom. The reaction then proceeds via the elimination of Oads by a CO or SO2 molecule. The obtained low activation energies clearly indicate that the metal-free C-BNNS surface can be regarded as a highly active catalyst for the reduction of N2O. The results of this study may open new avenues in searching low cost and highly active BN-based catalysts for low temperature reduction of N2O.

Quantitative assessment of the enamel machinability in tooth preparation with dental diamond burs.

PubMed

Song, Xiao-Fei; Jin, Chen-Xin; Yin, Ling

2015-01-01

Enamel cutting using dental handpieces is a critical process in tooth preparation for dental restorations and treatment but the machinability of enamel is poorly understood. This paper reports on the first quantitative assessment of the enamel machinability using computer-assisted numerical control, high-speed data acquisition, and force sensing systems. The enamel machinability in terms of cutting forces, force ratio, cutting torque, cutting speed and specific cutting energy were characterized in relation to enamel surface orientation, specific material removal rate and diamond bur grit size. The results show that enamel surface orientation, specific material removal rate and diamond bur grit size critically affected the enamel cutting capability. Cutting buccal/lingual surfaces resulted in significantly higher tangential and normal forces, torques and specific energy (p<0.05) but lower cutting speeds than occlusal surfaces (p<0.05). Increasing material removal rate for high cutting efficiencies using coarse burs yielded remarkable rises in cutting forces and torque (p<0.05) but significant reductions in cutting speed and specific cutting energy (p<0.05). In particular, great variations in cutting forces, torques and specific energy were observed at the specific material removal rate of 3mm(3)/min/mm using coarse burs, indicating the cutting limit. This work provides fundamental data and the scientific understanding of the enamel machinability for clinical dental practice. Copyright © 2014 Elsevier Ltd. All rights reserved.

Pt 3Re alloy nanoparticles as electrocatalysts for the oxygen reduction reaction

DOE PAGES

Raciti, David; Kubal, Joseph; Ma, Cheng; ...

2015-12-25

Development of renewable energy technologies requires advanced catalysts for efficient electrical-chemical energy conversion reactions. Here in this paper, we report the study of Pt-Re alloy nanoparticles as an electrocatalyst for the oxygen reduction reaction (ORR). An organic solution approach is developed to synthesize monodisperse and homogeneous Pt 3Re alloy nanoparticles. Electrochemical studies show that these nanoparticles exhibit an improvement factor of 4 in catalytic activity for the ORR compared to commercial Pt catalysts of similar particle sizes. Fundamental understanding of the structure-property relationship is established by combining material characterization using X-ray spectroscopy and atomically resolved electron microscopy, as well asmore » Density Functional Theory (DFT) calculations. Lastly, our work revealed that an electronic modification of the surface properties of Pt by subsurface Re (ligand effect) accounts for the catalytic enhancement.« less

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

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

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE PAGES

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira; ...

2017-12-18

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Changes in the morphology of interstellar ice analogues after hydrogen atom exposure.

PubMed

Accolla, Mario; Congiu, Emanuele; Dulieu, François; Manicò, Giulio; Chaabouni, Henda; Matar, Elie; Mokrane, Hakima; Lemaire, Jean Louis; Pirronello, Valerio

2011-05-07

The morphology of water ice in the interstellar medium is still an open question. Although accretion of gaseous water could not be the only possible origin of the observed icy mantles covering dust grains in cold molecular clouds, it is well known that water accreted from the gas phase on surfaces kept at 10 K forms ice films that exhibit a very high porosity. It is also known that in the dark clouds H(2) formation occurs on the icy surface of dust grains and that part of the energy (4.48 eV) released when adsorbed atoms react to form H(2) is deposited in the ice. The experimental study described in the present work focuses on how relevant changes of the ice morphology result from atomic hydrogen exposure and subsequent recombination. Using the temperature-programmed desorption (TPD) technique and a method of inversion analysis of TPD spectra, we show that there is an exponential decrease in the porosity of the amorphous water ice sample following D-atom irradiation. This decrease is inversely proportional to the thickness of the ice and has a value of ϕ(0) = 2 × 10(16) D-atoms cm(-2) per layer of H(2)O. We also use a model which confirms that the binding sites on the porous ice are destroyed regardless of their energy depth, and that the reduction of the porosity corresponds in fact to a reduction of the effective area. This reduction appears to be compatible with the fraction of D(2) formation energy transferred to the porous ice network. Under interstellar conditions, this effect is likely to be efficient and, together with other compaction processes, provides a good argument to believe that interstellar ice is amorphous and non-porous. This journal is © the Owner Societies 2011

Photoelectrochemical processes in polymer-tethered CdSe nanocrystals.

PubMed

Shallcross, R Clayton; D'Ambruoso, Gemma D; Pyun, Jeffrey; Armstrong, Neal R

2010-03-03

We demonstrate the electrochemical capture of CdSe semiconductor nanocrystals (NCs), with thiophene-terminated carboxylic acid capping ligands, at the surfaces of electrodeposited poly(thiophene) films (i) poly((diethyl)propylenedixoythiophene), P(Et)(2)ProDOT; (ii) poly(propylenedioxythiophene), PProDOT; and (iii) poly(ethylenedioxythiophene), PEDOT, coupled with the exploration of their photoelectrochemical properties. Host polymer films were created using a kinetically controlled electrodeposition protocol on activated indium-tin oxide electrodes (ITO), producing conformal films that facilitate high rates of electron transfer. ProDOT-terminated, ligand-capped CdSe-NCs were captured at the outer surface of the host polymer films using a unique pulse-potential step electrodeposition protocol, providing for nearly close-packed monolayers of the NCs at the host polymer/solution interface. These polymer-confined CdSe NCs were used as sensitizers in the photoelectrochemical reduction of methyl viologen (MV(+2)). High internal quantum efficiencies (IQEs) are estimated for photoelectrochemical sensitized MV(+2) reduction using CdSe NCs ranging from 3.1 to 7.0 nm diameters. Cathodic photocurrent at high MV(+2) concentrations are limited by the rate of hole-capture by the host polymer from photoexcited NCs. The rate of this hole-capture process is determined by (a) the onset potential for reductive dedoping of the host polymer film; (b) the concentration ratio of neutral to oxidized forms of the host polymer ([P(n)]/[P(ox)]); and (c) the NC diameter, which controls its valence band energy, E(VB). These relationships are consistent with control of photoinduced electron transfer by Marcus-like excess free energy relationships. Our electrochemical assembly methods provide an enabling route to the capture of functional NCs in conducting polymer hosts in both photoelectrochemical and photovoltaic energy conversion systems.

Self-Assembled Three-Dimensional Graphene Macrostructures: Synthesis and Applications in Supercapacitors.

PubMed

Xu, Yuxi; Shi, Gaoquan; Duan, Xiangfeng

2015-06-16

Graphene and its derivatives are versatile building blocks for bottom-up assembly of advanced functional materials. In particular, with exceptionally large specific surface area, excellent electrical conductivity, and superior chemical/electrochemical stability, graphene represents the ideal material for various electrochemical energy storage devices including supercapacitors. However, due to the strong π-π interaction between graphene sheets, the graphene flakes tend to restack to form graphite-like powders when they are processed into practical electrode materials, which can greatly reduce the specific surface area and lead to inefficient utilization of the graphene layers for electrochemical energy storage. The self-assembly of two-dimensional graphene sheets into three-dimensional (3D) framework structures can largely retain the unique properties of individual graphene sheets and has recently garnered intense interest for fundamental investigations and potential applications in diverse technologies. In this Account, we review the recent advances in preparing 3D graphene macrostructures and exploring them as a unique platform for supercapacitor applications. We first describe the synthetic strategies, in which reduction of a graphene oxide dispersion above a certain critical concentration can induce the reduced graphene oxide sheets to cross-link with each other via partial π-π stacking interactions to form a 3D interconnected porous macrostructure. Multiple reduction strategies, including hydrothermal/solvothermal reduction, chemical reduction, and electrochemical reduction, have been developed for the preparation of 3D graphene macrostructures. The versatile synthetic strategies allow for easy incorporation of heteroatoms, carbon nanomaterials, functional polymers, and inorganic nanostructures into the macrostructures to yield diverse composites with tailored structures and properties. We then summarize the applications of the 3D graphene macrostructures for high-performance supercapacitors. With a unique framework structure in which the graphene sheets are interlocked in 3D space to prevent their restacking, the graphene macrostructures feature very high specific surface areas, rapid electron and ion transport, and superior mechanical strength. They can thus be directly used as supercapacitor electrodes with excellent specific capacitances, rate capabilities, and cycling stabilities. We finally discuss the current challenges and future opportunities in this research field. By regarding the graphene as both a single-atom-thick carbon sheet and a conjugated macromolecule, our work opens a new avenue to bottom-up self-assembly of graphene macromolecule sheets into functional 3D graphene macrostructures with remarkable electrochemical performances. We hope that this Account will promote further efforts toward fundamental investigation of graphene self-assembly and the development of advanced 3D graphene materials for their real-world applications in electrochemical energy storage devices and beyond.

Effect of Temperature and Graphite Immersion Method on Carbothermic Reduction of Fayalite Slag

NASA Astrophysics Data System (ADS)

Mitrašinović, Aleksandar

2017-09-01

In this work, graphite flakes were used to reduce fayalite slag originated from the pyrometallurgical copper extraction process. Experiments were conducted with a significantly different contact area between graphite and slag at two temperatures, 1300°C and 1400°C. The process was continuously monitored via the concentration change of CO and CO2 in off-gas. Reduction rate values in experiments where 150-micron-diameter graphite flakes were submerged into the slag and left to float slowly to the top are about four times higher compared with when graphite flakes were dispersed at the top surface of liquid slag. The activation energy for instigating reduction was 302.61 kJ mol-1 and 306.67 kJ mol-1 in the case where graphite flakes were submerged into the slag and dispersed at the surface, respectively. The reduction process is characterized by two distinctive periods: an initial steep increase in the concentration of CO and CO2 controlled by the Boudouard reaction and a subsequent slow decrease of CO and CO2 concentrations in the off-gas controlled by mass transfer of reducible oxides from bulk to the gas-slag interface.

Method for producing chemical energy

DOEpatents

Jorgensen, Betty S.; Danen, Wayne C.

2004-09-21

Fluoroalkylsilane-coated metal particles having a central metal core, a buffer layer surrounding the core, and a fluoroalkylsilane layer attached to the buffer layer are prepared by combining a chemically reactive fluoroalkylsilane compound with an oxide coated metal particle having a hydroxylated surface. The resulting fluoroalkylsilane layer that coats the particles provides them with excellent resistance to aging. The particles can be blended with oxidant particles to form energetic powder that releases chemical energy when the buffer layer is physically disrupted so that the reductant metal core can react with the oxidant.

Nanostructures and surface hydrophobicity of self-assembled thermosets involving epoxy resin and poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) amphiphilic diblock copolymer.

PubMed

Yi, Fangping; Zheng, Sixun; Liu, Tianxi

2009-02-19

Poly(2,2,2-trifluoroethyl acrylate)-block-poly(ethylene oxide) (PTFEA-b-PEO) amphiphilic diblock copolymer was synthesized via the reversible addition-fragmentation transfer polymerization of 2,2,2-triffluroethyl acrylate with dithiobenzoyl-terminated poly(ethylene oxide) as a chain-transfer agent. The amphiphilic diblock copolymer was incorporated into epoxy resin to prepare the nanostructured epoxy thermosets. The nanostructures were investigated by means of atomic force microscopy, small-angle X-ray scattering, and dynamic mechanical analysis. In terms of the miscibility of the subchains of the block copolymer with epoxy after and before curing reaction, it is judged that the formation of the nanostructures follows the mechanism of self-assembly. The static contact angle measurements indicate that the nanostructured thermosets containing PTFEA-b-PEO diblock copolymer displayed a significant enhancement in surface hydrophobicity as well as a reduction in surface free energy. The improvement in surface properties was ascribed to the enrichment of the fluorine-containing subchain (i.e., PTFEA block) of the amphiphilic diblock copolymer on the surface of the nanostructured thermosets, which was evidenced by surface atomic force microscopy and energy-dispersive X-ray spectroscopy.

Energy Saving Melting and Revert Reduction Technology (E-SMARRT): Development of Surface Engineered Coating Systems for Aluminum Pressure Die Casting Dies: Towards a 'Smart' Die Coating

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

Dr. John J. Moore; Dr. Jianliang Lin,

2012-07-31

The main objective of this research program was to design and develop an optimal coating system that extends die life by minimizing premature die failure. In high-pressure aluminum die-casting, the die, core pins and inserts must withstand severe processing conditions. Many of the dies and tools in the industry are being coated to improve wear-resistance and decrease down-time for maintenance. However, thermal fatigue in metal itself can still be a major problem, especially since it often leads to catastrophic failure (i.e. die breakage) as opposed to a wear-based failure (parts begin to go out of tolerance). Tooling costs remain themore » largest portion of production costs for many of these parts, so the ability prevent catastrophic failures would be transformative for the manufacturing industry.The technology offers energy savings through reduced energy use in the die casting process from several factors, including increased life of the tools and dies, reuse of the dies and die components, reduction/elimination of lubricants, and reduced machine down time, and reduction of Al solder sticking on the die. The use of the optimized die coating system will also reduce environmental wastes and scrap parts. Current (2012) annual energy saving estimates, based on initial dissemination to the casting industry in 2010 and market penetration of 80% by 2020, is 3.1 trillion BTU's/year. The average annual estimate of CO2 reduction per year through 2020 is 0.63 Million Metric Tons of Carbon Equivalent (MM TCE).« less

Degradation of oxygen reduction reaction kinetics in porous La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes due to aging-induced changes in surface chemistry

NASA Astrophysics Data System (ADS)

Baqué, Laura C.; Soldati, Analía L.; Teixeira-Neto, Erico; Troiani, Horacio E.; Schreiber, Anja; Serquis, Adriana C.

2017-01-01

The modification of surface composition after long-term operation is one of the most reported degradation mechanisms of (La,Sr)(Co,Fe)O3-δ (LSCFO) cathodes for Solid Oxide Fuel Cells (SOFCs). Nevertheless, its effect on the oxygen reduction reaction kinetics of porous LSCFO cathodes has not been yet reliably established. In this work, La- and Sr-enrichment at the LSCFO surface of porous cathodes has been induced after 50 h aging at 800 °C under air. Such cation redistribution can extend up to ∼400 nm depth under the LSCFO surface as detected by high resolution Scanning Transmission Electron Microscopy-Energy Dispersive Spectroscopy maps acquired inside the cathode pores. The observed surface chemical changes hamper the oxygen surface exchange reaction at the LSCFO/gas interface. Accordingly, a suitable Electrochemical Impedance Spectroscopy analysis revealed that the oxygen ion conductivity remains practically unaltered during the aging treatment while the oxygen surface exchange resistance increases up to 1.8 times. As a result, the cathode impedance response deteriorates within the 10-0.1 Hz frequency range during the aging treatment, resulting in a total cathode area specific resistance increase of 150%. The methodology adopted has demonstrated to be very valuable for studying the degradation of SOFC cathodes produced by the modification of surface composition.

High-Performanced Cathode with a Two-Layered R-P Structure for Intermediate Temperature Solid Oxide Fuel Cells.

PubMed

Huan, Daoming; Wang, Zhiquan; Wang, Zhenbin; Peng, Ranran; Xia, Changrong; Lu, Yalin

2016-02-01

Driven by the mounting concerns on global warming and energy crisis, intermediate temperature solid-oxide fuel cells (IT-SOFCs) have attracted special attention for their high fuel efficiency, low toxic gas emission, and great fuel flexibility. A key obstacle to the practical operation of IT-SOFCs is their sluggish oxygen reduction reaction (ORR) kinetics. In this work, we applied a new two-layered Ruddlesden-Popper (R-P) oxide, Sr3Fe2O7-δ (SFO), as the material for oxygen ion conducting IT-SOFCs. Density functional theory calculation suggested that SFO has extremely low oxygen ion formation energy and considerable energy barrier for O(2-) diffusion. Unfortunately, the stable SrO surface of SFO was demonstrated to be inert to O2 adsorption and dissociation reaction, and thus restricts its catalytic activity toward ORR. Based on this observation, Co partially substituted SFO (SFCO) was then synthesized and applied to improve its surface vacancy concentration to accelerate the oxygen adsorptive reduction reaction rate. Electrochemical performance results suggested that the cell using the SFCO single phase cathode has a peak power density of 685 mW cm(-2) at 650 °C, about 15% higher than those when using LSCF cathode. Operating at 200 mA cm(-2), the new cell using SFCO is quite stable within the 100-h' test.

Forcings and feedbacks in the GeoMIP ensemble for a reduction in solar irradiance and increase in CO2

NASA Astrophysics Data System (ADS)

Huneeus, Nicolas; Boucher, Olivier; Alterskjær, Kari; Cole, Jason N. S.; Curry, Charles L.; Ji, Duoying; Jones, Andy; Kravitz, Ben; Kristjánsson, Jón Egill; Moore, John C.; Muri, Helene; Niemeier, Ulrike; Rasch, Phil; Robock, Alan; Singh, Balwinder; Schmidt, Hauke; Schulz, Michael; Tilmes, Simone; Watanabe, Shingo; Yoon, Jin-Ho

2014-05-01

The effective radiative forcings (including rapid adjustments) and feedbacks associated with an instantaneous quadrupling of the preindustrial CO2 concentration and a counterbalancing reduction of the solar constant are investigated in the context of the Geoengineering Model Intercomparison Project (GeoMIP). The forcing and feedback parameters of the net energy flux, as well as its different components at the top-of-atmosphere (TOA) and surface, were examined in 10 Earth System Models to better understand the impact of solar radiation management on the energy budget. In spite of their very different nature, the feedback parameter and its components at the TOA and surface are almost identical for the two forcing mechanisms, not only in the global mean but also in their geographical distributions. This conclusion holds for each of the individual models despite intermodel differences in how feedbacks affect the energy budget. This indicates that the climate sensitivity parameter is independent of the forcing (when measured as an effective radiative forcing). We also show the existence of a large contribution of the cloudy-sky component to the shortwave effective radiative forcing at the TOA suggesting rapid cloud adjustments to a change in solar irradiance. In addition, the models present significant diversity in the spatial distribution of the shortwave feedback parameter in cloudy regions, indicating persistent uncertainties in cloud feedback mechanisms.

Long-lasting antifog plasma modification of transparent plastics.

PubMed

Di Mundo, Rosa; d'Agostino, Riccardo; Palumbo, Fabio

2014-10-08

Antifog surfaces are necessary for any application requiring optical efficiency of transparent materials. Surface modification methods aimed toward increasing solid surface energy, even when supposed to be permanent, in fact result in a nondurable effect due to the instability in air of highly hydrophilic surfaces. We propose the strategy of combining a hydrophilic chemistry with a nanotextured topography, to tailor a long-lasting antifog modification on commercial transparent plastics. In particular, we investigated a two-step process consisting of self-masked plasma etching followed by plasma deposition of a silicon-based film. We show that the deposition of the silicon-based coatings on the flat (pristine) substrates allows a continuous variation of wettability from hydrophobic to superhydrophilic, due to a continuous reduction of carbon-containing groups, as assessed by Fourier transform infrared and X-ray photoelectron spectroscopies. By depositing these different coatings on previously nanotextured substrates, the surface wettability behavior is changed consistently, as well as the condensation phenomenon in terms of microdroplets/liquid film appearance. This variation is correlated with advancing and receding water contact angle features of the surfaces. More importantly, in the case of the superhydrophilic coating, though its surface energy decreases with time, when a nanotextured surface underlies it, the wetting behavior is maintained durably superhydrophilic, thus durably antifog.

Energy Savings Calculations for Heat Island Reduction Strategies in Baton Rouge, Sacramento and Salt Lake City

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

Konopacki, S.; Akbari, H.

2000-03-01

In 1997, the US Environmental Protection Agency (EPA) established the ''Heat Island Reduction Initiative'', to quantify the potential benefits of Heat Island Reduction (HIR) strategies (i.e., shade trees, reflective roofs, reflective pavements and urban vegetation) to reduce cooling energy use in buildings, lower the ambient air temperature and improve urban air quality in cities, and reduce CO2 emissions from power plants. Under this initiative, the Urban Heat Island Pilot Project (UHIPP) was created with the objective to investigate the potential of HIR strategies in residential and commercial buildings in three initial UHIPP cities: Baton Rouge, Sacramento and Salt Lake City.more » This paper summarizes our efforts to calculate the annual energy savings, peak power avoidance and annual C02 reduction of HIR strategies in the three initial cities. In this analysis, we focused on three building types that offer most savings potential: single-family residence, office and retail store. Each building type was characterized in detail by old or new construction and with a gas furnace or an electric heat pump. We defined prototypical building characteristics for each building type and simulated the impact of HIR strategies on building cooling and heating energy use and peak power demand using the DOE-2.IE model. Our simulations included the impact of (1) strategically-placed shade trees near buildings [direct effect], (2) use of high-albedo roofing material on building [direct effect], (3) combined strategies I and 2 [direct effect], (4) urban reforestation with high-albedo pavements and building surfaces [indirect effect] and (5) combined strategies 1, 2 and 4 [direct and indirect effects]. We then estimated the total roof area of air-conditioned buildings in each city using readily obtainable data to calculate the metropolitan-wide impact of HIR strategies. The results show, that in Baton Rouge, potential annual energy savings of $15M could be realized by rate-payers from the combined direct and indirect effects of HIR strategies. Additionally, peak power avoidance is estimated at 133 MW and the reduction in annual carbon emissions at 41 kt. In Sacramento, the potential annual energy savings is estimated at $26M, with an avoidance of 486 MW in peak power and a reduction in annual carbon of 92 kt. In Salt Lake City, the potential annual energy savings is estimated at $4M, with an avoidance of 85 MW in peak power and a reduction in annual carbon of 20 kt.« less

Linking Thermodynamics to Pollutant Reduction Kinetics by Fe2+ Bound to Iron Oxides.

PubMed

Stewart, Sydney M; Hofstetter, Thomas B; Joshi, Prachi; Gorski, Christopher A

2018-05-15

Numerous studies have reported that pollutant reduction rates by ferrous iron (Fe 2+ ) are substantially enhanced in the presence of an iron (oxyhydr)oxide mineral. Developing a thermodynamic framework to explain this phenomenon has been historically difficult due to challenges in quantifying reduction potential ( E H ) values for oxide-bound Fe 2+ species. Recently, our group demonstrated that E H values for hematite- and goethite-bound Fe 2+ can be accurately calculated using Gibbs free energy of formation values. Here, we tested if calculated E H values for oxide-bound Fe 2+ could be used to develop a free energy relationship capable of describing variations in reduction rate constants of substituted nitrobenzenes, a class of model pollutants that contain reducible aromatic nitro groups, using data collected here and compiled from the literature. All the data could be described by a single linear relationship between the logarithms of the surface-area-normalized rate constant ( k SA ) values and E H and pH values [log( k SA ) = - E H /0.059 V - pH + 3.42]. This framework provides mechanistic insights into how the thermodynamic favorability of electron transfer from oxide-bound Fe 2+ relates to redox reaction kinetics.

Microbial Electrosynthesis: Feeding Microbes Electricity To Convert Carbon Dioxide and Water to Multicarbon Extracellular Organic Compounds

PubMed Central

Nevin, Kelly P.; Woodard, Trevor L.; Franks, Ashley E.; Summers, Zarath M.; Lovley, Derek R.

2010-01-01

The possibility of providing the acetogenic microorganism Sporomusa ovata with electrons delivered directly to the cells with a graphite electrode for the reduction of carbon dioxide to organic compounds was investigated. Biofilms of S. ovata growing on graphite cathode surfaces consumed electrons with the reduction of carbon dioxide to acetate and small amounts of 2-oxobutyrate. Electrons appearing in these products accounted for over 85% of the electrons consumed. These results demonstrate that microbial production of multicarbon organic compounds from carbon dioxide and water with electricity as the energy source is feasible. PMID:20714445

The use of remote sensing and linear wave theory to model local wave energy around Alphonse Atoll, Seychelles

NASA Astrophysics Data System (ADS)

Hamylton, S.

2011-12-01

This paper demonstrates a practical step-wise method for modelling wave energy at the landscape scale using GIS and remote sensing techniques at Alphonse Atoll, Seychelles. Inputs are a map of the benthic surface (seabed) cover, a detailed bathymetric model derived from remotely sensed Compact Airborne Spectrographic Imager (CASI) data and information on regional wave heights. Incident energy at the reef crest around the atoll perimeter is calculated as a function of its deepwater value with wave parameters (significant wave height and period) hindcast in the offshore zone using the WaveWatch III application developed by the National Oceanographic and Atmospheric Administration. Energy modifications are calculated at constant intervals as waves transform over the forereef platform along a series of reef profile transects running into the atoll centre. Factors for shoaling, refraction and frictional attenuation are calculated at each interval for given changes in bathymetry and benthic coverage type and a nominal reduction in absolute energy is incorporated at the reef crest to account for wave breaking. Overall energy estimates are derived for a period of 5 years and related to spatial patterning of reef flat surface cover (sand and seagrass patches).

Energy saving and consumption reducing evaluation of thermal power plant

NASA Astrophysics Data System (ADS)

Tan, Xiu; Han, Miaomiao

2018-03-01

At present, energy saving and consumption reduction require energy saving and consumption reduction measures for thermal power plant, establishing an evaluation system for energy conservation and consumption reduction is instructive for the whole energy saving work of thermal power plant. By analysing the existing evaluation system of energy conservation and consumption reduction, this paper points out that in addition to the technical indicators of power plant, market activities should also be introduced in the evaluation of energy saving and consumption reduction in power plant. Ttherefore, a new evaluation index of energy saving and consumption reduction is set up and the example power plant is calculated in this paper. Rresults show that after introducing the new evaluation index of energy saving and consumption reduction, the energy saving effect of the power plant can be judged more comprehensively, so as to better guide the work of energy saving and consumption reduction in power plant.

KINETICS OF TRICHLOROETHENE REDUCTION BY ZEROVALENT IRON AND TIN: PRETREATMENT EFFECT, APPARENT ACTIVATION ENERGY, AND INTERMEDIATE PRODUCTS

EPA Science Inventory

The degradation of trichloroethene (TCE) at 2 mg L-1 in headspace free aqueous solution by zerovalent iron (Feo) and tin (Sno) was studied in batch tests at 10, 25, 40, and 55 degrees C and HCI-treated Feo and Sno at 25 and 55 degrees C. The HCI-washing increased metal surface a...

Trend in the Catalytic Activity of Transition Metals for the Oxygen Reduction Reaction by Lithium

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

Dathar, Gopi Krishna Phani; Shelton Jr, William Allison; Xu, Ye

2012-01-01

Periodic density functional theory (DFT) calculations indicate that the intrinsic activity of Au, Ag, Pt, Pd, Ir, and Ru for the oxygen reduction reaction by Li (Li-ORR) forms a volcano-like trend with respect to the adsorption energy of oxygen, with Pt and Pd being the most active. The trend is based on two mechanisms: the reduction of molecular O{sub 2} on Au and Ag and of atomic O on the remaining metals. Step edges are found to be more active for catalyzing the Li-ORR than close-packed surfaces. Our findings identify important considerations in the design of catalyst-promoted air cathodes formore » nonaqueous Li-air batteries.« less

Surface Immobilization of Transition Metal Ions on Nitrogen-Doped Graphene Realizing High-Efficient and Selective CO2 Reduction.

PubMed

Bi, Wentuan; Li, Xiaogang; You, Rui; Chen, Minglong; Yuan, Ruilin; Huang, Weixin; Wu, Xiaojun; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2018-05-01

Electrochemical conversion of CO 2 to value-added chemicals using renewable electricity provides a promising way to mitigate both global warming and the energy crisis. Here, a facile ion-adsorption strategy is reported to construct highly active graphene-based catalysts for CO 2 reduction to CO. The isolated transition metal cyclam-like moieties formed upon ion adsorption are found to contribute to the observed improvements. Free from the conventional harsh pyrolysis and acid-leaching procedures, this solution-chemistry strategy is easy to scale up and of general applicability, thus paving a rational avenue for the design of high-efficiency catalysts for CO 2 reduction and beyond. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of phosphate-based glass fibre surface properties on thermally produced poly(lactic acid) matrix composites.

PubMed

Mohammadi, Maziar Shah; Ahmed, Ifty; Muja, Naser; Rudd, Christopher D; Bureau, Martin N; Nazhat, Showan N

2011-12-01

Incorporation of soluble bioactive glass fibres into biodegradable polymers is an interesting approach for bone repair and regeneration. However, the glass composition and its surface properties significantly affect the nature of the fibre-matrix interface and composite properties. Herein, the effect of Si and Fe on the surface properties of calcium containing phosphate based glasses (PGs) in the system (50P(2)O(5)-40CaO-(10-x)SiO(2)-xFe(2)O(3), where x = 0, 5 and 10 mol.%) were investigated. Contact angle measurements revealed a higher surface energy, and surface polarity as well as increased hydrophilicity for Si doped PG which may account for the presence of surface hydroxyl groups. Two PG formulations, 50P(2)O(5)-40CaO-10Fe(2)O(3) (Fe10) and 50P(2)O(5)-40CaO-5Fe(2)O(3)-5SiO(2) (Fe5Si5), were melt drawn into fibres and randomly incorporated into poly(lactic acid) (PLA) produced by melt processing. The ageing in deionised water (DW), mechanical property changes in phosphate buffered saline (PBS) and cytocompatibility properties of these composites were investigated. In contrast to Fe10 and as a consequence of the higher surface energy and polarity of Fe5Si5, its incorporation into PLA led to increased inorganic/organic interaction indicated by a reduction in the carbonyl group of the matrix. PLA chain scission was confirmed by a greater reduction in its molecular weight in PLA-Fe5Si5 composites. In DW, the dissolution rate of PLA-Fe5Si5 was significantly higher than that of PLA-Fe10. Dissolution of the glass fibres resulted in the formation of channels within the matrix. Initial flexural strength was significantly increased through PGF incorporation. After PBS ageing, the reduction in mechanical properties was greater for PLA-Fe5Si5 compared to PLA-Fe10. MC3T3-E1 preosteoblasts seeded onto PG discs, PLA and PLA-PGF composites were evaluated for up to 7 days indicating that the materials were generally cytocompatible. In addition, cell alignment along the PGF orientation was observed showing cell preference towards PGF.

Method and Apparatus for the Quantification of Particulate Adhesion Forces on Various Substrates

NASA Technical Reports Server (NTRS)

Wohl, Christopher J.; Atkins, Brad M.; Connell, John W.

2011-01-01

Mitigation strategies for lunar dust adhesion have typically been limited to qualitative analysis. This technical memorandum describes the generation and operation of an adhesion testing device capable of quantitative assessment of adhesion forces between particulates and substrates. An aerosolization technique is described to coat a surface with a monolayer of particulates. Agitation of this surface, via sonication, causes particles to dislodge and be gravitationally fed into an optical particle counter. Experimentally determined adhesion force values are compared to forces calculated from van der Waals interactions and are used to calculate the work of adhesion using Johnson-Kendall-Roberts (JKR) theory. Preliminary results indicate that a reduction in surface energy and available surface area, through topographical modification, improve mitigation of particulate adhesion.

Mechanistic insights into electrochemical reduction of CO2 over Ag using density functional theory and transport models

PubMed Central

Goodpaster, Jason D.; Weber, Adam Z.

2017-01-01

Electrochemical reduction of CO2 using renewable sources of electrical energy holds promise for converting CO2 to fuels and chemicals. Since this process is complex and involves a large number of species and physical phenomena, a comprehensive understanding of the factors controlling product distribution is required. While the most plausible reaction pathway is usually identified from quantum-chemical calculation of the lowest free-energy pathway, this approach can be misleading when coverages of adsorbed species determined for alternative mechanism differ significantly, since elementary reaction rates depend on the product of the rate coefficient and the coverage of species involved in the reaction. Moreover, cathode polarization can influence the kinetics of CO2 reduction. Here, we present a multiscale framework for ab initio simulation of the electrochemical reduction of CO2 over an Ag(110) surface. A continuum model for species transport is combined with a microkinetic model for the cathode reaction dynamics. Free energies of activation for all elementary reactions are determined from density functional theory calculations. Using this approach, three alternative mechanisms for CO2 reduction were examined. The rate-limiting step in each mechanism is **COOH formation at higher negative potentials. However, only via the multiscale simulation was it possible to identify the mechanism that leads to a dependence of the rate of CO formation on the partial pressure of CO2 that is consistent with experiments. Simulations based on this mechanism also describe the dependence of the H2 and CO current densities on cathode voltage that are in strikingly good agreement with experimental observation. PMID:28973926

Solid-State Kinetic Investigations of Nonisothermal Reduction of Iron Species Supported on SBA-15

PubMed Central

2017-01-01

Iron oxide catalysts supported on nanostructured silica SBA-15 were synthesized with various iron loadings using two different precursors. Structural characterization of the as-prepared FexOy/SBA-15 samples was performed by nitrogen physisorption, X-ray diffraction, DR-UV-Vis spectroscopy, and Mössbauer spectroscopy. An increasing size of the resulting iron species correlated with an increasing iron loading. Significantly smaller iron species were obtained from (Fe(III), NH4)-citrate precursors compared to Fe(III)-nitrate precursors. Moreover, smaller iron species resulted in a smoother surface of the support material. Temperature-programmed reduction (TPR) of the FexOy/SBA-15 samples with H2 revealed better reducibility of the samples originating from Fe(III)-nitrate precursors. Varying the iron loading led to a change in reduction mechanism. TPR traces were analyzed by model-independent Kissinger method, Ozawa, Flynn, and Wall (OFW) method, and model-dependent Coats-Redfern method. JMAK kinetic analysis afforded a one-dimensional reduction process for the FexOy/SBA-15 samples. The Kissinger method yielded the lowest apparent activation energy for the lowest loaded citrate sample (Ea ≈ 39 kJ/mol). Conversely, the lowest loaded nitrate sample possessed the highest apparent activation energy (Ea ≈ 88 kJ/mol). For samples obtained from Fe(III)-nitrate precursors, Ea decreased with increasing iron loading. Apparent activation energies from model-independent analysis methods agreed well with those from model-dependent methods. Nucleation as rate-determining step in the reduction of the iron oxide species was consistent with the Mampel solid-state reaction model. PMID:29230346

Methanol synthesis on ZnO(0001{sup ¯}). IV. Reaction mechanisms and electronic structure

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

Frenzel, Johannes, E-mail: johannes.frenzel@theochem.rub.de; Marx, Dominik

2014-09-28

Methanol synthesis from CO and H{sub 2} over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partiallymore » hydroxylated and defective ZnO(0001{sup ¯}) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving “near-surface” molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H{sub 2} stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are discussed based on extensive electronic structure analysis.« less

Etude de l'electrocatalyse de la reduction de l'oxygene sur des alliages de palladium cuivre

NASA Astrophysics Data System (ADS)

Fouda-Onana, Frederic

This thesis is on the development of the ORR on Pd-Cu alloys in acid medium. Density Functional Theory (DFT) was used to determine the intrinsic properties of the alloys. The alloys were fabricated by RF sputtering on glassy carbon support and chemical salt reduction on carbon support. They characterised by electrochemical methods and correlations were made between the intrinsic properties and the experimental electrochemical parameters. These correlations were used to explain the electrocatalytic performance of the ORR on these aklooys and to determine the mechanism of this reaction on these electrocatalysts. Accordingly the following aspects were studied in details. In the first step, ab initio investigations of the effect of the intermediate adsorption on the variation of the reversible potential of the ORR on Pt(100) was shown. Density Functional Theory (DFT) was used to determine the energies and the geometry parameters of the intermediates which can be adsorbed on Pt(100) during the oxygen reduction reaction (ORR) and their effect on the . The Comparison of these energies and parameters using the Bridge or the Griffiths sites adsorption mechanism suggests that the two paths are feasible. In both mechanisms, the total adsorption energies of the intermediates species continuously decrease. Moreover, according to the geometry analysis, the O-O bond distance in H2O2 is higher in both (Bridge and Griffiths) processes compared to the gas phase. Such a result suggests a dissociative H2O2 adsorption whatever the type of the involved mechanism involved. In the second step, the Oxygen reduction reaction (ORR) on palladium-copper alloys was studied through two approaches. The first one is based on the correlations between the surface chemical composition and the kinetics parameters of the ORR. The second approach is focused on the correlations between the adsorption energies of O2 and OH of Pd-Cu(111) surfaces and the electronic properties of the alloys. The adsorbtion energy calculations are based on on ab initio calculation using the program VASP (Vienna ab initio program) in a MeDeA environnement (software purchased from Materials Design, Inc. The studies of the oxygen reduction reaction were performed in an acidic media on Palladium-Copper alloys as catalyst. The variation of the intrinsic metal surface properties (lattice parameter, binding energy, work function (Wf), d-band filling and d-band center epsilond) and O2 and OH adsorption energies of on (111) Pd-Cu surface alloys were determined using ab initio program. Calculations of these parameters were based on plane waves approach on slab system with density functional theory (DFT) using the Vienna ab initio simulation program (VASP). It was shown that insertion of Cu atoms in Pd lattice affects geometric and electronic properties of Pd. These changes influence significantly O2 and OH adsorption. In the third step, the oxygen reduction reaction (ORR) on Pd-Cu catalyst has been studied in acidic media. The palladium alloys were prepared by RF magnetron using a palladium and a copper wafer as targets on the glassy carbon substrate. The dual sputtering we used allowed the deposition of about 1micrometer thin film of Pd-Cu on glassy carbon (GC). The ORR kinetics was studied on these catalysts in 0,1M HClO4. Cyclic voltammetry (CV) was used to determine the electrochemical active surface area (Sa). An increase in Sa with the Cu content in the alloy was observed for the alloys containing more than 50% in Cu. The Pd-Cu alloys containing more than 50% in Cu exhibits a constant value of 23 cm2 for Sa. It was further shown that the ORR on the Pd-Cu alloys proceeds through the 4 electrons transfer mechanism and a Tafel slope of 60 mV/dec. The Pd 50Cu50 exhibits the highest activity for this reaction. The enhancement of the electro catalytic activity is attributed to an optimal d band property that makes easier the OOH dissociative adsorption which is considered as chemical rate determining step (RDS) for the ORR. It was also found that all the Pd-Cu alloys exhibited better electrocatalystic performances for the ORR than Pd or Cu alone. From the polarisation of the ORR in 0,1 M HClO4 it was shown that the curve of the Pd electrode was shifted to the lower potentials than those of the Pd-Cu alooys. In addition, the variation of the kinetic current of the ORR at 0,6 V vs. SCE (0,841 V vs. RHE) on the Pd-Cu alloys with the composition of in Cu content exhibited a volcano-shape. (Abstract shortened by UMI.)

Improving Density Functional Tight Binding Predictions of Free Energy Surfaces for Slow Chemical Reactions in Solution

NASA Astrophysics Data System (ADS)

Kroonblawd, Matthew; Goldman, Nir

2017-06-01

First principles molecular dynamics using highly accurate density functional theory (DFT) is a common tool for predicting chemistry, but the accessible time and space scales are often orders of magnitude beyond the resolution of experiments. Semi-empirical methods such as density functional tight binding (DFTB) offer up to a thousand-fold reduction in required CPU hours and can approach experimental scales. However, standard DFTB parameter sets lack good transferability and calibration for a particular system is usually necessary. Force matching the pairwise repulsive energy term in DFTB to short DFT trajectories can improve the former's accuracy for reactions that are fast relative to DFT simulation times (<10 ps), but the effects on slow reactions and the free energy surface are not well-known. We present a force matching approach to improve the chemical accuracy of DFTB. Accelerated sampling techniques are combined with path collective variables to generate the reference DFT data set and validate fitted DFTB potentials. Accuracy of force-matched DFTB free energy surfaces is assessed for slow peptide-forming reactions by direct comparison to DFT for particular paths. Extensions to model prebiotic chemistry under shock conditions are discussed. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Boiling and quenching heat transfer advancement by nanoscale surface modification.

PubMed

Hu, Hong; Xu, Cheng; Zhao, Yang; Ziegler, Kirk J; Chung, J N

2017-07-21

All power production, refrigeration, and advanced electronic systems depend on efficient heat transfer mechanisms for achieving high power density and best system efficiency. Breakthrough advancement in boiling and quenching phase-change heat transfer processes by nanoscale surface texturing can lead to higher energy transfer efficiencies, substantial energy savings, and global reduction in greenhouse gas emissions. This paper reports breakthrough advancements on both fronts of boiling and quenching. The critical heat flux (CHF) in boiling and the Leidenfrost point temperature (LPT) in quenching are the bottlenecks to the heat transfer advancements. As compared to a conventional aluminum surface, the current research reports a substantial enhancement of the CHF by 112% and an increase of the LPT by 40 K using an aluminum surface with anodized aluminum oxide (AAO) nanoporous texture finish. These heat transfer enhancements imply that the power density would increase by more than 100% and the quenching efficiency would be raised by 33%. A theory that links the nucleation potential of the surface to heat transfer rates has been developed and it successfully explains the current finding by revealing that the heat transfer modification and enhancement are mainly attributed to the superhydrophilic surface property and excessive nanoscale nucleation sites created by the nanoporous surface.

The influence of implantoplasty on the diameter, chemical surface composition, and biocompatibility of titanium implants.

PubMed

Schwarz, Frank; John, Gordon; Becker, Jürgen

2017-09-01

The objective of the study was to assess the influence of implantoplasty (IP) on the diameter, chemical surface composition, and biocompatibility of titanium implants in vitro. Twenty soft tissue-level (TL; machined transmucosal-M and rough endosseous part-SLA) and 20 bone-level (BL; SLA) implants were allocated to IP covering 3 or 6 mm of the structured surface (SLA) area. The samples were subjected to diameter, energy-dispersive X-ray spectroscopy (EDX), and cell viability (ginigval fibroblasts, 6 days) assessments. Median diameter reductions varied between 0.1 (TL 3 mm) and 0.2 mm (TL 6 mm). EDX analysis revealed that IP and M surfaces were characterized by a comparable quantity (Wt%) of elements C, O, Na, Cl, K, and Si, but a significantly different quantity of elements Ti and Al. When compared to SLA surfaces, significant differences were noted for elements C, O, Na, Ti, and Al. At BL implants, the extension of IP (i.e., 3 to 6 mm) was associated with a significant increase in cell viability. IP applied to SLA implants was associated with (i) a minimal diameter reduction, (ii) an undisturbed cell viability, and (iii) a chemical elemental composition comparable to M surfaces. This specific IP procedure appears to be suitable for the management of exposed SLA implant surfaces.

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

Chemke, Rei; Kaspi, Yohai, E-mail: rei.chemke@weizmann.ac.il

The many recently discovered terrestrial exoplanets are expected to hold a wide range of atmospheric masses. Here the dynamic-thermodynamic effects of atmospheric mass on atmospheric circulation are studied using an idealized global circulation model by systematically varying the atmospheric surface pressure. On an Earth analog planet, an increase in atmospheric mass weakens the Hadley circulation and decreases its latitudinal extent. These changes are found to be related to the reduction of the convective fluxes and net radiative cooling (due to the higher atmospheric heat capacity), which, respectively, cool the upper troposphere at mid-low latitudes and warm the troposphere at highmore » latitudes. These together decrease the meridional temperature gradient, tropopause height and static stability. The reduction of these parameters, which play a key role in affecting the flow properties of the tropical circulation, weakens and contracts the Hadley circulation. The reduction of the meridional temperature gradient also decreases the extraction of mean potential energy to the eddy fields and the mean kinetic energy, which weakens the extratropical circulation. The decrease of the eddy kinetic energy decreases the Rhines wavelength, which is found to follow the meridional jet scale. The contraction of the jet scale in the extratropics results in multiple jets and meridional circulation cells as the atmospheric mass increases.« less

Albedo as a modulator of climate response to tropical deforestation

NASA Technical Reports Server (NTRS)

Dirmeyer, Paul A.; Shukla, J.

1994-01-01

An atmospheric general circulation model with land surface properties represented by the simplified Simple Biosphere model is used to investigate the effects on local climate due to tropical deforestation for the Amazon basin. One control and three anomaly integrations of 4 years' duration are performed. In the anomaly integrations, rain forest in South America is replaced by degraded grassland. The anomaly integrations differ only in the optical properties of the grassland vegetation, with net surface albedos ranging from the same as to 0.09 lighter than that of rain forest. It is found that the change in climate, particularly rainfall, is strongly dependent on the change in surface albedo that accompanies deforestation. Replacement of forest by grass causes a reduction in transpiration and reduces frictional convergence by decreasing surface roughness. However, precipitation averaged over the deforested area is not necessarily reduced. Average precipitation decreases when the increase in albedo is greater than 0.03. If surface albedo is not increased appreciably as a result of deforestation, moisture flux convergence driven by the increase in surface temperature can offset the other effects, and average precipitation increases. As albedo is increased, surface temperature does not change, but surface latent and sensible heat flux decreases due to reduced radiational energy absorbed at the surface, resulting in a reduction in convection and precipitation. A change in the distribution of precipitation due to deforestation that appears to be independent of the albedo is observed.

Albedo as a modulator of climate response to tropical deforestation

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

Dirmeyer, P.A.; Shukla, J.

1994-10-01

An atmospheric general circulation model with land surface properties represented by the simplified Simple Biosphere model is used to investigate the effects on local climate due to tropical deforestation for the Amazon basin. One control and three anomaly integrations of 4 years` duration are performed. In the anomaly integrations, rain forest in South America is replaced by degraded grassland. The anomaly integrations differ only in the optical properties of the grassland vegetation, with net surface albedos ranging from the same as to 0.09 lighter than that of rain forest. It is found that the change in climate, particularly rainfall, ismore » strongly dependent on the change in surface albedo that accompanies deforestation. Replacement of forest by grass causes a reduction in transpiration and reduces frictional convergence by decreasing surface roughness. However, precipitation averaged over the deforested area is not necessarily reduced. Average precipitation decreases when the increase in albedo is greater than 0.03. If surface albedo is not increased appreciably as a result of deforestation, moisture flux convergence driven by the increase in surface temperature can offset the other effects, and average precipitation increases. As albedo is increased, surface temperature does not change, but surface latent and sensible heat flux decreases due to reduced radiational energy absorbed at the surface, resulting in a reduction in convection and precipitation. A change in the distribution of precipitation due to deforestation that appears to be independent of the albedo is observed.« less

Effect of Machining Parameters on Oxidation Behavior of Mild Steel

NASA Astrophysics Data System (ADS)

Majumdar, P.; Shekhar, S.; Mondal, K.

2015-01-01

This study aims to find out a correlation between machining parameters, resultant microstructure, and isothermal oxidation behavior of lathe-machined mild steel in the temperature range of 660-710 °C. The tool rake angles "α" used were +20°, 0°, and -20°, and cutting speeds used were 41, 232, and 541 mm/s. Under isothermal conditions, non-machined and machined mild steel samples follow parabolic oxidation kinetics with activation energy of 181 and ~400 kJ/mol, respectively. Exaggerated grain growth of the machined surface was observed, whereas, the center part of the machined sample showed minimal grain growth during oxidation at higher temperatures. Grain growth on the surface was attributed to the reduction of strain energy at high temperature oxidation, which was accumulated on the sub-region of the machined surface during machining. It was also observed that characteristic surface oxide controlled the oxidation behavior of the machined samples. This study clearly demonstrates the effect of equivalent strain, roughness, and grain size due to machining, and subsequent grain growth on the oxidation behavior of the mild steel.

Aerosol contribution to the rapid warming of near-term climate under RCP 2.6

NASA Astrophysics Data System (ADS)

Chalmers, N.; Highwood, E. J.; Hawkins, E.; Sutton, R.; Wilcox, L. J.

2012-09-01

The importance of aerosol emissions for near term climate projections is investigated by analysing simulations with the HadGEM2-ES model under two different emissions scenarios: RCP2.6 and RCP4.5. It is shown that the near term warming projected under RCP2.6 is greater than under RCP4.5, even though the greenhouse gas forcing is lower. Rapid and substantial reductions in sulphate aerosol emissions due to a reduction of coal burning in RCP2.6 lead to a reduction in the negative shortwave forcing due to aerosol direct and indirect effects. Indirect effects play an important role over the northern hemisphere oceans, especially the subtropical northeastern Pacific where an anomaly of 5-10 Wm-2 develops. The pattern of surface temperature change is consistent with the expected response to this surface radiation anomaly, whilst also exhibiting features that reflect redistribution of energy, and feedbacks, within the climate system. These results demonstrate the importance of aerosol emissions as a key source of uncertainty in near term projections of global and regional climate.

The O2 reduction at the IFC modified O2 fuel cell electrode

NASA Technical Reports Server (NTRS)

Fielder, William L.; Singer, Joseph; Baldwin, Richard S.; Johnson, Richard E.

1992-01-01

The International Fuel Corporation (IFC) state of the art (SOA) O2 electrode (Au-10 percent Pt electrocatalyst by weight) is currently being used in the alkaline H2-O2 fuel cell in the NASA Space Shuttle. Recently, IFC modified O2 electrode, as a possible replacement for the SOA electrode. In the present study, O2 reduction data were obtained for the modified electrode at temperatures between 23.3 and 91.7 C. BET measurements gave an electrode BET surface area of about 2070 sq. cm/sq. cm of geometric surface area. The Tafel data could be fitted to two straight line regions. The slope for the lower region, designated as the 0.04 V/decade region, was temperature dependent, and the transfer coefficient was about 1.5. The 'apparent' energy of activation for this region was about 19 kcal/mol. An O2 reduction mechanism for this 0.04 region is presented. In the upper region, designated as the 0.08 V/decade region, diffusion may be the controlling process. Tafel data are presented to illustrate the increase in performance with increasing temperature.

Radiation induced deposition of copper nanoparticles inside the nanochannels of poly(acrylic acid)-grafted poly(ethylene terephthalate) track-etched membranes

NASA Astrophysics Data System (ADS)

Korolkov, Ilya V.; Güven, Olgun; Mashentseva, Anastassiya A.; Atıcı, Ayse Bakar; Gorin, Yevgeniy G.; Zdorovets, Maxim V.; Taltenov, Abzal A.

2017-01-01

Poly(ethylene terephthalate) PET, track-etched membranes (TeMs) with 400 nm average pore size were UV-grafted with poly(acrylic acid) (PAA) after oxidation of inner surfaces by H2O2/UV system. Carboxylate groups of grafted PAA chains were easily complexed with Cu2+ ions in aqueous solutions. These ions were converted into metallic copper nanoparticles (NPs) by radiation-induced reduction of copper ions in aqueous-alcohol solution by gamma rays in the dose range of 46-250 kGy. Copper ions chelating with -COOH groups of PAA chains grafted on PET TeMs form polymer-metal ion complex that prevent the formation of agglomerates during reduction of copper ions to metallic nanoparticles. The detailed analysis by X-Ray diffraction technique (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) confirmed the deposition of copper nanoparticles with the average size of 70 nm on the inner surface of nanochannels of PET TeMs. Samples were also investigated by FTIR, ESR spectroscopies to follow copper ion reduction.

Storage of Renewable Energy by Reduction of CO2 with Hydrogen.

PubMed

Züttel, Andreas; Mauron, Philippe; Kato, Shunsuke; Callini, Elsa; Holzer, Marco; Huang, Jianmei

2015-01-01

The main difference between the past energy economy during the industrialization period which was mainly based on mining of fossil fuels, e.g. coal, oil and methane and the future energy economy based on renewable energy is the requirement for storage of the energy fluxes. Renewable energy, except biomass, appears in time- and location-dependent energy fluxes as heat or electricity upon conversion. Storage and transport of energy requires a high energy density and has to be realized in a closed materials cycle. The hydrogen cycle, i.e. production of hydrogen from water by renewable energy, storage and use of hydrogen in fuel cells, combustion engines or turbines, is a closed cycle. However, the hydrogen density in a storage system is limited to 20 mass% and 150 kg/m(3) which limits the energy density to about half of the energy density in fossil fuels. Introducing CO(2) into the cycle and storing hydrogen by the reduction of CO(2) to hydrocarbons allows renewable energy to be converted into synthetic fuels with the same energy density as fossil fuels. The resulting cycle is a closed cycle (CO(2) neutral) if CO(2) is extracted from the atmosphere. Today's technology allows CO(2) to be reduced either by the Sabatier reaction to methane, by the reversed water gas shift reaction to CO and further reduction of CO by the Fischer-Tropsch synthesis (FTS) to hydrocarbons or over methanol to gasoline. The overall process can only be realized on a very large scale, because the large number of by-products of FTS requires the use of a refinery. Therefore, a well-controlled reaction to a specific product is required for the efficient conversion of renewable energy (electricity) into an easy to store liquid hydrocarbon (fuel). In order to realize a closed hydrocarbon cycle the two major challenges are to extract CO(2) from the atmosphere close to the thermodynamic limit and to reduce CO(2) with hydrogen in a controlled reaction to a specific hydrocarbon. Nanomaterials with nanopores and the unique surface structures of metallic clusters offer new opportunities for the production of synthetic fuels.

Biotransformation of carbon dioxide in bioelectrochemical systems: State of the art and future prospects

NASA Astrophysics Data System (ADS)

Bajracharya, Suman; Srikanth, Sandipam; Mohanakrishna, Gunda; Zacharia, Renju; Strik, David PBTB; Pant, Deepak

2017-07-01

Carbon dioxide (CO2) utilization/recycling for the production of chemicals and gaseous/liquid energy-carriers is a way to moderate the rising CO2 in the atmosphere. One of the possible solutions for the CO2 sequestration is the electrochemical reduction of this stable molecule to useful fuel/products. Nevertheless, the surface chemistry of CO2 reduction is a challenge due to the presence of large energy barriers, requiring noticeable catalysis. The recent approach of microbial electrocatalysis of CO2 reduction has promising prospects to reduce the carbon level sustainably, taking full advantage of CO2-derived chemical commodities. We review the currently investigated bioelectrochemical approaches that could possibly be implemented to enable the handling of CO2 emissions. This review covers the most recent advances in the bioelectrochemical approaches of CO2 transformations in terms of biocatalysts development and process design. Furthermore, the extensive research on carbon fixation and conversion to different value added chemicals is reviewed. The review concludes by detailing the key challenges and future prospects that could enable economically feasible microbial electrosynthesis technology.

Delayed warming hiatus over the Tibetan Plateau

NASA Astrophysics Data System (ADS)

An, Wenling; Hou, Shugui; Hu, Yongyun; Wu, Shuangye

2017-03-01

A reduction in the warming rate for the global surface temperature since the late 1990s has attracted much attention and caused a great deal of controversy. During the same time period, however, most previous studies have reported enhanced warming over the Tibetan Plateau (TP). In this study we further examined the temperature trend of the TP and surrounding areas based on the homogenized temperature records for the period 1980-2014, we found that for the TP regions lower than 4000 m the warming rate has started to slow down since the late 1990s, a similar pattern consistent with the whole China and the global temperature trend. However, for the TP regions higher than 4000 m, this reduction in warming rate did not occur until the mid-2000s. This delayed warming hiatus could be related to changes in regional radiative, energy, and land surface processes in recent years.

Identification of Molecular and Cellular Responses of Desulfovibrio vulgaris Biofilms under Culture Conditions Relevant to Field Conditions for Bioreduction of Toxic Metals and Radionuclides

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

Judy D. Wall

2011-06-09

Our findings demonstrated that D. vulgaris surface-adhered populations produce extracellular structures, and that that the cells have altered carbon and energy flux compared to planktonic cells. Biofilms did not have greatly increased carbohydrate accumulation. Interestingly genes present on the native plasmid found in D. vulgaris Hildenborough were necessary for wild type biofilm formation. In addition, extracellular appendages dependent on functions or proteins encoded by flaG or fliA also contributed to biofilm formation. Studies with SRB biofilms have indicated that the reduction and precipitation of metals can occur within the biofilm matrix; however, little work has been done to elucidate themore » physiological state of surface-adhered cells during metal reduction (Cr6+, U6+) and how this process is affected by nutrient feed levels (i.e., the stimulant).« less

Evidence of enzymatic catalysis of oxygen reduction on stainless steels under marine biofilm.

PubMed

Faimali, Marco; Benedetti, Alessandro; Pavanello, Giovanni; Chelossi, Elisabetta; Wrubl, Federico; Mollica, Alfonso

2011-04-01

Cathodic current trends on stainless steel samples with different surface percentages covered by biofilm and potentiostatically polarized in natural seawater were studied under oxygen concentration changes, temperature increases, and additions of enzymic inhibitors to the solution. The results showed that on each surface fraction covered by biofilm the oxygen reduction kinetics resembled a reaction catalyzed by an immobilised enzyme with high oxygen affinity (apparent Michaelis-Menten dissociation constant close to K(O(2))(M)  ≈ 10 μM) and low activation energy (W ≈ 20 KJ mole(-1)). The proposed enzyme rapidly degraded when the temperature was increased above the ambient (half-life time of ∼1 day at 25°C, and of a few minutes at 50°C). Furthermore, when reversible enzymic inhibitors (eg sodium azide and cyanide) were added, the cathodic current induced by biofilm growth was inhibited.

Effect of Fermi surface nesting on resonant spin excitations in Ba{<_1-x}K{<_x}Fe{<_2}As{<_2}.

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

Castellan, J.-P.; Rosenkranz, S.; Goremychkin, E.A.

2011-01-01

We report inelastic neutron scattering measurements of the resonant spin excitations in Ba{sub 1-x}K{sub x}Fe{sub 2}As{sub 2} over a broad range of electron band filling. The fall in the superconducting transition temperature with hole doping coincides with the magnetic excitations splitting into two incommensurate peaks because of the growing mismatch in the hole and electron Fermi surface volumes, as confirmed by a tight-binding model with s{sub {+-}}-symmetry pairing. The reduction in Fermi surface nesting is accompanied by a collapse of the resonance binding energy and its spectral weight, caused by the weakening of electron-electron correlations.

Modeling hydrological controls on variations in peat water content, water table depth, and surface energy exchange of a boreal western Canadian fen peatland

NASA Astrophysics Data System (ADS)

Mezbahuddin, M.; Grant, R. F.; Flanagan, L. B.

2016-08-01

Improved predictive capacity of hydrology and surface energy exchange is critical for conserving boreal peatland carbon sequestration under drier and warmer climates. We represented basic processes for water and O2 transport and their effects on ecosystem water, energy, carbon, and nutrient cycling in a process-based model ecosys to simulate effects of seasonal and interannual variations in hydrology on peat water content, water table depth (WTD), and surface energy exchange of a Western Canadian fen peatland. Substituting a van Genuchten model (VGM) for a modified Campbell model (MCM) in ecosys enabled a significantly better simulation of peat moisture retention as indicated by higher modeled versus measured R2 and Willmot's index (d) with VGM (R2 0.7, d 0.8) than with MCM (R2 0.25, d 0.35) for daily peat water contents from a wetter year 2004 to a drier year 2009. With the improved peat moisture simulation, ecosys modeled hourly WTD and energy fluxes reasonably well (modeled versus measured R2: WTD 0.6, net radiation 0.99, sensible heat >0.8, and latent heat >0.85). Gradually declining ratios of precipitation to evapotranspiration and of lateral recharge to discharge enabled simulation of a gradual drawdown of growing season WTD and a consequent peat drying from 2004 to 2009. When WTD fell below a threshold of 0.35 m below the hollow surface, intense drying of mosses in ecosys caused a simulated reduction in evapotranspiration and an increase in Bowen ratio during late growing season that were consistent with measurements. Hence, using appropriate water desorption curve coupled with vertical-lateral hydraulic schemes is vital to accurately simulate peatland hydrology and energy balance.

Rational design of competitive electrocatalysts for the oxygen reduction reaction in hydrogen fuel cells

NASA Astrophysics Data System (ADS)

Stolbov, Sergey; Alcántara Ortigoza, Marisol

2012-02-01

The large-scale application of one of the most promising clean and renewable sources of energy, hydrogen fuel cells, still awaits efficient and cost-effective electrocatalysts for the oxygen reduction reaction (ORR) occurring on the cathode. We demonstrate that truly rational design renders electrocatalysts possessing both qualities. By unifying the knowledge on surface morphology, composition, electronic structure and reactivity, we solve that sandwich-like structures are an excellent choice for optimization. Their constituting species couple synergistically yielding reaction-environment stability, cost-effectiveness and tunable reactivity. This cooperative-action concept enabled us to predict two advantageous ORR electrocatalysts. Density functional theory calculations of the reaction free-energy diagrams confirm that these materials are more active toward ORR than the so far best Pt-based catalysts. Our designing concept advances also a general approach for engineering materials in heterogeneous catalysis.

The reduction of carbon dioxide in iron biocatalyst catalytic hydrogenation reaction: a theoretical study.

PubMed

Yang, Longhua; Wang, Hongming; Zhang, Ning; Hong, Sanguo

2013-08-21

The reaction mechanism of CO₂ hydrogenation catalyzed by [FeH(PP₃)]BF₄ (PP₃ = P(CH₂CH₂PPh₂)₃) had been investigated by DFT calculations. Our calculations indicated that the reduction of carbon dioxide could be carried out via two spin states, the high-spin (HS) triplet state and the low-spin (LS) singlet state. The minimum energy crossing points (MECPs) on the seam of two intersecting PESs (potential energy surfaces) were searched out. Some interesting phenomena, such as the open-loop phenomenon, and the O-rebound process, were demonstrated to be the important causes of the spin crossover. All these calculations gave us insight into the essence of the related experiment from the macro point of view, and helped to verify which spin states the related complexes pertinent were in. All of these researches would help advance the development of efficient and structurally tailorable CO₂ hydrogenation catalysts.

Slippery Liquid-Infused Porous Surfaces and Droplet Transportation by Surface Acoustic Waves

NASA Astrophysics Data System (ADS)

Luo, J. T.; Geraldi, N. R.; Guan, J. H.; McHale, G.; Wells, G. G.; Fu, Y. Q.

2017-01-01

On a solid surface, a droplet of liquid will stick due to the capillary adhesion, and this causes low droplet mobility. To reduce contact line pinning, surface chemistry can be coupled to micro- and/or nanostructures to create superhydrophobic surfaces on which a droplet balls up into an almost spherical shape, thus, minimizing the contact area. Recent progress in soft matter has now led to alternative lubricant-impregnated surfaces capable of almost zero contact line pinning and high droplet mobility without causing droplets to ball up and minimize the contact area. Here we report an approach to surface-acoustic-wave- (SAW) actuated droplet transportation enabled using such a surface. These surfaces maintain the contact area required for efficient energy and momentum transfer of the wave energy into the droplet while achieving high droplet mobility and a large footprint, therefore, reducing the threshold power required to induce droplet motion. In our approach, we use a slippery layer of lubricating oil infused into a self-assembled porous hydrophobic layer, which is significantly thinner than the SAW wavelength, and avoid damping of the wave. We find a significant reduction (up to 85%) in the threshold power for droplet transportation compared to that using a conventional surface-treatment method. Moreover, unlike droplets on superhydrophobic surfaces, where interaction with the SAW induces a transition from a Cassie-Baxter state to a Wenzel state, the droplets on our liquid-impregnated surfaces remain in a mobile state after interaction with the SAW.

Modifying Surface Chemistry of Metal Oxides for Boosting Dissolution Kinetics in Water by Liquid Cell Electron Microscopy.

PubMed

Lu, Yue; Geng, Jiguo; Wang, Kuan; Zhang, Wei; Ding, Wenqiang; Zhang, Zhenhua; Xie, Shaohua; Dai, Hongxing; Chen, Fu-Rong; Sui, Manling

2017-08-22

Dissolution of metal oxides is fundamentally important for understanding mineral evolution and micromachining oxide functional materials. In general, dissolution of metal oxides is a slow and inefficient chemical reaction. Here, by introducing oxygen deficiencies to modify the surface chemistry of oxides, we can boost the dissolution kinetics of metal oxides in water, as in situ demonstrated in a liquid environmental transmission electron microscope (LETEM). The dissolution rate constant significantly increases by 16-19 orders of magnitude, equivalent to a reduction of 0.97-1.11 eV in activation energy, as compared with the normal dissolution in acid. It is evidenced from the high-resolution TEM imaging, electron energy loss spectra, and first-principle calculations where the dissolution route of metal oxides is dynamically changed by local interoperability between altered water chemistry and surface oxygen deficiencies via electron radiolysis. This discovery inspires the development of a highly efficient electron lithography method for metal oxide films in ecofriendly water, which offers an advanced technique for nanodevice fabrication.

Morphological Evolution of Pit-Patterned Si(001) Substrates Driven by Surface-Energy Reduction

NASA Astrophysics Data System (ADS)

Salvalaglio, Marco; Backofen, Rainer; Voigt, Axel; Montalenti, Francesco

2017-09-01

Lateral ordering of heteroepitaxial islands can be conveniently achieved by suitable pit-patterning of the substrate prior to deposition. Controlling shape, orientation, and size of the pits is not trivial as, being metastable, they can significantly evolve during deposition/annealing. In this paper, we exploit a continuum model to explore the typical metastable pit morphologies that can be expected on Si(001), depending on the initial depth/shape. Evolution is predicted using a surface-diffusion model, formulated in a phase-field framework, and tackling surface-energy anisotropy. Results are shown to nicely reproduce typical metastable shapes reported in the literature. Moreover, long time scale evolutions of pit profiles with different depths are found to follow a similar kinetic pathway. The model is also exploited to treat the case of heteroepitaxial growth involving two materials characterized by different facets in their equilibrium Wulff's shape. This can lead to significant changes in morphologies, such as a rotation of the pit during deposition as evidenced in Ge/Si experiments.

Morphological Evolution of Pit-Patterned Si(001) Substrates Driven by Surface-Energy Reduction.

PubMed

Salvalaglio, Marco; Backofen, Rainer; Voigt, Axel; Montalenti, Francesco

2017-09-29

Lateral ordering of heteroepitaxial islands can be conveniently achieved by suitable pit-patterning of the substrate prior to deposition. Controlling shape, orientation, and size of the pits is not trivial as, being metastable, they can significantly evolve during deposition/annealing. In this paper, we exploit a continuum model to explore the typical metastable pit morphologies that can be expected on Si(001), depending on the initial depth/shape. Evolution is predicted using a surface-diffusion model, formulated in a phase-field framework, and tackling surface-energy anisotropy. Results are shown to nicely reproduce typical metastable shapes reported in the literature. Moreover, long time scale evolutions of pit profiles with different depths are found to follow a similar kinetic pathway. The model is also exploited to treat the case of heteroepitaxial growth involving two materials characterized by different facets in their equilibrium Wulff's shape. This can lead to significant changes in morphologies, such as a rotation of the pit during deposition as evidenced in Ge/Si experiments.

Observation of a well-defined hybridization gap and in-gap states on the SmB6 (001) surface

NASA Astrophysics Data System (ADS)

Sun, Zhixiang; Maldonado, Ana; Paz, Wendel S.; Inosov, Dmytro S.; Schnyder, Andreas P.; Palacios, J. J.; Shitsevalova, Natalya Yu.; Filipov, Vladimir B.; Wahl, Peter

2018-06-01

The rise of topology in condensed-matter physics has generated strong interest in identifying novel quantum materials in which topological protection is driven by electronic correlations. Samarium hexaboride is a Kondo insulator for which it has been proposed that a band inversion between 5 d and 4 f bands gives rise to topologically protected surface states. However, unambiguous proof of the existence and topological nature of these surface states is still missing, and its low-energy electronic structure is still not fully established. Here we present a study of samarium hexaboride by ultralow-temperature scanning tunneling microscopy and spectroscopy. We obtain clear atomically resolved topographic images of the sample surface. Our tunneling spectra reveal signatures of a hybridization gap with a size of about 8 meV and with a reduction of the differential conductance inside the gap by almost half, and surprisingly, several strong resonances below the Fermi level. The spatial variations of the energy of the resonances point toward a microscopic variation of the electronic states by the different surface terminations. High-resolution tunneling spectra acquired at 100 mK reveal a splitting of the Kondo resonance, possibly due to the crystal electric field.

Enhanced photoelectrochemical water splitting performance of anodic TiO(2) nanotube arrays by surface passivation.

PubMed

Gui, Qunfang; Xu, Zhen; Zhang, Haifeng; Cheng, Chuanwei; Zhu, Xufei; Yin, Min; Song, Ye; Lu, Linfeng; Chen, Xiaoyuan; Li, Dongdong

2014-10-08

One-dimensional anodic titanium oxide nanotube (TONT) arrays provide a direct pathway for charge transport, and thus hold great potential as working electrodes for electrochemical energy conversion and storage devices. However, the prominent surface recombination due to the large amount surface defects hinders the performance improvement. In this work, the surface states of TONTs were passivated by conformal coating of high-quality Al2O3 onto the tubular structures using atomic layer deposition (ALD). The modified TONT films were subsequently employed as anodes for photoelectrochemical (PEC) water splitting. The photocurrent (0.5 V vs Ag/AgCl) recorded under air mass 1.5 global illumination presented 0.8 times enhancement on the electrode with passivation coating. The reduction of surface recombination rate is responsible for the substantially improved performance, which is proposed to have originated from a decreased interface defect density in combination with a field-effect passivation induced by a negative fixed charge in the Al2O3 shells. These results not only provide a physical insight into the passivation effect, but also can be utilized as a guideline to design other energy conversion devices.

Synthesis of mono-dispersed nanofluids using solution plasma

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

Heo, Yong Kang, E-mail: yk@rd.numse.nagoya-u.ac.jp; Bratescu, Maria Antoaneta, E-mail: maria@rd.numse.nagoya-u.ac.jp; Knowledge Hub Aichi, Yakusa-cho, Nagakute-ku, Toyota

2014-07-14

Small-sized and well-dispersed gold nanoparticles (NPs) for nanofluidics have been synthesized by electrical discharge in liquid environment using termed solution plasma processing (SPP). Electrons and the hydrogen radicals are reducing the gold ions to the neutral form in plasma gas phase and liquid phase, respectively. The gold NPs have the smallest diameter of 4.9 nm when the solution temperature was kept at 20 °C. Nucleation and growth theory describe the evolution of the NP diameter right after the reduction reaction in function of the system temperature, NP surface energy, dispersion energy barrier, and nucleation rate. Negative charges on the NPs surface duringmore » and after SPP generate repulsive forces among the NPs avoiding their agglomeration in solution. Increasing the average energy in the SPP determines a decrease of the zeta potential and an increase of the NPs diameter. An important enhancement of the thermal conductivity of 9.4% was measured for the synthesized nanofluids containing NPs with the smallest size.« less

High brightness microwave lamp

DOEpatents

Kirkpatrick, Douglas A.; Dolan, James T.; MacLennan, Donald A.; Turner, Brian P.; Simpson, James E.

2003-09-09

An electrodeless microwave discharge lamp includes a source of microwave energy, a microwave cavity, a structure configured to transmit the microwave energy from the source to the microwave cavity, a bulb disposed within the microwave cavity, the bulb including a discharge forming fill which emits light when excited by the microwave energy, and a reflector disposed within the microwave cavity, wherein the reflector defines a reflective cavity which encompasses the bulb within its volume and has an inside surface area which is sufficiently less than an inside surface area of the microwave cavity. A portion of the reflector may define a light emitting aperture which extends from a position closely spaced to the bulb to a light transmissive end of the microwave cavity. Preferably, at least a portion of the reflector is spaced from a wall of the microwave cavity. The lamp may be substantially sealed from environmental contamination. The cavity may include a dielectric material is a sufficient amount to require a reduction in the size of the cavity to support the desired resonant mode.

Surface tension prevails over solute effect in organic-influenced cloud droplet activation.

PubMed

Ovadnevaite, Jurgita; Zuend, Andreas; Laaksonen, Ari; Sanchez, Kevin J; Roberts, Greg; Ceburnis, Darius; Decesari, Stefano; Rinaldi, Matteo; Hodas, Natasha; Facchini, Maria Cristina; Seinfeld, John H; O' Dowd, Colin

2017-06-29

The spontaneous growth of cloud condensation nuclei (CCN) into cloud droplets under supersaturated water vapour conditions is described by classic Köhler theory. This spontaneous activation of CCN depends on the interplay between the Raoult effect, whereby activation potential increases with decreasing water activity or increasing solute concentration, and the Kelvin effect, whereby activation potential decreases with decreasing droplet size or increases with decreasing surface tension, which is sensitive to surfactants. Surface tension lowering caused by organic surfactants, which diminishes the Kelvin effect, is expected to be negated by a concomitant reduction in the Raoult effect, driven by the displacement of surfactant molecules from the droplet bulk to the droplet-vapour interface. Here we present observational and theoretical evidence illustrating that, in ambient air, surface tension lowering can prevail over the reduction in the Raoult effect, leading to substantial increases in cloud droplet concentrations. We suggest that consideration of liquid-liquid phase separation, leading to complete or partial engulfing of a hygroscopic particle core by a hydrophobic organic-rich phase, can explain the lack of concomitant reduction of the Raoult effect, while maintaining substantial lowering of surface tension, even for partial surface coverage. Apart from the importance of particle size and composition in droplet activation, we show by observation and modelling that incorporation of phase-separation effects into activation thermodynamics can lead to a CCN number concentration that is up to ten times what is predicted by climate models, changing the properties of clouds. An adequate representation of the CCN activation process is essential to the prediction of clouds in climate models, and given the effect of clouds on the Earth's energy balance, improved prediction of aerosol-cloud-climate interactions is likely to result in improved assessments of future climate change.

Electron and hole relaxation pathways in semiconductor quantum dots

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

Klimov, V.I.; McBranch, D.W.; Leatherdale, C.A.

1999-11-01

Femtosecond (fs) broad-band transient absorption (TA) is used to study the intraband relaxation and depopulation dynamics of electron and hole quantized states in CdSe nanocrystals (NC{close_quote}s) with a range of surface properties. Instead of the drastic reduction in the energy relaxation rate expected due to a {open_quotes}phonon bottleneck,{close_quotes} we observe a fast subpicosecond 1P-to-1S electron relaxation, with the rate exceeding that due to phonon emission in bulk semiconductors. The energy relaxation is enhanced with reducing the NC{close_quote}s radius, and does not show any dependence on the NC surface properties (quality of the surface passivation). These data indicate that electron energymore » relaxation occurs by neither multiphonon emission nor by coupling to surface defects, but is likely meditated by Auger-type electron-hole energy transfer. We use fs infrared TA to probe electron and hole intraband transitions, which allows us to distinguish between electron and hole relaxation pathways leading to the depopulation of NC quantized states. In contrast to the electron relaxation, which is controlled by NC surface passivation, the depopulation of hole quantized states is extremely fast (sub-ps-to-ps time scales) in all types of samples, independent of NC surface treatment (including NC{close_quote}s overcoated with a ZnS layer). Our results indicate that ultrafast hole dynamics are not due to trapping at localized surface defects such as a vacancy, but rather arise from relaxation into intrinsic NC states or intrinsically unpassivated interface states. {copyright} {ital 1999} {ital The American Physical Society}« less

Drastic reduction of adsorption of CO and H2 on (111)-type Pd layers

NASA Technical Reports Server (NTRS)

Poppa, H.; Soria, F.

1983-01-01

Clean surfaces of (111)-type Pd layers, grown from the vapor phase on Mo(110) at room temperature, were used to study the adsorption of CO and H2 by temperature-programmed desorption, Auger electron spectroscopy, and low-energy electron diffraction. Mild annealing of the as-grown layers during a single desorption cycle (to about 600 K) drastically reduces the adsorption for both adsorbates. Low-dose argon-ion bombardment introduces surface imperfections which restore a high adsorption probability. The results are interpreted in terms of particular (111)-type surface structures that persist tp layer thicknesses of about four monolayers; the results raise questions with respect to the surface structure of supported thin epitaxial islands and particles of Pd and possibly also with respect to conventional methods of preparing bulk surfaces of Pd for adsorption studies.

Unique isothermal crystallization behavior of novel polyphenylene sulfide/inorganic fullerene-like WS2 nanocomposites.

PubMed

Naffakh, Mohammed; Marco, Carlos; Gómez, Marián A; Jiménez, Ignacio

2008-11-27

The isothermal crystallization of polyphenylene sulfide (PPS) nanocomposites with inorganic fullerene-like tungsten disulfide nanoparticles (IF-WS2) has been studied from a thermal and morphological point of view, using differential scanning calorimetry (DSC), scanning electron microscopy (SEM), polarized optical microscopy (POM) and time-resolved synchrotron X-ray diffraction. All the analyses revealed that the incorporation of the IF-WS2 altered significantly the crystallization behavior of PPS, in a way strongly dependent with the nanocomposite composition. The addition of IF-WS2 in 0.1 wt % proportion retarded the crystallization of PPS by increasing its fold surface free energy in a 10%. However, addition of the nanoparticles in excess of 1 wt % results in a promotion of the crystallization rate with reduction of the fold surface free energy to half the value of pure PPS.

On the evolution of morphology of zirconium sponge during reduction and distillation

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

Kapoor, K.; Padmaprabu, C.; Nandi, D.

2008-03-15

High purity zirconium metal is produced by magnesio-thermic reduction of zirconium tetrachloride followed by vacuum distillation. The reduction process is carried out in a batch giving metal sponge and magnesium chloride in the reduced mass. The sponge is purified to using by vacuum distillation. The morphology of the sponge formed during the reduction and its influence on further processing has significant importance. In the present study, a detailed investigation involving evolution of the morphology of sponge particles and its implication during the vacuum distillation was carried out. The study of the microstructure was done using scanning electron microscopy and X-raymore » diffraction. It is observed that the nascent sponge formed is highly unstable which transforms to a needle-like morphology almost immediately, which further transforms to rounded and finally to a bulk shape. Faceting of the surface and needle-shape formation were observed in these particles, this is probably due to anisotropy in the surface energy. The morphology of the sponge formed during the reduction influences the distillation process. The fine needle-like shape sponge morphology leads to particle ejection, which is explained to be due to curvature effect. This is responsible for the formation of unwanted mass during distillation. XRD line broadening analysis indicates that the individual sponge particles are free from structural defects (dislocation) and are nearly single crystalline in nature.« less

The impact of greenhouse climate change on the energetics and hydrologic processes of mid-latitude transient eddies

NASA Technical Reports Server (NTRS)

Branscome, Lee E.; Gutowski, William J., Jr.

1991-01-01

Atmospheric transient eddies contribute significantly to mid-latitude energy and water vapor transports. Changes in the global climate, as induced by greenhouse enhancement, will likely alter transient eddy behavior. Unraveling all the feedbacks that occur in general circulation models (GCMs) can be difficult. The transient eddies are isolated from the feedbacks and are focused on the response of the eddies to zonal-mean climate changes that result from CO2-doubling. Using a primitive-equation spectral model, the impact of climate change on the life cycles of transient eddies is examined. Transient eddy behavior in experiments is compared with initial conditions that are given by the zonal-mean climates of the GCMs with current and doubled amounts of CO2. The smaller meridional temperature gradient in a doubled CO2 climate leads to a reduction in eddy kinetic energy, especially in the subtropics. The decrease in subtropical eddy energy is related to a substantial reduction in equatorward flux of eddy activity during the latter part of the life cycle. The reduction in equatorward energy flux alters the moisture cycle. Eddy meridional transport of water vapor is shifted slightly poleward and subtropical precipitation is reduced. The water vapor transport exhibits a relatively small change in magnitude, compared to changes in eddy energy, due to the compensating effect of higher specific humidity in the doubled-CO2 climate. An increase in high-latitude precipitation is related to the poleward shift in eddy water vapor flux. Surface evaporation amplifies climatic changes in water vapor transport and precipitation in the experiments.

Effect of natural ageing on surface of silver loaded TPE and its influence in antimicrobial efficacy

NASA Astrophysics Data System (ADS)

Tomacheski, Daiane; Pittol, Michele; Simões, Douglas Naue; Ribeiro, Vanda Ferreira; Santana, Ruth Marlene Campomanes

2017-05-01

The aim of this study is to characterize the modifications in silver loaded TPE surfaces exposed to weathering and their relation to susceptibility to microbial attack. Silver loaded TPE materials were exposed to natural ageing for nine months and modifications in antimicrobial properties and surface characteristics were evaluated. Chemical changes were investigated by using the infrared spectra. The average surface roughness and topography were determined by atomic force microscopy. Contact angle was measured to verify wettability conditions and surface free energy (SFE). After nine months of exposure, a decrease in the antimicrobial properties of loaded TPE compounds was observed. A reduction in surface roughness and improvement in wettability and high values of polar component of SFE were verified. The best antibacterial action was noticed in the sample with high Lewis acid force, lower roughness and lower carbonyl index.

Experimental and FDTD study of silicon surface morphology induced by femtosecond laser irradiation at a high substrate temperature.

PubMed

Deng, Guoliang; Feng, Guoying; Zhou, Shouhuan

2017-04-03

Substrate temperature is an important parameter for controlling the properties of femtosecond laser induced surface structures besides traditional ways. The morphology on silicon surface at different temperatures are studied experimentally. Compared to those formed at 300 K, smoother ripples, micro-grooves and nano/micro-holes are formed at 700 K. A two temperature model and FDTD method are used to discuss the temperature dependence of surface structures. The results show that the increased light absorption at elevated temperature leads to the reduction of surface roughness. The type-g feature in the FDTD-η map at 700 K, which corresponds to the energy deposition modulation parallel to the laser polarization with a periodicity bigger than the wavelength, is the origin of the formation of grooves. This work can benefit both surface structures based applications and the study of femtosecond laser-matter interactions.

Electrochemical Reduction of Oxygen in Aprotic Ionic Liquids Containing Metal Cations: A Case Study on the Na-O2 system.

PubMed

Azaceta, Eneko; Lutz, Lukas; Grimaud, Alexis; Vicent-Luna, Jose Manuel; Hamad, Said; Yate, Luis; Cabañero, German; Grande, Hans-Jurgen; Anta, Juan A; Tarascon, Jean-Marie; Tena-Zaera, Ramon

2017-04-10

Metal-air batteries are intensively studied because of their high theoretical energy-storage capability. However, the fundamental science of electrodes, electrolytes, and reaction products still needs to be better understood. In this work, the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) was chosen to study the influence of a wide range of metal cations (M n+ ) on the electrochemical behavior of oxygen. The relevance of the theory of Lewis hard and soft acids and bases to predict satisfactorily the reduction potential of oxygen in electrolytes containing metal cations is demonstrated. Systems with soft and intermediate M n+ acidity are shown to facilitate oxygen reduction and metal oxide formation, whereas oxygen reduction is hampered by hard acid cations such as sodium and lithium. Furthermore, DFT calculations on the energy of formation of the resulting metal oxides rationalize the effect of M n+ on oxygen reduction. A case study on the Na-O 2 system is described in detail. Among other things, the Na + concentration of the electrolyte is shown to control the electrochemical pathway (solution precipitation vs. surface deposition) by which the discharge product grows. All in all, fundamental insights for the design of advanced electrolytes for metal-air batteries, and Na-air batteries in particular, are provided. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Discrete Element Method Simulation of a Boulder Extraction From an Asteroid

NASA Technical Reports Server (NTRS)

Kulchitsky, Anton K.; Johnson, Jerome B.; Reeves, David M.; Wilkinson, Allen

2014-01-01

The force required to pull 7t and 40t polyhedral boulders from the surface of an asteroid is simulated using the discrete element method considering the effects of microgravity, regolith cohesion and boulder acceleration. The connection between particle surface energy and regolith cohesion is estimated by simulating a cohesion sample tearing test. An optimal constant acceleration is found where the peak net force from inertia and cohesion is a minimum. Peak pulling forces can be further reduced by using linear and quadratic acceleration functions with up to a 40% reduction in force for quadratic acceleration.

Importance of interatomic spacing in catalytic reduction of oxygen in phosphoric acid

NASA Technical Reports Server (NTRS)

Jalan, V.; Taylor, E. J.

1983-01-01

A correlation between the nearest-neighbor distance and the oxygen reduction activity of various platinum alloys is reported. It is proposed that the distance between nearest-neighbor Pt atoms on the surface of a supported catalyst is not ideal for dual site absorption of O2 or 'HO2' and that the introduction of foreign atoms which reduce the Pt nearest-neighbor spacing would result in higher oxygen reduction activity. This may allow the critical 0-0 bond interatomic distance and hence the optimum Pt-Pt separation for bond rupture to be determined from quantum chemical calculations. A composite analysis shows that the data on supported Pt alloys are consistent with Appleby's (1970) data on bulk metals with respect to specific activity, activation energy, preexponential factor, and percent d-band character.

Application of superconducting technology to earth-to-orbit electromagnetic launch systems

NASA Technical Reports Server (NTRS)

Hull, J. R.; Carney, L. M.

1988-01-01

Benefits may occur by incorporating superconductors, both existing and those currently under development, in one or more parts of a large-scale electromagnetic launch (EML) system that is capable of delivering payloads from the surface of the Earth to space. The use of superconductors for many of the EML components results in lower system losses; consequently, reductions in the size and number of energy storage devices are possible. Applied high-temperature superconductivity may eventually enable novel design concepts for energy distribution and switching. All of these technical improvements have the potential to reduce system complexity and lower payload launch costs.

Changing Surface-Atmosphere Energy Exchange and Refreezing Capacity of the Lower Accumulation Area, West Greenland

NASA Astrophysics Data System (ADS)

Charalampidis, C.; van As, D.; Machguth, H.; Smeets, P.; van den Broeke, M. R.; Box, J. E.

2014-12-01

We present five years (2009-2013) of automatic weather station (AWS) data from the lower accumulation area (1840 m above sea level) of the Kangerlussuaq region, western Greenland ice sheet. The summers of 2010 and 2012 were both exceptionally warm, but only 2012 resulted in negative surface mass budget (SMB) and surface runoff. The observed runoff was due to a large ice fraction in the upper 10 m of firn that prevented melt water from percolating to available pore space below. Analysis of the in situ data reveals a relatively low 2012 summer albedo of ~0.7 as melt water was present at the surface. Consequently, during the 2012 melt season the surface absorbed 30% (213 MJ m-2) more solar radiation than in 2010. We drive a surface energy balance model with the AWS data to evaluate the seasonal and interannual variability of all surface energy fluxes. The model is able to reproduce the observed melt rates as well as the SMB for each season. While the drive for melt is solar radiation, year-to-year differences are controlled by terrestrial radiation, apart from 2012 when solar radiation dominated melt. Sensitivity tests reveal that 72% of the excess solar energy in 2012 was used for melt, corresponding to 40% (0.67 m) of the 2012 surface ablation. The remaining ablation (0.99 m) was primarily due to the relatively high atmospheric temperatures up to +2.6 °C daily average, indicating that 2012 would have been a negative SMB year in the lower accumulation area even without the melt-albedo feedback. Longer time series of SMB, regional temperature and remotely sensed albedo (MODIS) suggest that 2012 was the first negative SMB year with the lowest albedo at this elevation on record. The warming conditions of the last years resulted in enhanced melt and reduction of the refreezing capacity of the lower accumulation area. If the warming continues the lower accumulation area will be transformed into superimposed ice.

Conservation voltage regulation (CVR) applied to energy savings by voltage-adjusting equipment through AMI

NASA Astrophysics Data System (ADS)

Lan, B.-R.; Chang, C.-A.; Huang, P.-Y.; Kuo, C.-H.; Ye, Z.-J.; Shen, B.-C.; Chen, B.-K.

2017-11-01

Conservation voltage reduction (CVR) includes peak demand reduction, energy conservation, carbon emission reduction, and electricity bill reduction. This paper analyzes the energy-reduction of Siwei Feeders with applying CVR, which are situated in Penghu region and equipped with smart meters. Furthermore, the applicable voltage reduction range for the feeders will be explored. This study will also investigate how the CVR effect and energy conservation are improved with the voltage control devices integrated. The results of this study can serve as a reference for the Taiwan Power Company to promote and implement voltage reduction and energy conservation techniques. This study is expected to enhance the energy-reduction performance of the Penghu Low Carbon Island Project.

Diagnosing land management and climate change impacts on snowmelt in semi-arid agricultural cold regions with an improved snowmelt model

NASA Astrophysics Data System (ADS)

Harder, P.; Pomeroy, J. W.; Helgason, W.

2017-12-01

Spring snowmelt is the most important hydrological event in semi-arid agricultural cold regions, recharging soil moisture and generating the majority of annual runoff. Adoption of no-till agricultural practices means vast areas of the Canadian Prairies, and other analogous regions, are characterized by standing crop stubble. The emergence of stubble during snowmelt will have important implications for the snowpack energy balance. In addition, spatiotemporally dynamic snowcover heterogeneity leads to enhancement of turbulent flux contributions to melt by advection of energy from warm moist bare ground to snow. Stubble emergence and advection are generally unaccounted for in snow models. To address these challenges a stubble-snow-atmosphere surface energy balance model is developed that relates stubble parameters to the snow surface energy balance. Existing fractal understandings of snowcover geometry are applied to a conceptualized boundary layer integration model to estimate a sensible and latent heat advection efficiency. The small-scale nature of stubble-snow-atmosphere interactions makes direct validation of the energy balance terms challenging. However, the energy balance estimates are assessed by comparing to measured snow and stubble surface temperatures, snow surface incoming shortwave radiation and areal average turbulent fluxes. Advection estimates are validated from a two-dimensional air temperature, water vapor and windspeed profiles. Snowcover geometry relationships are validated/updated with unmanned air vehicle observations. Observations for model assessment occurred in 2015 and 2016 on wheat and canola stubble fields in north-central Saskatchewan, Canada. The model is not calibrated to melt rates, yet compares well with available observations, providing confidence in the model structure and parameterization. Sensitivity analysis using the model revealed compensatory relationships in energy balance terms resulting in limited reduction of energy available for snowmelt as stubble height increases. The proposed model is used to diagnose the influence of stubble management and climate change on melt processes to reveal the potential implications on runoff generation, infiltration and land-atmosphere interactions.

Toward a durable superhydrophobic aluminum surface by etching and ZnO nanoparticle deposition.

PubMed

Rezayi, Toktam; Entezari, Mohammad H

2016-02-01

Fabrication of suitable roughness is a fundamental step for acquiring superhydrophobic surfaces. For this purpose, a deposition of ZnO nanoparticles on Al surface was carried out by simple immersion and ultrasound approaches. Then, surface energy reduction was performed using stearic acid (STA) ethanol solution for both methods. The results demonstrated that ultrasound would lead to more stable superhydrophobic Al surfaces (STA-ZnO-Al-U) in comparison with simple immersion method (STA-ZnO-Al-I). Besides, etching in HCl solution in another sample was carried out before ZnO deposition for acquiring more mechanically stable superhydrophobic surface. The potentiodynamic measurements demonstrate that etching in HCl solution under ultrasound leads to superhydrophobic surface (STA-ZnO-Al(E)-U). This sample shows remarkable decrease in corrosion current density (icorr) and long-term stability improvement versus immersion in NaCl solution (3.5%) in comparison with the sample prepared without etching (STA-ZnO-Al-U). Scanning electron micrograph (SEM) and energy-dispersive X-ray spectroscopy (EDX) confirmed a more condense and further particle deposition on Al substrate when ultrasound was applied in the system. The crystallite evaluation of deposited ZnO nanoparticles was carried out using X-ray diffractometer (XRD). Finally, for STA grafting verification on Al surface, Fourier transform infrared in conjunction with attenuated total reflection (FTIR-ATR) was used as a proper technique. Copyright © 2015 Elsevier Inc. All rights reserved.

Determination of the mechanism and extent of surface degradation in Ni-based cathode materials after repeated electrochemical cycling

NASA Astrophysics Data System (ADS)

Hwang, Sooyeon; Kim, Se Young; Chung, Kyung Yoon; Stach, Eric A.; Kim, Seung Min; Chang, Wonyoung

2016-09-01

We take advantage of scanning transmission electron microscopy and electron energy loss spectroscopy to investigate the changes in near-surface electronic structure and quantify the degree of local degradation of Ni-based cathode materials with the layered structure (LiNi0.8Mn0.1Co0.1O2 and LiNi0.4Mn0.3Co0.3O2) after 20 cycles of delithiation and lithiation. Reduction of transition metals occurs in the near-surface region of cathode materials: Mn is the major element to be reduced in the case of relatively Mn-rich composition, while reduction of Ni ions is dominant in Ni-rich materials. The valences of Ni and Mn ions are complementary, i.e., when one is reduced, the other is oxidized in order to maintain charge neutrality. The depth of degradation zone is found to be much deeper in Ni-rich materials. This comparative analysis provides important insights needed for the devising of new cathode materials with high capacity as well as long lifetime.

An Integrated Tool for the Coupled Thermal and Mechanical Analysis of Pyrolyzing Heatshield Materials

NASA Technical Reports Server (NTRS)

Pronchick, Stephen W.

1998-01-01

Materials that pyrolyze at elevated temperature have been commonly used as thermal protection materials in hypersonic flight, and advanced pyrolyzing materials for this purpose continue to be developed. Because of the large temperature gradients that can arise in thermal protection materials, significant thermal stresses can develop. Advanced applications of pyrolytic materials are calling for more complex heatshield configurations, making accurate thermal stress analysis more important, and more challenging. For non-pyrolyzing materials, many finite element codes are available and capable of performing coupled thermal-mechanical analyses. These codes do not, however, have a built-in capability to perform analyses that include pyrolysis effects. When a pyrolyzing material is heated, one or more components of the original virgin material pyrolyze and create a gas. This gas flows away from the pyrolysis zone to the surface, resulting in a reduction in surface heating. A porous residue, referred to as char, remains in place of the virgin material. While the processes involved can be complex, it has been found that a simple physical model in which virgin material reacts to form char and pyrolysis gas, will yield satisfactory analytical results. Specifically, the effects that must be modeled include: (1) Variation of thermal properties (density, specific heat, thermal conductivity) as the material composition changes; (2) Energy released or absorbed by the pyrolysis reactions; (3) Energy convected by the flow of pyrolysis gas from the interior to the surface; (4) The reduction in surface heating due to surface blowing; and (5) Chemical and mass diffusion effects at the surface between the pyrolysis gas and edge gas Computational tools for the one-dimensional thermal analysis these materials exist and have proven to be reliable design tools. The objective of the present work is to extend the analysis capabilities of pyrolyzing materials to axisymmetric configurations, and to couple thermal and mechanical analyses so that thermal stresses may be efficiently and accurately calculated.

Controlling the surface termination of NdGaO3 (110): the role of the gas atmosphere.

PubMed

Cavallaro, Andrea; Harrington, George F; Skinner, Stephen J; Kilner, John A

2014-07-07

In this work the effect of gas atmosphere on the surface termination reconstruction of single crystal NdGaO3 (110) (NGO) during thermal annealing was analyzed. Using Low Energy Ion Scattering (LEIS) it has been possible to study the chemical composition of the first atomic layer of treated NGO single crystal samples. NGO has been analyzed both as-received and after a specific thermal treatment at 1000 °C under different gas fluxes (argon, nitrogen, static air, synthetic air, nitrogen plus 5% hydrogen and wet synthetic air respectively). Thermal annealing of perovskite single crystals, as already reported in the literature, is used to obtain a fully A-cation surface termination. Nevertheless the effect of the gas-atmosphere on this process has not been previously reported. By the use of sequential low energy Ar(+) sputtering combined with the primary ion LEIS analysis, the reconstruction of the outermost atomic layers has allowed the clarification of the mechanism of NGO neodymium surface enrichment. It is proposed that the gallium at the surface is submitted to a reduction/evaporation mechanism caused by low oxygen partial pressure and/or high water pressure in the vector gas. Below the first surface atomic layers of an as-received NGO single-crystal a gallium-rich phase has also been observed.

Mediatorless solar energy conversion by covalently bonded thylakoid monolayer on the glassy carbon electrode.

PubMed

Lee, Jinhwan; Im, Jaekyun; Kim, Sunghyun

2016-04-01

Light reactions of photosynthesis that take place in thylakoid membranes found in plants or cyanobacteria are among the most effective ways of utilizing light. Unlike most researches that use photosystem I or photosystem II as conversion units for converting light to electricity, we have developed a simple method in which the thylakoid monolayer was covalently immobilized on the glassy carbon electrode surface. The activity of isolated thylakoid membrane was confirmed by measuring evolving oxygen under illumination. Glassy carbon surfaces were first modified with partial or full monolayers of carboxyphenyl groups by reductive C-C coupling using 4-aminobenzoic acid and aniline and then thylakoid membrane was bioconjugated through the peptide bond between amine residues of thylakoid and carboxyl groups on the surface. Surface properties of modified surfaces were characterized by cyclic voltammetry, contact angle measurements, and electrochemical impedance spectroscopy. Photocurrent of 230 nA cm(-2) was observed when the thylakoid monolayer was formed on the mixed monolayer of 4-carboxylpheny and benzene at applied potential of 0.4V vs. Ag/AgCl. A small photocurrent resulted when the 4-carboxyphenyl full monolayer was used. This work shows the possibility of solar energy conversion by directly employing the whole thylakoid membrane through simple surface modification. Copyright © 2015 Elsevier B.V. All rights reserved.

Analysis of surface segregation in polymer mixtures: A combination of mean field and statistical associated fluid theories

NASA Astrophysics Data System (ADS)

Krawczyk, Jaroslaw; Croce, Salvatore; Chakrabarti, Buddhapriya; Tasche, Jos

The surface segregation in polymer mixtures remains a challenging problem for both academic exploration as well as industrial applications. Despite its ubiquity and several theoretical attempts a good agreement between computed and experimentally observed profiles has not yet been achieved. A simple theoretical model proposed in this context by Schmidt and Binder combines Flory-Huggins free energy of mixing with the square gradient theory of wetting of a wall by fluid. While the theory gives us a qualitative understanding of the surface induced segregation and the surface enrichment it lacks the quantitative comparison with the experiment. The statistical associating fluid theory (SAFT) allows us to calculate accurate free energy for a real polymeric materials. In an earlier work we had shown that increasing the bulk modulus of a polymer matrix through which small molecules migrate to the free surface causes reduction in the surface migrant fraction using Schmidt-Binder and self-consistent field theories. In this work we validate this idea by combining mean field theories and SAFT to identify parameter ranges where such an effect should be observable. Department of Molecular Physics, Łódź University of Technology, Żeromskiego 116, 90-924 Łódź, Poland.

Femtosecond laser processing of NiPd single and 5x(Ni/Pd) multilayer thin films

NASA Astrophysics Data System (ADS)

Petrović, S.; Gaković, B.; Zamfirescu, M.; Radu, C.; Peruško, D.; Radak, B.; Ristoscu, C.; Zdravković, S.; Luculescu, C. L.; Mihailescu, I. N.

2017-09-01

Modification of single and complex nickel-palladium samples by laser processing in the femtosecond time domain was studied. The samples were processed by focused Ti:Sapphire laser beam (Clark CPA-2101) with 775 nm laser wavelength, 2 kHz repetition rate, 200 fs pulse duration. The laser-induced morphological modifications have shown dependence on the applied fluences and number of laser pulses. The formed surface nanostructures on the single NiPd/Si and multilayer 5x(Ni/Pd)/Si systems are compared with individual Ni and Pd thin films. The results show an increase in surface roughness, formation of parallel periodic surface structures, appearance of hydrodynamic features and ablation of surface material. At low number of pulses (less than 10 pulses) and low pulse energies range (not over 1.7 μJ), the two types of laser-induced periodic surface structure (LIPSS) can be observed: low and high spatial frequency LIPSS (HSFL and LSFL). For all samples, the measured LSFL periods were 720 nm for the ripples created solely on thin film surfaces during the single pulse action. In the case of the multi-pulse irradiation, the periodicities of created LSFLs on the all investigated thin films have shown tendency to reduction with increasing of pulse energies.

Possibilities of a metal surface radioactive decontamination using a pulsed CO2 laser

NASA Astrophysics Data System (ADS)

Milijanic, Scepan S.; Stjepanovic, Natasa N.; Trtica, Milan S.

2000-01-01

There is a growing interest in the laser radioactive decontamination of metal surfaces. It offers advantages over conventional methods: improved safety, reduction of secondary waste, reduced waste volume, acceptable cost. A main mechanism of cleaning in by lasers is ablation. In this work a pulsed TEA CO2 laser was used for surface cleaning, primarily in order to demonstrate that the ablation from metal surfaces with this laser is possible even with relatively low pulse energies, and secondary, that it could be competitive with other lasers because of much higher energy efficiencies. The laser pulse contains two parts, one strong and shot peak at the beginning, followed with a tail. The beam was focused onto a contaminated surface with a KBr lens. The surface was contaminated with 137Cs. Three different metals were used: stainless steel, copper and aluminum. The evaporated material was pumped out in air atmosphere and transferred to a filter. Presence of the activity on the filter was proved by a germanium detector-multichannel analyzer. Activity levels were measured by a GM counter. Calculated decontamination factors as well as collection factors have shown that ablation takes place with relatively high efficiency of decontamination. This investigation suggests that decontamination using the CO2 laser should be seriously considered.

Self-assembled hierarchical direct Z-scheme g-C3N4/ZnO microspheres with enhanced photocatalytic CO2 reduction performance

NASA Astrophysics Data System (ADS)

Nie, Ning; Zhang, Liuyang; Fu, Junwei; Cheng, Bei; Yu, Jiaguo

2018-05-01

Photocatalytic reduction of CO2 into hydrocarbon fuels has been regarded as a promising approach to ease the greenhouse effect and the energy shortage. Herein, an electrostatic self-assembly method was exploited to prepare g-C3N4/ZnO composite microsphere. This method simply utilized the opposite surface charge of each component, achieving a hierarchical structure with intimate contact between them. A much improved photocatalytic CO2 reduction activity was attained. The CH3OH production rate was 1.32 μmol h-1 g-1, which was 2.1 and 4.1 times more than that of the pristine ZnO and g-C3N4, respectively. This facile design bestowed the g-C3N4/ZnO composite an extended light adsorption caused by multi-light scattering effect. It also guaranteed the uniform distribution of g-C3N4 nanosheets on the surface of ZnO microspheres, maximizing their advantage and synergistic effect. Most importantly, the preeminent performance was proposed and validated based on the direct Z-scheme. The recombination rate was considerably suppressed. This work features the meliority of constructing hierarchical direct Z-scheme structures in photocatalytic CO2 reduction reactions.

Using supramolecular binding motifs to provide precise control over the ratio and distribution of species in multiple component films grafted on surfaces: demonstration using electrochemical assembly from aryl diazonium salts.

PubMed

Gui, Alicia L; Yau, Hon Man; Thomas, Donald S; Chockalingam, Muthukumar; Harper, Jason B; Gooding, J Justin

2013-04-16

Supramolecular interactions between two surface modification species are explored to control the ratio and distribution of these species on the resultant surface. A binary mixture of aryl diazonium salts bearing oppositely charged para-substituents (either -SO3(-) or -N(+)(Me)3), which also reduce at different potentials, has been examined on glassy carbon surfaces using cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). Striking features were observed: (1) the two aryl diazonium salts in the mixed solution undergo reductive adsorption at the same potential which is distinctively less negative than the potential required for the reduction of either of the two aryl diazonium salts alone; (2) the surface ratio of the two phenyl derivatives is consistently 1:1 regardless of the ratio of the two aryl diazonium salts in the modification solutions. Homogeneous distribution of the two oppositely charged phenyl species on the modified surface has also been suggested by XPS survey spectra. Diffusion coefficient measurements by DOSY NMR and DFT based computation have indicated the association of the two aryl diazonium species in the solution, which has led to changes in the molecular orbital energies of the two species. This study highlights the potential of using intermolecular interactions to control the assembly of multicomponent thin layers.

Multifunctional nanostructured electrocatalysts for energy conversion and storage: current status and perspectives.

PubMed

Ghosh, Srabanti; Basu, Rajendra N

2018-06-21

Electrocatalytic oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) have attracted widespread attention because of their important role in the application of various energy storage and conversion devices, such as fuel cells, metal-air batteries and water splitting devices. However, the sluggish kinetics of the HER/OER/ORR and their dependency on expensive noble metal catalysts (e.g., Pt) obstruct their large-scale application. Hence, the development of efficient and robust bifunctional or trifunctional electrocatalysts in nanodimension for both oxygen reduction/evolution and hydrogen evolution reactions is highly desired and challenging for their commercialization in renewable energy technologies. This review describes some recent developments in the discovery of bifunctional or trifunctional nanostructured catalysts with improved performances for application in rechargeable metal-air batteries and fuel cells. The role of the electronic structure and surface redox chemistry of nanocatalysts in the improvement of their performance for the ORR/OER/HER under an alkaline medium is highlighted and the associated reaction mechanisms developed in the recent literature are also summarized.

Mechanistic insights into electrochemical reduction of CO 2 over Ag using density functional theory and transport models

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

Singh, Meenesh R.; Goodpaster, Jason D.; Weber, Adam Z.

Electrochemical reduction of CO 2 using renewable sources of electrical energy holds promise for converting CO 2 to fuels and chemicals. Since this process is complex and involves a large number of species and physical phenomena, a comprehensive understanding of the factors controlling product distribution is required. While the most plausible reaction pathway is usually identified from quantum-chemical calculation of the lowest free-energy pathway, this approach can be misleading when coverages of adsorbed species determined for alternative mechanism differ significantly, since elementary reaction rates depend on the product of the rate coefficient and the coverage of species involved in themore » reaction. Moreover, cathode polarization can influence the kinetics of CO 2 reduction. Here in this work, we present a multiscale framework for ab initio simulation of the electrochemical reduction of CO 2 over an Ag(110) surface. A continuum model for species transport is combined with a microkinetic model for the cathode reaction dynamics. Free energies of activation for all elementary reactions are determined from density functional theory calculations. Using this approach, three alternative mechanisms for CO 2 reduction were examined. The rate-limiting step in each mechanism is **COOH formation at higher negative potentials. However, only via the multiscale simulation was it possible to identify the mechanism that leads to a dependence of the rate of CO formation on the partial pressure of CO 2 that is consistent with experiments. Additionally, simulations based on this mechanism also describe the dependence of the H 2 and CO current densities on cathode voltage that are in strikingly good agreement with experimental observation.« less

Mechanistic insights into electrochemical reduction of CO 2 over Ag using density functional theory and transport models

DOE PAGES

Singh, Meenesh R.; Goodpaster, Jason D.; Weber, Adam Z.; ...

2017-10-02

Electrochemical reduction of CO 2 using renewable sources of electrical energy holds promise for converting CO 2 to fuels and chemicals. Since this process is complex and involves a large number of species and physical phenomena, a comprehensive understanding of the factors controlling product distribution is required. While the most plausible reaction pathway is usually identified from quantum-chemical calculation of the lowest free-energy pathway, this approach can be misleading when coverages of adsorbed species determined for alternative mechanism differ significantly, since elementary reaction rates depend on the product of the rate coefficient and the coverage of species involved in themore » reaction. Moreover, cathode polarization can influence the kinetics of CO 2 reduction. Here in this work, we present a multiscale framework for ab initio simulation of the electrochemical reduction of CO 2 over an Ag(110) surface. A continuum model for species transport is combined with a microkinetic model for the cathode reaction dynamics. Free energies of activation for all elementary reactions are determined from density functional theory calculations. Using this approach, three alternative mechanisms for CO 2 reduction were examined. The rate-limiting step in each mechanism is **COOH formation at higher negative potentials. However, only via the multiscale simulation was it possible to identify the mechanism that leads to a dependence of the rate of CO formation on the partial pressure of CO 2 that is consistent with experiments. Additionally, simulations based on this mechanism also describe the dependence of the H 2 and CO current densities on cathode voltage that are in strikingly good agreement with experimental observation.« less

Continuous Steelmaking Directly from Ore

NASA Astrophysics Data System (ADS)

Warner, Noel A.

2014-12-01

In-line continuous processing of high-grade hematite ore (crushed ore or fines) with a pure hydrogen reductant is assessed. An appraisal is made of the rate controlling mechanisms involved in the reduction of a pure layer of molten wustite being transported by floating on a molten carrier iron carbon-free medium at temperatures just in excess of the iron melting point. Published research clearly indicates that under these conditions the kinetics are principally controlled by molecular gaseous diffusion. Thus, the rate is essentially not influenced by total gas pressure above 1 atmosphere. Accordingly, on safety grounds it is recommended that high pressure should not be used for hydrogen steelmaking in the future, but the operation should be conducted close to atmospheric pressure with low pressure steam encapsulation of the plant items involved. Using hydrogen as the reductant means that sub-surface nucleation of CO bubbles cannot disrupt continuous processing. The operation is then no different to processing a normal liquid phase. The off-gases from the reduction zone of a melt circulation loop are super-clean and only contaminated with iron vapor. Accordingly, the best available technology becomes available for energy conservation without risk of non-fusible solids deposition. The net result is that the energy requirements are expected to be superior to other potential processes.

Ice ages and the thermal equilibrium of the earth, II

USGS Publications Warehouse

Adam, D.P.

1975-01-01

The energy required to sustain midlatitude continental glaciations comes from solar radiation absorbed by the oceans. It is made available through changes in relative amounts of energy lost from the sea surface as net outgoing infrared radiation, sensible heat loss, and latent heat loss. Ice sheets form in response to the initial occurrence of a large perennial snowfield in the subarctic. When such a snowfield forms, it undergoes a drastic reduction in absorbed solar energy because of its high albedo. When the absorbed solar energy cannot supply local infrared radiation losses, the snowfield cools, thus increasing the energy gradient between itself and external, warmer areas that can act as energy sources. Cooling of the snowfield progresses until the energy gradients between the snowfield and external heat sources are sufficient to bring in enough (latent plus sensible) energy to balance the energy budget over the snowfield. Much of the energy is imported as latent heat. The snow that falls and nourishes the ice sheet is a by-product of the process used to satisfy the energy balance requirements of the snowfield. The oceans are the primary energy source for the ice sheet because only the ocean can supply large amounts of latent heat. At first, some of the energy extracted by the ice sheet from the ocean is stored heat, so the ocean cools. As it cools, less energy is lost as net outgoing infrared radiation, and the energy thus saved is then available to augment evaporation. The ratio between sensible and latent heat lost by the ocean is the Bowen ratio; it depends in part on the sea surface temperature. As the sea surface temperature falls during a glaciation, the Bowen ratio increases, until most of the available energy leaves the oceans as sensible, rather than latent heat. The ice sheet starves, and an interglacial period begins. The oscillations between stadial and interstadial intervals within a glaciation are caused by the effects of varying amounts of glacial meltwater entering the oceans as a surface layer that acts to reduce the amount of energy available for glacial nourishment. This causes the ice sheet to melt back, which continues the supply of meltwater until the ice sheet diminishes to a size consistent with the reduced rate of nourishment. The meltwater supply then decreases, the rate of nourishment increases, and a new stadial begins. ?? 1975.

Experimental study of the impact of large-scale wind farms on land-atmosphere exchanges

NASA Astrophysics Data System (ADS)

Zhang, wei; Markfort, Corey; Porté-Agel, Fernando

2013-04-01

Wind energy is one of the fastest growing sources of renewable energy world-wide, and it is expected that many more large-scale wind farms will be built and cover a significant portion of land and ocean surfaces. By extracting kinetic energy from the atmospheric boundary layer and converting it to electricity, wind farms may affect the transport of momentum, heat, moisture and trace gases (e.g. CO2) between the atmosphere and the land surface locally and globally. Understanding wind farm-atmosphere interactions and subsequent environmental impacts are complicated by the effects of turbine array configuration, wind farm size, land-surface characteristics and atmospheric thermal stability. In particular, surface scalar flux is influenced by wind farms and needs to be appropriately parameterized in meso-scale and/or high-resolution numerical models. Wind-tunnel experiments of model wind farms with perfectly aligned and staggered configurations, having the same turbine distribution density, were conducted in a neutral turbulent boundary layer with a surface heat source. Turbulent flow and fluxes over and through the wind farm were measured using a custom x-wire/cold-wire anemometer; and surface scalar flux was measured with an array of surface-mounted heat flux sensors within the quasi-developed flow regime. Although the overall surface heat flux change produced by the wind farms was found to be small, with a net reduction of 4% for the staggered wind farm and nearly zero for the aligned wind farm, the highly heterogeneous spatial distribution of the surface heat flux, dependent on wind farm layout, is significant. The difference between the minimum and maximum surface heat fluxes could be up to 12% and 7% in aligned and staggered wind farms, respectively. This finding is important for planning intensive agriculture practices and optimizing agricultural land use with regard to wind energy project development. The well-controlled wind-tunnel experiments presented here also provide a first comprehensive dataset on turbulent flow and scalar transport in wind farms, which can be further used to develop and validate new parameterizations for surface scalar fluxes in numerical models.

Wind-tunnel experiments of scalar transport in aligned and staggered wind farms

NASA Astrophysics Data System (ADS)

Zhang, W.; Markfort, C. D.; Porté-Agel, F.

2012-04-01

Wind energy is the fastest growing renewable energy worldwide, and it is expected that many more large-scale wind farms will be built and will cover a significant portion of land and ocean surfaces. By extracting kinetic energy from the atmospheric boundary layer, wind farms may affect the exchange/transport of momentum, heat and moisture between the atmosphere and land surface. To ensure the long-term sustainability of wind energy, it is important to understand the influence of large-scale wind farms on land-atmosphere interaction. Knowledge of this impact will also be useful to improve parameterizations of wind farms in numerical prediction tools, such as large-scale weather models and large-eddy simulation. Here, we present wind-tunnel measurements of the surface scalar (heat) flux from model wind farms, consisting of more than 10 rows of wind turbines, in a turbulent boundary layer with a surface heat source. Spatially distributed surface heat flux was obtained in idealized aligned and staggered wind farm layouts, having the same turbine distribution density. Measurements, using surface-mounted heat flux sensors, were taken at the 11th out of 12 rows of wind turbines, where the mean flow achieves a quasi-equilibrium state. In the aligned farm, there exist two distinct regions of increased and decreased surface heat flux on either side of turbine columns. The regions are correlated with coherent wake rotation in the turbine-array. On the upwelling side there is decreased flux, while on the downwelling side cool air moves towards the surface causing increased flux. For the staggered farm, the surface heat flux exhibits a relatively uniform distribution and an overall reduction with respect to the boundary layer flow, except in the vicinity of the turbine tower. This observation is also supported by near-surface temperature and turbulent heat flux measured using a customized x-wire/cold-wire. The overall surface heat flux, relative to that of the boundary layer flow without wind turbines, is reduced by approximately 4% in the staggered wind farm and remains nearly the same in the aligned wind farm.

Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Nadesalingam, M. P.; Maddox, W.; Weiss, A. H.

2011-06-01

Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 °C. The PAES intensity then decreases monotonically as the annealing temperature is increased to ˜550 °C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M2,3VV and O KLL Auger transitions. PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 °C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.

Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

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

Fazleev, N. G.; Department of Physics, Kazan State University, Kazan 420008; Nadesalingam, M. P.

2011-06-01

Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 deg. C. The PAES intensity then decreases monotonically as the annealing temperature is increased to {approx}550 deg. C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M{sub 2,3}VV and O KLL Auger transitions. PAESmore » results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 deg. C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.« less

Reduced graphene oxide as photocatalyst for CO2 reduction reaction(Conference Presentation)

NASA Astrophysics Data System (ADS)

Chang, Yu-Chung

2016-10-01

Photocatalytic conversion of carbon dioxide (CO2) to hydrocarbons such as methanol makes possible simultaneous solar energy harvesting and CO2 reduction. Our previous work is using graphene oxide (GO) as a promising photocatalyst for photocatalytic conversion of CO2 to methanol[1].When using graphene oxide as photocatalyst, the photocatalytic efficiency is 4-flod higher than TiO2 powder. GO has a lot of defects on the surface and those defects make sp2 carbon structure become sp3 carbon structure. The carbon structure change cause the GO has large energy gap about 2.7 eV to 3.2 eV. In order to remove the defect and reduce the energy gap of GO, Zhao et al. try to annealing GO powder in the nitrogen atmosphere at 900oC, the GO structure can be reduced to near graphene structure[2]. Zhu et al. do some low temperature annealing, it can control the structure and energy bandgap of GO by control annealing temperature. If the annealing temperature increase the bandgap of GO will be reduce[3]. So, we can using this annealing process to reduce the bandgap of the GO. In the varying temperature thermal reduction process, as the temperature increases from 130oC to 170oC, the functional groups of the graphene oxide will be reduced and band gap of graphene oxide will be narrowed at same time. The characteristic of thermal reduced graphene oxide were analyzed by SEM, XRD and Raman measurements. The band position was determined by UV/Vis. The reduction of functional groups correlates to red shift in light absorption and eventual quenching in the PL signal of RGOs. Combining hydrophobicity, light harvesting and PL quench, we get the highest yield of RGO150 (0.31 μmole g-1 -cat hr-1) is 1.7-fold higher than that of GO (0.18μmole g-1 -cat hr-1). This work investigates a modified method for using a thermal reduction process to reduce the energy gap of graphene oxide.

Hydrodynamic and transport responses to land reclamation in different areas of semi-enclosed subtropical bay

NASA Astrophysics Data System (ADS)

Yang, Ye; Chui, Ting Fong May

2017-07-01

Many coastal areas worldwide have been reclaimed to meet the increasing land demand. Understanding the effects of land reclamation on the hydrodynamics and transport processes of a semi-enclosed bay is therefore of significance. From a case study of Deep Bay (DB) in China and referring to idealized bay models, the effects of two types of land reclamation, one that narrows the bay mouth and another that reduces the water area inside the bay, were examined in this study. Simulation results of idealized models show that the current velocity at the bay mouth and the incoming tidal energy flux are negatively correlated with the width of bay mouth, as the tidal prism remains almost constant when the bay mouth width reduces. The bay mouth width reduction would also increase the tidal energy dissipation inside of the bay due to friction increase. In DB, a 30% reduction in the mouth width increased the bay mouth current velocity by up to 5% and the total incoming energy flux by 18%. The narrowed bay mouth also substantially changed the bay's vertical structure of salinity, increasing the stratification strength by 1.7×10-4 s-2. For reductions in the water surface area in the head of the bay, results from idealized bay simulations show that the current velocity throughout the bay, the incoming tidal energy flux, and salinity at the inner bay all decrease with water area reduction. Reclaiming 14% of area in DB, the current velocity reduced by 9% at the bay mouth, but increased in the middle and inner parts. The incoming tidal energy flux also increased as the coastline became more streamlined after reclamation, and the salinity at inner bay decreased. Both reclamation types have substantially altered the water and salt transport processes and increased the water exchange ability of the bay with the adjacent sea.

Free-Mass and Interface Configurations of Hammering Mechanisms

NASA Technical Reports Server (NTRS)

Bao, Xiaoqi (Inventor); Sherrit, Stewart (Inventor); Badescu, Mircea (Inventor); Bar-Cohen, Yoseph (Inventor); Askins, Steve (Inventor); Ostlund, Patrick (Inventor)

2015-01-01

The design of the free-mass in an ultrasonic driller/corer (USDC) has been refined in order to improve the performance and operational reliability of the system. In one embodiment, the improvements in performance and operational reliability include decreasing the impact surface area of the free-mass to increase the transfer of impact energy from the piezoelectric transducer and reductions in the likelihood that the system will jam.

Mechanisms of Forming Intergranular Microcracks and Microscopic Surface Discontinuities in Welds

DTIC Science & Technology

1992-06-01

SCC) is defined as slow stable crack extension occurring under static loading in sea water at stress intensity values below KIc (critical stress...preheating on the cold cracking resistance is reflected mainly in a reduction of the degree of localization of microplastic strains, their...deconcentration and an increase of the basis over which microplastic yielding takes place. This increases the amount of energy used for local plastic deformation

Carbon Textile Decorated with Pseudocapacitive VC/Vx Oy for High-Performance Flexible Supercapacitors.

PubMed

Van Lam, Do; Shim, Hyung Cheoul; Kim, Jae-Hyun; Lee, Hak-Joo; Lee, Seung-Mo

2017-11-01

It is demonstrated that, via V 2 O 5 coating by low temperature atomic layer deposition and subsequent pyrolysis, ubiquitous cotton textile can readily turn into high-surface-area carbon textile fully decorated with pseudocapacitive V x O y /VC widely usable as electrodes of high-performance supercapacitor. It is found that carbothermic reduction of V 2 O 5 (C + V 2 O 5 → C' + VC + CO/CO 2 (g)) leads to chemical/mechanical activation of carbon textile, thereby producing high-surface-area conductive carbon textile. In addition, sequential phase transformation and carbide formation (V 2 O 5 → V x O y → VC) occurred by carbothermic reduction trigger decoration of the carbon textile with redox-active V x O y /VC. Thanks to the synergistic effect of electrical double layer and pseudocapacitance, the supercapacitors made of the hybrid carbon textile exhibit far better energy density (over 30-fold increase) with excellent cycling stability than the carbon textile simply undergone pyrolysis. The method can open up a promising and facile way to synthesize hybrid electrode materials for electrochemical energy storages possessing advantages of both electrical double layer and pseudocapacitive material. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Theoretical predictions for hexagonal BN based nanomaterials as electrocatalysts for the oxygen reduction reaction.

PubMed

Lyalin, Andrey; Nakayama, Akira; Uosaki, Kohei; Taketsugu, Tetsuya

2013-02-28

The catalytic activity for the oxygen reduction reaction (ORR) of both the pristine and defect-possessing hexagonal boron nitride (h-BN) monolayer and H-terminated nanoribbon have been studied theoretically using density functional theory. It is demonstrated that an inert h-BN monolayer can be functionalized and become catalytically active by nitrogen doping. It is shown that the energetics of adsorption of O(2), O, OH, OOH, and H(2)O on N atom impurities in the h-BN monolayer (N(B)@h-BN) is quite similar to that known for a Pt(111) surface. The specific mechanism of destructive and cooperative adsorption of ORR intermediates on the surface point defects is discussed. It is demonstrated that accounting for entropy and zero-point energy (ZPE) corrections results in destabilization of the ORR intermediates adsorbed on N(B)@h-BN, while solvent effects lead to their stabilization. Therefore, entropy, ZPE and solvent effects partly cancel each other and have to be taken into account simultaneously. Analysis of the free energy changes along the ORR pathway allows us to suggest that a N-doped h-BN monolayer can demonstrate catalytic properties for the ORR under the condition that electron transport to the catalytically active center is provided.

Energy Efficient High-Pressure Turbine Leakage Technology Report

NASA Technical Reports Server (NTRS)

Gardner, W. B.

1980-01-01

The leakage test program was one of such supporting technology programs structured to provide guidance to the Energy Efficient Engine High Pressure Turbine Component Design Effort. Leakage reduction techniques were identified and evaluated. Test models were used to simulate component leak paths and to evaluate leakage reduction techniques. These models simulated the blade/disk attachment, the vane inner platform attachment, and the vane outer platform attachment combined with the blade outer airseal. Disk blade attachment testing indicated that leakage in this area could be reduced to very low levels by paying careful attention to the tolerances along the contact surface between the blade vibration damper and the blade platform contact surface. The aim of feather seal testing was to achieve a goal for an effective leakage gap of one mil (.001 inch) per inch of feather seal length. Results indicated that effective gaps even below the goal level were achievable by (1) maintaining close tolerances between feather seals and their slots to minimize end gaps and limit seal rotation, (2) avoiding feather seal overlap, and (3) minimizing feather seal intersections. W seals were shown to be effective leakage control devices. Wire rope, in its present state of development, was shown not to be an effective sealing concept for application to the component design.

Surface segregation of additives on SnO 2 based powders and their relationship with macroscopic properties

NASA Astrophysics Data System (ADS)

Pereira, Gilberto J.; Castro, Ricardo H. R.; Hidalgo, Pilar; Gouvêa, Douglas

2002-07-01

Surface properties of ceramic powders frequently play an important role in producing high-quality, high-performance, and reliable ceramic products. These properties are related to the surface bond types and interactions with the surroundings. Oxide surfaces generally contain adsorbed hydroxyl groups and modifications in the chemical composition of the surface may be studied by infrared spectroscopy. In this work, we prepared SnO 2 containing Fe or Mg ions by organic chemical route derived from Pechini's method. The prepared powders were characterized by infrared spectroscopy (FT-IR), X-ray diffraction (XRD), dynamic electrophoretic mobility and surface area determination. Results demonstrated that the studied additives segregate onto the oxide surface and modify the hydroxyl IR bands of the adsorbed hydroxyl groups. These surface modifications change some macroscopic properties of the powder such as the isoelectric point (IEP) in aqueous suspensions and the final specific surface area. The increase of the surface area with additive concentration is supposedly due to the reduction of surface energy of the powders when additives segregate on the powder surface.

The influence of biopreparations on the reduction of energy consumption and CO2 emissions in shallow and deep soil tillage.

PubMed

Naujokienė, Vilma; Šarauskis, Egidijus; Lekavičienė, Kristina; Adamavičienė, Aida; Buragienė, Sidona; Kriaučiūnienė, Zita

2018-06-01

The application of innovation in agriculture technologies is very important for increasing the efficiency of agricultural production, ensuring the high productivity of plants, production quality, farm profitability, the positive balance of used energy, and the requirements of environmental protection. Therefore, it is a scientific problem that solid and soil surfaces covered with plant residue have a negative impact on the work, traction resistance, energy consumption, and environmental pollution of tillage machines. The objective of this work was to determine the dependence of the reduction of energy consumption and CO 2 gas emissions on different biopreparations. Experimental research was carried out in a control (SC1) and seven different biopreparations using scenarios (SC2-SC8) using bacterial and non-bacterial biopreparations in different consistencies (with essential and mineral oils, extracts of various grasses and sea algae, phosphorus, potassium, humic and gibberellic acids, copper, zinc, manganese, iron, and calcium), estimating discing and plowing as the energy consumption parameters of shallow and deep soil tillage machines, respectively. CO 2 emissions were determined by evaluating soil characteristics (such as hardness, total porosity and density). Meteorological conditions such average daily temperatures (2015-20.3 °C; 2016-16.90 °C) and precipitations (2015-6.9 mm; 2016-114.9 mm) during the month strongly influenced different results in 2015 and 2016. Substantial differences between the averages of energy consumption identified in approximately 62% of biological preparation combinations created usage scenarios. Experimental research established that crop field treatments with biological preparations at the beginning of vegetation could reduce the energy consumption of shallow tillage machines by up to approximately 23%, whereas the energy consumption of deep tillage could be reduced by up to approximately 19.2% compared with the control treatment. The experimental research results reveal the reduction of CO 2 emissions in shallow tillage to approximately 20.14% (and that in deep tillage to approximately 19.16%) when works were performed by different biological preparation usage scenarios. This experimental research demonstrates the efficient use of the special adaptation of a new biotechnological method for the reduction of the energy consumption and CO 2 gas emissions of agricultural machinery. Copyright © 2018 Elsevier B.V. All rights reserved.

Combining Satellite Data and Models to Assess the Impacts of Urbanization on the Continental US Surface Climate

NASA Technical Reports Server (NTRS)

Bounoua, L.; Zhang, P.; Imhoff, M.; Santanello, J.; Kumar, S.; Shepherd, M.; Quattrochi, D.; Silva, J.; Rosenzweigh, C.; Gaffin, S.;

Hybrid-PIC Simulation of Backsputtered Carbon Transport in the Near-Field Plume of a Hall Thruster

NASA Technical Reports Server (NTRS)

Choi, Maria; Yim, John T.; Williams, George J.; Herman, Daniel A.; Gilland, James H.

2017-01-01

Magnetic shielding has eliminated boron nitride erosion as the life limiting mechanism in a Hall thruster but has resulted in erosion of the front magnetic field pole pieces. Recent experiments show that the erosion of graphite pole covers, which are added to protect the magnetic field pole pieces, causes carbon to redeposit on other surfaces, such as boron nitride discharge channel and cathode keeper surfaces. As a part of the risk-reduction activities for AEPS thruster development, this study models transport of backsputtered carbon from the graphite front pole covers and vacuum facility walls. Fluxes, energy distributions, and redeposition rates of backsputtered carbon on the anode, discharge channel, and graphite cathode keeper surfaces are predicted.

Grain-boundary-dependent CO2 electroreduction activity.

PubMed

Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan; Kanan, Matthew W

2015-04-15

Uncovering new structure-activity relationships for metal nanoparticle (NP) electrocatalysts is crucial for advancing many energy conversion technologies. Grain boundaries (GBs) could be used to stabilize unique active surfaces, but a quantitative correlation between GBs and catalytic activity has not been established. Here we use vapor deposition to prepare Au NPs on carbon nanotubes (Au/CNT). As deposited, the Au NPs have a relatively high density of GBs that are readily imaged by transmission electron microscopy (TEM); thermal annealing lowers the density in a controlled manner. We show that the surface-area-normalized activity for CO2 reduction is linearly correlated with GB surface density on Au/CNT, demonstrating that GB engineering is a powerful approach to improving the catalytic activity of metal NPs.

Relevance of impacter shape to nonvisible damage and residual tensile strength of a thick graphite/epoxy laminate

NASA Technical Reports Server (NTRS)

Poe, Clarence C., Jr.

1991-01-01

A study was made to determine the relevance of impacter shape to nonvisible damage and tensile residual strength of a 36 mm thick graphite/epoxy motor case. The shapes of the impacters were as follows: 12.7 mm and 25.4 mm diameter hemispheres, a sharp corner, and a 6.3 mm diameter bolt-like rod. The investigation revealed that damage initiated when the contact pressure exceeded a critical level. However, the damage was not visible on the surface until an even higher pressure was exceeded. The impact energy to initiate damage or cause visible damage on the surface increased approximately with impacter diameter to the third power. The reduction in strength for nonvisible damage increased with increasing diameter, 9 and 30 percent for the 12.7 mm and 25.4 mm diameter hemispheres, respectively. The corner impacter made visible damage on the surface for even the smallest impact energy. The rod impacter acted like a punch and sliced through the composite. Even so, the critical level of pressure to initiate damage was the same for the rod and hemispherical impacters. Factors of safety for nonvisible damage increased with increasing kinetic energy of impact. The effects of impacter shape on impact force, damage size, damage visibility, and residual tensile strength were predicted quite well assuming Hertzian contact and using maximum stress criteria and a surface crack analysis.

Work function and quantum efficiency study of metal oxide thin films on Ag(100)

NASA Astrophysics Data System (ADS)

Chang, V.; Noakes, T. C. Q.; Harrison, N. M.

2018-04-01

Increasing the quantum efficiency (QE) of metal photocathodes is in the design and development of photocathodes for free-electron laser applications. The growth of metal oxide thin films on certain metal surfaces has previously been shown to reduce the work function (WF). Using a photoemission model B. Camino et al. [Comput. Mater. Sci. 122, 331 (2016), 10.1016/j.commatsci.2016.05.025] based on the three-step model combined with density functional theory calculations we predict that the growth of a finite number of MgO(100) or BaO(100) layers on the Ag(100) surface increases significantly the QE compared with the clean Ag(100) surface for a photon energy of 4.7 eV. Different mechanisms for affecting the QE are identified for the different metal oxide thin films. The addition of MgO(100) increases the QE due to the reduction of the WF and the direct excitation of electrons from the Ag surface to the MgO conduction band. For BaO(100) thin films, an additional mechanism is in operation as the oxide film also photoemits at this energy. We also note that a significant increase in the QE for photons with an energy of a few eV above the WF is achieved due to an increase in the inelastic mean-free path of the electrons.

Promotional Effect of Molten Carbonates on Proton Conductivity and Oxygen Reduction Reaction - an Experimental and Computational Study

NASA Astrophysics Data System (ADS)

Xiong, Xiaolei

Recent research of Solid oxide fuel cells (SOFCs) is aimed to lower the operating temperature to an intermediate temperature (IT) range of 500 to 700°C, while maintaining a proper performance. This Ph.D. research project investigates the promotional effects of alkaline carbonate eutectics on the proton conductivity of proton conducting electrolytes and cathodic ORR reactivity in SOFCs by both experimental and computational methods. The ionic conductivity of the MC-BZY composite above 500°C increases with the higher loading of MC. The sample exhibited nearly a factor of two higher conductivity in H2-containing atmosphere than in air. First-principles DFT modeling further investigated proton transfer at the interface of BaZrO 3 and molten carbonate. With the presence of carbonate ion, the energy barrier for proton migration becomes as low as 0.332 eV. The modeling indicates the reduction of energy barrier is resulted from the change of rate-determining step from proton transfer between oxygen atoms to proton rotation around oxygen atom. Infiltration of MC into porous cathode can reduce the polarization of resistance (Rp), i.e., enhance the oxygen reduction reaction (ORR) activity. The EIS analysis shows that MC has a beneficial effect on reducing Rp for different cathodes including Au, La0.8Sr 0.2MnO3-delta(LSM), La0.6Sr0.4Co 0.2Fe0.8O3-delta(LSCF) and La2NiO 4+delta (LNO). Specifically, the study on MC loading effect was carried out on LSCF cathode. It shows that a higher loading makes a greater reduction on Rp and the degree of reduction is the same from 500 to 600°C. As the loading increases to 1.4 wt%, the degree of Rp reduction tends to reach a limit. First-principles DFT modeling was further used to investigate the incorporation of oxygen into MC. The formation of CO 52- in molten carbonate was considered as a chemisorption of gas oxygen on the surface of MC infiltrated cathodes. After the formation of CO52-, it reacts with another CO3 2- to form two CO42-, which is a rate-limiting step on potential energy surface. After dissociation, oxygen atoms migrate in molten carbonate, which is energetically favor by intermolecular pathways. An O-O-O linkage is formed between carbonate ions, which facilitates the oxygen migration between carbonate ions.

The Surface Chemical Composition of Lunar Samples and Its Significance for Optical Properties

NASA Technical Reports Server (NTRS)

Gold, T.; Bilson, E.; Baron, R. L.

1976-01-01

The surface iron, titanium, calcium, and silicon concentration in numerous lunar soil and rock samples was determined by Auger electron spectroscopy. All soil samples show a large increase in the iron to oxygen ratio compared with samples of pulverized rock or with results of the bulk chemical analysis. A solar wind simulation experiment using 2 keV energy alpha -particles showed that an ion dose corresponding to approximately 30,000 years of solar wind increased the iron concentration on the surface of the pulverized Apollo 14 rock sample 14310 to the concentration measured in the Apollo 14 soil sample 14163, and the albedo of the pulverized rock decreased from 0.36 to 0.07. The low albedo of the lunar soil is related to the iron + titanium concentration on its surface. A solar wind sputter reduction mechanism is discussed as a possible cause for both the surface chemical and optical properties of the soil.

Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

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

Beste, Ariana; Overbury, Steven H.

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed productmore » selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.« less

Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

DOE PAGES

Beste, Ariana; Overbury, Steven H.

2016-03-09

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed productmore » selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.« less

Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces.

PubMed

Beste, Ariana; Overbury, Steven H

2016-04-21

We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed product selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.

Potassium and water coadsorption on TiO 2(110): OH-induced anchoring of potassium and the generation of single-site catalysts

DOE PAGES

Grinter, David C.; R. Remesal, Elena; Luo, Si; ...

2016-09-15

Potassium deposition on TiO 2(110) results in reduction of the substrate and formation of loosely bound potassium species that can move easily on the oxide surface to promote catalytic activity. The results of density functional calculations predict a large adsorption energy (~3.2 eV) with a small barrier (~0.25 eV) for diffusion on the oxide surface. In scanning tunneling microscopy images, the adsorbed alkali atoms lose their mobility when in contact with surface OH groups. Furthermore, K adatoms facilitate the dissociation of water on the titania surface. Lastly, the K–(OH) species generated are good sites for the binding of gold clustersmore » on the TiO 2(110) surface, producing Au/K/TiO 2(110) systems with high activity for the water–gas shift.« less

Dish concentrators for solar thermal energy - Status and technology development

NASA Technical Reports Server (NTRS)

Jaffe, L. D.

1981-01-01

Comparisons are presented of point-focusing, or 'dish' solar concentrator system features, development status, and performance levels demonstrated to date. In addition to the requirements of good optical efficiency and high geometric concentration ratios, the most important future consideration in solar thermal energy dish concentrator design will be the reduction of installed and lifetime costs, as well as the materials and labor costs of production. It is determined that technology development initiatives are needed in such areas as optical materials, design wind speeds and wind loads, structural configuration and materials resistance to prolonged exposure, and the maintenance of optical surfaces. The testing of complete concentrator systems, with energy-converting receivers and controls, is also necessary. Both reflector and Fresnel lens concentrator systems are considered.

All silicon electrode photocapacitor for integrated energy storage and conversion.

PubMed

Cohn, Adam P; Erwin, William R; Share, Keith; Oakes, Landon; Westover, Andrew S; Carter, Rachel E; Bardhan, Rizia; Pint, Cary L

2015-04-08

We demonstrate a simple wafer-scale process by which an individual silicon wafer can be processed into a multifunctional platform where one side is adapted to replace platinum and enable triiodide reduction in a dye-sensitized solar cell and the other side provides on-board charge storage as an electrochemical supercapacitor. This builds upon electrochemical fabrication of dual-sided porous silicon and subsequent carbon surface passivation for silicon electrochemical stability. The utilization of this silicon multifunctional platform as a combined energy storage and conversion system yields a total device efficiency of 2.1%, where the high frequency discharge capability of the integrated supercapacitor gives promise for dynamic load-leveling operations to overcome current and voltage fluctuations during solar energy harvesting.

Field theoretic approach to roughness corrections

NASA Astrophysics Data System (ADS)

Wu, Hua Yao; Schaden, Martin

2012-02-01

We develop a systematic field theoretic description of roughness corrections to the Casimir free energy of a massless scalar field in the presence of parallel plates with mean separation a. Roughness is modeled by specifying a generating functional for correlation functions of the height profile. The two-point correlation function being characterized by its variance, σ2, and correlation length, ℓ. We obtain the partition function of a massless scalar quantum field interacting with the height profile of the surface via a δ-function potential. The partition function is given by a holographic reduction of this model to three coupled scalar fields on a two-dimensional plane. The original three-dimensional space with a flat parallel plate at a distance a from the rough plate is encoded in the nonlocal propagators of the surface fields on its boundary. Feynman rules for this equivalent 2+1-dimensional model are derived and its counterterms constructed. The two-loop contribution to the free energy of this model gives the leading roughness correction. The effective separation, aeff, to a rough plate is measured to a plane that is displaced a distance ρ∝σ2/ℓ from the mean of its profile. This definition of the separation eliminates corrections to the free energy of order 1/a4 and results in unitary scattering matrices. We obtain an effective low-energy model in the limit ℓ≪a. It determines the scattering matrix and equivalent planar scattering surface of a very rough plate in terms of the single length scale ρ. The Casimir force on a rough plate is found to always weaken with decreasing correlation length ℓ. The two-loop approximation to the free energy interpolates between the free energy of the effective low-energy model and that of the proximity force approximation - the force on a very rough plate with σ≳0.5ℓ being weaker than on a planar Dirichlet surface at any separation.

Creating micro-scale surface topology to achieve anisotropic wettability on an aluminum surface

NASA Astrophysics Data System (ADS)

Sommers, Andrew D.; Jacobi, Anthony M.

2006-08-01

A technique for fabricating micropatterned aluminum surfaces with parallel grooves 30 µm wide and tens of microns in depth is described. Standard photolithographic techniques are used to obtain this precise surface-feature patterning. Positive photoresists, S1813 and AZ4620, are selected to mask the surface, and a mixture of BCl3 and Cl2 gases is used to perform the etching. Experimental data show that a droplet placed on the micro-grooved aluminum surface using a micro-syringe exhibits an increased apparent contact angle, and for droplets condensed on these etched surfaces, more than a 50% reduction in the volume needed for the onset of droplet sliding is manifest. No chemical surface treatment is necessary to achieve this water repellency; it is accomplished solely by an anisotropic surface morphology that manipulates droplet geometry and creates and exploits discontinuities in the three-phase contact line. These micro-structured surfaces are proposed for use in a broad range of air-cooling applications, where the management of condensate and defrost liquid on the heat transfer surface is essential to the energy-efficient operation of the machine.

Investigation of the graphene-electrolyte interface in Li-air batteries: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Pavlov, S. V.; Kislenko, S. A.

2018-01-01

In this work the behavior of the main reactants (Li+, O2) of the oxygen reduction reaction (ORR) in acetonitrile solvent near the multi-layer graphene edge has been studied. It was observed by molecular dynamics simulations that the concentration distributions of the Li+ and O2 represent a “chessboard” structure. It was ascertained that the concentrations of the lithium ions and oxygen molecules reach their maximum values near the graphene edges pushed out from the surface, which may act as nucleation centers for the formation of crystalline products of the ORR. The maps of the free energy were estimated for the Li+ and O2. Energy optimal trajectories for the adsorption of oxygen molecules and lithium ions were found. Moreover, the distributions of the electric potential were obtained near the following carbon surfaces: single- and multi-layer graphene edge, graphene plane, which shows the qualitative differences in the double-layer structure.

Large aperture and wide field of view space telescope for the detection of ultra high energy cosmic rays and neutrinos

NASA Astrophysics Data System (ADS)

Mazzinghi, Piero; Bratina, Vojko; Gambicorti, Lisa; Simonetti, Francesca; Zuccaro Marchi, Alessandro

2017-11-01

New technologies are proposed for large aperture and wide Field of View (FOV) space telescopes dedicated to detection of Ultra High Energy Cosmic Rays and Neutrinos flux, through observation of fluorescence traces in atmosphere and diffused Cerenkov signals. The presented advanced detection system is a spaceborne LEO telescope, with better performance than ground-based observatories, detecting up to 103 - 104 events/year. Different design approaches are implemented, all with very large FOV and focal surface detectors with sufficient segmentation and time resolution to allow precise reconstructions of the arrival direction. In particular, two Schmidt cameras are suggested as an appropriate solution to match most of the optical and technical requirements: large FOV, low f/#, reduction of stray light, optionally flat focal surface, already proven low-cost construction technologies. Finally, a preliminary proposal of a wideFOV retrofocus catadioptric telescope is explained.

Improved Electrochromic Characteristics of a Honeycomb-Structured Film Composed of NiO.

PubMed

Yang, Hyeeun; Lee, Yulhee; Kim, Dong In; Seo, Hyeon Jin; Yu, Jung-Hoon; Nam, Sang-Hun; Boo, Jin-Hyo

2018-09-01

Color changes controlled by electronic energies have been studied for many years in order to fabricate energy-efficient smart windows. Reduction and oxidization of nickel oxide under the appropriate voltage can change the color of a window. For a superior nickel oxide (NiO) electrochromic device (ECD), it is important to control the chemical and physical characteristics of the surface. In this study, we applied polystyrene bead templates to nickel oxide films to fabricate a honeycomb-structured electrochromic (EC) layer. We synthesized uniform polystyrene beads using the chemical wet method and placed them on substrates to create honeycomb-structured NiO films. Then, the EC characteristics of the nickel oxide films with a honeycomb structure were evaluated with UV-Visible and cyclic voltammetry. FE-SEM and AFM were used to measure the morphologies of the nanostructures and the efficiencies of the redox reactions related to the specific surface area.

Surface reflectance degradation by microbial communities

DOE PAGES

Cheng, Meng -Dawn; Allman, Steve L.; Graham, David E.; ...

2015-11-05

Building envelope, such as a roof, is the interface between a building structure and the environment. Understanding of the physics of microbial interactions with the building envelope is limited. In addition to the natural weathering, microorganisms and airborne particulate matter that attach to a cool roof tend to reduce the roof reflectance over time, compromising the energy efficiency advantages of the reflective coating designs. We applied microbial ecology analysis to identify the natural communities present on the exposed coatings and investigated the reduction kinetics of the surface reflectance upon the introduction of a defined mixture of both photoautotrophic and heterotrophicmore » microorganisms representing the natural communities. The result are (1) reflectance degradation by microbial communities follows a first-order kinetic relationship and (2) more than 50% of degradation from the initial reflectance value can be caused by microbial species alone in much less time than 3 years required by the current standard ENERGY STAR® test methods.« less

Mechanisms of ilmenite reduction and their impact on the design of effective reactor systems

NASA Technical Reports Server (NTRS)

Briggs, R. A.; Sacco, A.

1991-01-01

One of the first activities at a lunar base could be oxygen recovery from ilmenite (FeTiO3). Oxygen produced from lunar soils could be used to fuel transportation vehicles operating in near-earth space. The first step in developing a suitable reactor system for lunar operation is to determine the mechanisms and rates of oxygen removal from ilmenite. In-situ gravimetric measurements and microscopic examinations were used to determine the hydrogen reduction mechanisms of synthetic ilmenite discs between 823 to 1353 K. A shrinking core reaction model, modified to account for the growth of an iron film on the surface of discs, was capable of predicting experimentally observed conversion-time relationships. The observed reduction mechanism, kinetic rates, and associated activation energy established a base line from which comparisons could be made to improve oxygen yield and removal rates. One proposed technique to improve the rate and extent of oxygen removal was to preoxidize ilmenite. Preoxidation is commonly used during the reduction of ilmenite ores in the iron industry and has been employed for many years to lower operating temperatures and increase reduction rates. This technology could prove beneficial for oxygen production facilities on the Moon as less massive reactor vessels and/or less energy could be associated with a process including preoxidation. X ray diffraction and energy dispersive spectroscopy were utilized to follow the progression of ilmenite oxidation at 1123 and 1140 K and the reduction of pseudobrookite (Fe2TiO5) at 873 and 973 K. Structures formed during the progress of oxidation were related to the system's phase diagrams. Results indicated that after initially producing ilmenite-hematite solutions and rutile (TiO2), pseudobrookite was the end product of oxidation at all temperatures examined (1049 to 1273 K). Initial results from the reduction of pseudobrookite indicate a series of phases are produced including ferropseudobrookite (FeTi2O5), ulvospinel (Fe2TiO4), and ilmenite. Rates of pseudobrookite reduction were typically 50 to 200 times that of ilmenite.

A Microelectromechanical High-Density Energy Storage/Rapid Release System

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

Rodgers, M. Steven; Allen, Jim J.; Meeks, Kent D.

1999-07-21

One highly desirable characteristic of electrostatically driven microelectromechanical systems (MEMS) is that they consume very little power. The corresponding drawback is that the force they produce may be inadequate for many applications. It has previously been demonstrated that gear reduction units or microtransmissions can substantially increase the torque generated by microengines. Operating speed, however, is also reduced by the transmission gear ratio. Some applications require both high speed and high force. If this output is only required for a limited period of time, then energy could be stored in a mechanical system and rapidly released upon demand. We have designed,more » fabricated, and demonstrated a high-density energy storage/rapid release system that accomplishes this task. Built using a 5-level surface micromachining technology, the assembly closely resembles a medieval crossbow. Energy releases on the order of tens of nanojoules have already been demonstrated, and significantly higher energy systems are under development.« less

Effects of He implantation on radiation induced segregation in Cu-Au and Ni-Si alloys

NASA Astrophysics Data System (ADS)

Iwase, A.; Rehn, L. E.; Baldo, P. M.; Funk, L.

Effects of He implantation on radiation induced segregation (RIS) in Cu-Au and Ni-Si alloys were investigated using in situ Rutherford backscattering spectrometry during simultaneous irradiation with 1.5-MeV He and low-energy (100 or 400-keV) He ions at elevated temperatures. RIS during single He ion irradiation, and the effects of pre-implantation with low-energy He ions, were also studied. RIS near the specimen surface, which was pronounced during 1.5-MeV He single-ion irradiation, was strongly reduced under low-energy He single-ion irradiation, and during simultaneous irradiation with 1.5-MeV He and low-energy He ions. A similar RIS reduction was also observed in the specimens pre-implanted with low-energy He ions. The experimental results indicate that the accumulated He atoms cause the formation of small bubbles, which provide additional recombination sites for freely migrating defects.

Microelectromechanical high-density energy storage/rapid release system

NASA Astrophysics Data System (ADS)

Rodgers, M. Steven; Allen, James J.; Meeks, Kent D.; Jensen, Brian D.; Miller, Samuel L.

1999-08-01

One highly desirable characteristic of electrostatically driven microelectromechanical systems (MEMS) is that they consume very little power. The corresponding drawback is that the force they produce may be inadequate for many applications. It has previously been demonstrated that gear reduction units or microtransmissions can substantially increase the torque generated by microengines. Operating speed, however, is also reduced by the transmission gear ratio. Some applications require both high speed and high force. If this output is only required for a limited period of time, then energy could be stored in a mechanical system and rapidly released upon demand. We have designed, fabricated, and demonstrated a high-density energy storage/rapid release system that accomplishes this task. Built using a 5-level surface micromachining technology, the assembly closely resembles a medieval crossbow. Energy releases on the order of tens of nanojoules have already been demonstrated, and significantly higher energy systems are under development.

Effect of design factors on surface temperature and wear in disk brakes

NASA Technical Reports Server (NTRS)

Santini, J. J.; Kennedy, F. E.; Ling, F. F.

1976-01-01

The temperatures, friction, wear and contact conditions that occur in high energy disk brakes are studied. Surface and near surface temperatures were monitored at various locations in a caliper disk brake during drag type testing, with friction coefficient and wear rates also being determined. The recorded transient temperature distributions in the friction pads and infrared photographs of the rotor disk surface both showed that contact at the friction surface was not uniform, with contact areas constantly shifting due to nonuniform thermal expansion and wear. The effect of external cooling and of design modifications on friction, wear and temperatures was also investigated. It was found that significant decreases in surface temperature and in wear rate can be achieved without a reduction in friction either by slotting the contacting face of the brake pad or by modifying the design of the pad support to improve pad compliance. Both design changes result in more uniform contact conditions on the friction surface.

An investigation of enhanced secondary ion emission under Au(n)+ (n = 1-7) bombardment.

PubMed

Nagy, G; Gelb, L D; Walker, A V

2005-05-01

We investigate the mechanism of the nonlinear secondary ion yield enhancement using Au(n)+ (n = 1, 2, 3, 5, 7) primary ions bombarding thin films of Irganox 1010, DL-phenylalanine and polystyrene on Si, Al, and Ag substrates. The largest differences in secondary ion yields are found using Au+, Au2+, and Au3+ primary ion beams. A smaller increase in secondary ion yield is observed using Au5+ and Au7+ primary ions. The yield enhancement is found to be larger on Si than on Al, while the ion yield is smaller using an Au+ beam on Si than on Al. Using Au(n)+ ion structures obtained from Density Functional Theory, we demonstrate that the secondary yield enhancement is not simply due to an increase in energy per area deposited into the surface (energy deposition density). Instead, based on simple mechanical arguments and molecular dynamics results from Medvedeva et al, we suggest a mechanism for nonlinear secondary ion yield enhancement wherein the action of multiple concerted Au impacts leads to efficient energy transfer to substrate atoms in the near surface region and an increase in the number of secondary ions ejected from the surface. Such concerted impacts involve one, two, or three Au atoms, which explains well the large nonlinear yield enhancements observed going from Au+ to Au2+ to Au3+ primary ions. This model is also able to explain the observed substrate effect. For an Au+ ion passing through the more open Si surface, it contacts fewer substrate atoms than in the more dense Al surface. Less energy is deposited in the Si surface region by the Au+ primary ion and the secondary ion yield will be lower for adsorbates on Si than on Al. In the case of Au(n)+ the greater density of Al leads to earlier break-up of the primary ion and a consequent reduction in energy transfer to the near-surface region when compared with Si. This results in higher secondary ion yields and yield enhancements on silicon than aluminum substrates.

Repulsion-based model for contact angle saturation in electrowetting

PubMed Central

2015-01-01

We introduce a new model for contact angle saturation phenomenon in electrowetting on dielectric systems. This new model attributes contact angle saturation to repulsion between trapped charges on the cap and base surfaces of the droplet in the vicinity of the three-phase contact line, which prevents these surfaces from converging during contact angle reduction. This repulsion-based saturation is similar to repulsion between charges accumulated on the surfaces of conducting droplets which causes the well known Coulombic fission and Taylor cone formation phenomena. In our model, both the droplet and dielectric coating were treated as lossy dielectric media (i.e., having finite electrical conductivities and permittivities) contrary to the more common assumption of a perfectly conducting droplet and perfectly insulating dielectric. We used theoretical analysis and numerical simulations to find actual charge distribution on droplet surface, calculate repulsion energy, and minimize energy of the total system as a function of droplet contact angle. Resulting saturation curves were in good agreement with previously reported experimental results. We used this proposed model to predict effect of changing liquid properties, such as electrical conductivity, and system parameters, such as thickness of the dielectric layer, on the saturation angle, which also matched experimental results. PMID:25759748

Repulsion-based model for contact angle saturation in electrowetting.

PubMed

Ali, Hassan Abdelmoumen Abdellah; Mohamed, Hany Ahmed; Abdelgawad, Mohamed

2015-01-01

We introduce a new model for contact angle saturation phenomenon in electrowetting on dielectric systems. This new model attributes contact angle saturation to repulsion between trapped charges on the cap and base surfaces of the droplet in the vicinity of the three-phase contact line, which prevents these surfaces from converging during contact angle reduction. This repulsion-based saturation is similar to repulsion between charges accumulated on the surfaces of conducting droplets which causes the well known Coulombic fission and Taylor cone formation phenomena. In our model, both the droplet and dielectric coating were treated as lossy dielectric media (i.e., having finite electrical conductivities and permittivities) contrary to the more common assumption of a perfectly conducting droplet and perfectly insulating dielectric. We used theoretical analysis and numerical simulations to find actual charge distribution on droplet surface, calculate repulsion energy, and minimize energy of the total system as a function of droplet contact angle. Resulting saturation curves were in good agreement with previously reported experimental results. We used this proposed model to predict effect of changing liquid properties, such as electrical conductivity, and system parameters, such as thickness of the dielectric layer, on the saturation angle, which also matched experimental results.

Energy savings for heat-island reduction strategies in Chicago and Houston (including updates for Baton Rouge, Sacramento, and Salt Lake City)

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

Konopacki, S.; Akbari, H.

2002-02-28

In 1997, the U.S. Environmental Protection Agency (EPA) established the ''Heat Island Reduction Initiative'' to quantify the potential benefits of Heat-Island Reduction (HIR) strategies (i.e., shade trees, reflective roofs, reflective pavements and urban vegetation) to reduce cooling-energy use in buildings, lower the ambient air temperature and improve urban air quality in cities, and reduce CO2 emissions from power plants. Under this initiative, the Urban Heat Island Pilot Project (UHIPP) was created with the objective of investigating the potential of HIR strategies in residential and commercial buildings in three initial UHIPP cities: Baton Rouge, LA; Sacramento, CA; and Salt Lake City,more » UT. Later two other cities, Chicago, IL and Houston, TX were added to the UHIPP. In an earlier report we summarized our efforts to calculate the annual energy savings, peak power avoidance, and annual CO2 reduction obtainable from the introduction of HIR strategies in the initial three cities. This report summarizes the results of our study for Chicago and Houston. In this analysis, we focused on three building types that offer the highest potential savings: single-family residence, office and retail store. Each building type was characterized in detail by vintage and system type (i.e., old and new building constructions, and gas and electric heat). We used the prototypical building characteristics developed earlier for each building type and simulated the impact of HIR strategies on building cooling- and heating-energy use and peak power demand using the DOE-2.1E model. Our simulations included the impact of (1) strategically-placed shade trees near buildings [direct effect], (2) use of high-albedo roofing material on the building [direct effect], (3) urban reforestation with high-albedo pavements and building surfaces [indirect effect] and (4) combined strategies 1, 2, and 3 [direct and indirect effects]. We then estimated the total roof area of air-conditioned buildings in each city using readily obtainable data to calculate the metropolitan-wide impact of HIR strategies. The results show that in Chicago, potential annual energy savings of $30M could be realized by ratepayers from the combined direct and indirect effects of HIR strategies. Additionally, peak power avoidance is estimated at 400 MW and the reduction in annual carbon emissions at 58 ktC. In Houston, the potential annual energy savings are estimated at $82M, with an avoidance of 730 MW in peak power and a reduction in annual carbon emissions of 170 ktC.« less

Dissecting the steps of CO2 reduction: 2. The interaction of CO and CO2 with Pd/γ-Al2O3: an in situ FTIR study

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

Szanyi, Janos; Kwak, Ja Hun

2014-08-07

Alumina supported Pd catalysts with metal loadings of 0.5, 2.5 and 10 wt% were investigated by in situ FTIR spectroscopy in order to understand the nature of adsorbed species formed during their exposure to CO2 and CO. Exposing the annealed samples to CO2 at 295 K resulted in the formation of alumina support-bound surface species only: linear adsorbed CO2, bidentate carbonates and bicarbonates. Room temperature exposure of all three samples to CO produced IR features characteristic of both ionic and metallic Pd, as well as bands we observed upon CO2 adsorption (alumina support-bound species). Low temperature (100 K) adsorption ofmore » CO on the three samples provided information about the state of Pd after oxidation and reduction. Oxidized samples contained exclusively ionic Pd, while mostly metallic Pd was present in the reduced samples. Subsequent annealing of the CO-saturated samples revealed the facile (low temperature) reduction of PdOx species by adsorbed CO. This process was evidenced by the variations in IR bands characteristic of ionic and metallic Pd-bound CO, as well as by the appearance of IR bands associated with CO2 adsorption as a function of annealing temperature. Samples containing oxidized Pd species (oxidized, annealed or reduced) always produced CO2 upon their exposure to CO, while CO2-related surface entities were observed on samples having only fully reduced (metallic) Pd. Acknowledgements: The catalyst preparation was supported by a Laboratory Directed Research and Development (LDRD) project. This work was supported by the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. JHK also acknowledges the support of this work by the 2013 Research Fund of UNIST (Ulsan National Institute of Science and Technology, Ulsan, Korea).« less

From two-dimension to one-dimension: the curvature effect of silicon-doped graphene and carbon nanotubes for oxygen reduction reaction.

PubMed

Zhang, Peng; Hou, Xiuli; Mi, Jianli; He, Yanqiong; Lin, Lin; Jiang, Qing; Dong, Mingdong

2014-09-07

For the goal of practical industrial development of fuel cells, inexpensive, sustainable, and highly efficient electrocatalysts for oxygen reduction reactions (ORR) are highly desirable alternatives to platinum (Pt) and other rare metals. In this work, based on density functional theory, silicon (Si)-doped carbon nanotubes (CNTs) and graphene as metal-free, low cost, and high-performance electrocatalysts for ORR are studied systematically. It is found that the curvature effect plays an important role in the adsorption and reduction of oxygen. The adsorption of O2 becomes weaker as the curvature varies from positive values (outside CNTs) to negative values (inside CNTs). The free energy change of the rate-determining step of ORR on the concave inner surface of Si-doped CNTs is smaller than that on the counterpart of Si-doped graphene, while that on the convex outer surface of Si-doped CNTs is larger than that on Si-doped graphene. Uncovering this new ORR mechanism on silicon-doped carbon electrodes is significant as the same principle could be applied to the development of various other metal-free efficient ORR catalysts for fuel cell applications.

Electrochemical CO2 Reduction via Gas-Phase Catholyte

NASA Astrophysics Data System (ADS)

Carter, Brittany E.; Nesbitt, Nathan T.; D'Imperio, Luke A.; Naughton, Jeffrey R.; Courtney, Dave T.; Shepard, Steve; Burns, Michael J.; Vermaas, David A.; Smith, Wilson A.; Naughton, Michael J.

Reducing CO2 to CO through electrolysis, for the eventual conversion to hydrocarbons, provides a path towards utility-scale seasonal storage of renewable energy. Electrochemical reduction of CO2 has previously been achieved using a two chamber system. The chambers are typically separated by a semipermeable Nafion membrane, with an oxygen evolution catalyst anode on one side, a gold cathode on the other, and a solution containing CO2 on both sides. If instead, CO2 gas was in the second chamber, the reaction should yield more CO formed from CO2 at a given overpotential; this would result from the increased concentration of CO2 at the cathode surface and more facile mass transport of the CO and CO2. With liquid in one chamber and gas in the other, electrolysis is performed by integrating the cathode onto the semipermeable Nafion membrane. This membrane electrode assembly is fabricated via nanoimprint lithography (NIL), simultaneously achieving high active surface area and permeability. Challenges to the Nafion NIL process, and the performance of the system in CO2 reduction, will be presented. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

On the nanostructuring and catalytic promotion of intermediate temperature solid oxide fuel cell (IT-SOFC) cathodes

NASA Astrophysics Data System (ADS)

Serra, José M.; Buchkremer, Hans-Peter

Solid oxide fuel cells (SOFCs) are highly efficient energy converters for both stationary and mobile purposes. However, their market introduction still demands the reduction of manufacture costs and one possible way to reach this goal is the decrease of the operating temperatures, which entails the improvement of the cathode electrocatalytic properties. An ideal cathode material may have mixed ionic and electronic conductivity as well as proper catalytic properties. Nanostructuring and catalytic promotion of mixed conducting perovskites (e.g. La 0.58Sr 0.4Fe 0.8Co 0.2O 3- δ) seem to be promising approaches to overcoming cathode polarization problems and are briefly illustrated here. The preparation of nanostructured cathodes with relatively high surface area and enough thermal stability enables to improve the oxygen exchange rate and therefore the overall SOFC performance. A similar effect was obtained by catalytic promoting the perovskite surface, allowing decoupling the catalytic and ionic-transport properties in the cathode design. Noble metal incorporation may improve the reversibility of the reduction cycles involved in the oxygen reduction. Under the cathode oxidizing conditions, Pd seems to be partially dissolved in the perovskite structure and as a result very well dispersed.

Driving forces for adsorption of amphiphilic peptides to the air-water interface.

PubMed

Engin, Ozge; Villa, Alessandra; Sayar, Mehmet; Hess, Berk

2010-09-02

We have studied the partitioning of amphiphilic peptides at the air-water interface. The free energy of adsorption from bulk to interface was calculated by determining the potential of mean force via atomistic molecular dynamics simulations. To this end a method is introduced to restrain or constrain the center of mass of a group of molecules in a periodic system. The model amphiphilic peptides are composed of alternating valine and asparagine residues. The decomposition of the free energy difference between the bulk and interface is studied for different peptide block lengths. Our analysis revealed that for short amphiphilic peptides the surface driving force dominantly stems from the dehydration of hydrophobic side chains. The only opposing force is associated with the loss of orientational freedom of the peptide at the interface. For the peptides studied, the free energy difference scales linearly with the size of the molecule, since the peptides mainly adopt extended conformations both in bulk and at the interface. The free energy difference depends strongly on the water model, which can be rationalized through the hydration thermodynamics of hydrophobic solutes. Finally, we measured the reduction of the surface tension associated with complete coverage of the interface with peptides.

CROSS-DISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: Surface diffusion of Si, Ge and C adatoms on Si (001) substrate studied by the molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Chen, Zhi-Hui; Yu, Zhong-Yuan; Lu, Peng-Fei; Liu, Yu-Min

2009-10-01

Depositions of Si, Ge and C atoms onto a preliminary Si (001) substrate at different temperatures are investigated by using the molecular dynamics method. The mechanism of atomic self-assembling occurring locally on the flat terraces between steps is suggested. Diffusion and arrangement patterns of adatoms at different temperatures are observed. At 900 K, the deposited atoms are more likely to form dimers in the perpendicular [110] direction due to the more favourable movement along the perpendicular [110] direction. C adatoms are more likely to break or reconstruct the dimers on the substrate surface and have larger diffusion distances than Ge and Si adatoms. Exchange between C adatoms and substrate atoms are obvious and the epitaxial thickness is small. Total potential energies of adatoms and substrate atoms involved in the simulation cell are computed. When a newly arrived adatom reaches the stable position, the potential energy of the system will decrease and the curves turns into a ladder-like shape. It is found that C adatoms can lead to more reduction of the system energy and the potential energy of the system will increase as temperature increases.

Impact of the urban heat island on residents’ energy consumption: a case study of Qingdao

NASA Astrophysics Data System (ADS)

Ding, Feng; Pang, Huaji; Guo, Wenhui

2018-02-01

This paper examines impact of urban heat island on residents’ energy consumption through comparative analyses of monthly air temperature data observed in Qingdao, Laoshan and Huangdao weather stations. The results show effect of urban heat island is close related with urbanization speed. Recently, effects of urban heat island of Laoshan and Huangdao exceed that of Qingdao, consistent with rapid urbanization in Laoshan and Huangdao. Enhanced effect of urban heat island induces surface air temperature to rise up, further increase electricity energy consumption for air conditioning use in summer and reduce coal consumption for residents heating in winter. Comparing change of residents’ energy consumption in summer and winter, increments in summer are less than reduction in winter. This implicates effect of urban heat island is more obvious in winter than in summer.

Relationship between light scattering and absorption due to cytochrome c oxidase reduction during loss of tissue viability in brains of rats

NASA Astrophysics Data System (ADS)

Kawauchi, Satoko; Sato, Shunichi; Ooigawa, Hidetoshi; Nawashiro, Hiroshi; Ishihara, Miya; Kikuchi, Makoto

2008-02-01

We performed simultaneous measurement of light scattering and absorption due to reduction of cytochrome c oxidase as intrinsic optical signals that are related to morphological characteristics and energy metabolism, respectively, for rat brains after oxygen/glucose deprivation by saline infusion. To detect change in light scattering, we determined the wavelength that was the most insensitive to change in light absorption due to the reduction of cytochrome c oxidase on the basis of multiwavelength analysis of diffuse reflectance data set for each rat. Then the relationships between scattering signal and absorption signals related to the reductions of heme aa 3 (605 nm) and CuA (830 nm) in cytochrome c oxidase were examined. Measurements showed that after starting saline infusion, the reduction of heme aa 3 started first; thereafter triphasic, large scattering change occurred (200-300 s), during which the reduction of CuA started. Despite such complex behaviors of IOSs, almost linear correlations were seen between the scattering signal and the heme aa 3-related absorption signal, while a relatively large animal-to-animal variation was observed in the correlation between the scattering signal and CuA-related absorption signal. Transmission electron microscopic observation revealed that dendritic swelling and mitochondrial deformation occurred in the cortical surface tissue after the triphasic scattering change. These results suggest that mitochondrial energy failure accompanies morphological alteration in the brain tissue and results in change in light scattering; light scattering will become an important indicator of tissue viability in brain.

Polyoxometalate-Promoted Electrocatalytic CO2 Reduction at Nanostructured Silver in Dimethylformamide.

PubMed

Guo, Si-Xuan; Li, Fengwang; Chen, Lu; MacFarlane, Douglas R; Zhang, Jie

2018-04-18

Electrochemical reduction of CO 2 is a promising method to convert CO 2 into fuels or useful chemicals, such as carbon monoxide (CO), hydrocarbons, and alcohols. In this study, nanostructured Ag was obtained by electrodeposition of Ag in the presence of a Keggin type polyoxometalate, [PMo 12 O 40 ] 3- (PMo). Metallic Ag is formed upon reduction of Ag + . Adsorption of PMo on the surface of the newly formed Ag lowers its surface energy thus stabilizes the nanostructure. The electrocatalytic performance of this Ag-PMo nanocomposite for CO 2 reduction was evaluated in a CO 2 saturated dimethylformamide medium containing 0.1 M [ n-Bu 4 N]PF 6 and 0.5% (v/v) added H 2 O. The results show that this Ag-PMo nanocomposite can catalyze the reduction of CO 2 to CO with an onset potential of -1.70 V versus Fc 0/+ , which is only 0.29 V more negative than the estimated reversible potential (-1.41 V) for this process and 0.70 V more positive than that on bulk Ag metal. High faradaic efficiencies of about 90% were obtained over a wide range of applied potentials. A Tafel slope of 60 mV dec -1 suggests that rapid formation of *CO 2 •- is followed by the rate-determining protonation step. This is consistent with the voltammetric data which suggest that the reduced PMo interacts strongly with CO 2 (and presumably CO 2 •- ) and hence promotes the formation of CO 2 •- .

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

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

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

DOE PAGES

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.; ...

2016-12-12

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

The effect of polar end of long-chain fluorocarbon oligomers in promoting the superamphiphobic property over multi-scale rough Al alloy surfaces

NASA Astrophysics Data System (ADS)

Saifaldeen, Zubayda S.; Khedir, Khedir R.; Camci, Merve T.; Ucar, Ahmet; Suzer, Sefik; Karabacak, Tansel

2016-08-01

Rough structures with re-entrant property and their subsequent surface energy reduction with long-chain fluorocarbon oligomers are both critical in developing superamphiphobic (SAP, i.e. both super hydrophobic and superoleophobic) surfaces. However, morphology of the low-surface energy layer on a rough re-entrant substrate can strongly depend on the fluorocarbon oligomers used. In this study, the effect of polar end of different kinds of long-chain fluorocarbon oligomers in promoting a self-assembled monolayer with close packed molecules and robust adhesion on multi-scale rough Al alloy surfaces was investigated. Hierarchical Al alloy surfaces with microgrooves and nanograss structures were developed by a simple combination of one-directional mechanical sanding and post treatment in boiling de-ionized water (DIW). Three types of long-chain fluorocarbon oligomers of 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDTS), 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (PFDCS), and perfluorooctanoic acid (PFOA) were chemically vaporized onto these rough Al alloy surfaces. The PFDCS exhibited the lowest surface free energy of less than 10 mN/m. The contact angle and sliding angle measurements for water, ethylene glycol, and peanut oil verified the SAP property of hierarchical rough Al alloy surfaces treated with alkylsilane oligomers (PFDTS, PFDCS). However, the hierarchical surfaces treated with fluorocarbon oligomer with polar acidic tail (PFOA) showed highly amphiphobic properties but could not reach the threshold for SAP. Chemical stability of the hierarchical Al alloy surfaces treated with the fluorocarbon oligomers was tested under the harsh conditions of ultra-sonication in acetone and annealing at high temperature after different treatment times. Contact angle measurements revealed the robustness of the alkylsilane oligomers and deterioration of the PFOA coating particularly for low surface tension liquids. The robust adhesion and close-packing of the alkylsilane molecules as well as their vertical orientation with exposure of more CF3 groups instead of CF2 groups due to the polar silane-based tail are believed to be the main reasons behind their improved chemical stability. The selection of fluorocarbon oligomer with proper polar tail which can promote a self-assembled monolayer with close-packed molecules could make it possible for utilizing shorter fluorocarbon oligomers, which is environmentally favorable, to develop high surface energy materials with SAP properties.

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

Tewari, Somesh Vinayak, E-mail: somesh-vinayak@yahoo.com, E-mail: svtewari@barc.gov.in; Sharma, Archana; Mittal, K. C.

An experimental investigation of surface flashover characteristics of PMMA and POM is studied in compressed nitrogen gas environment with nitrogen as the background gas. The operating pressure range is from 1kg/cm{sup 2} to 4kg/cm{sup 2}. It is observed that the breakdown voltage of PMMA is higher than POM owing to a higher permittivity mismatch between POM- nitrogen interface as compared to the PMMA- nitrogen interface. The reduction in spacer efficiency with pressure for PMMA is 11% as compared to POM which shows a higher reduction of 18%. This paper further emphasizes on the role of energy level and density ofmore » charge carrier trapping centers for a reduced breakdown voltage in POM as compared to PMMA.« less

Analysis of fixed bed data for the extraction of a rate mechanism for the reaction of hematite with methane

DOE PAGES

Breault, Ronald W.; Monazam, Esmail R.

2015-04-01

In this study, chemical looping combustion is a promising technology for the capture of CO 2 involving redox materials as oxygen carriers. The effects of reduction conditions, namely, temperature and fuel partial pressure on the conversion products are investigated. The experiments were conducted in a laboratory fixed-bed reactor that was operated cyclically with alternating reduction and oxidation periods. Reactions are assumed to occur in the shell surrounding the particle grains with diffusion of oxygen to the surface from the grain core. Activation energies for the shell and core reactions range from 9 to 209 kJ/mol depending on the reaction step.

Low-E Retrofit Demonstration and Educational Program

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

Culp, Thomas D; Wiehagen, Joseph; Drumheller, S Craig

The objective of this project was to demonstrate the capability of low-emissivity (low-E) storm windows / panels and low-E retrofit glazing systems to significantly and cost effectively improve the energy efficiency of both existing residential and commercial buildings. The key outcomes are listed below: RESIDENTIAL CASE STUDIES: (a) A residential case study in two large multifamily apartment buildings in Philadelphia showed a substantial 18-22% reduction in heating energy use and a 9% reduction in cooling energy use by replacing old clear glass storm windows with modern low-E storm windows. Furthermore, the new low-E storm windows reduced the overall apartment airmore » leakage by an average of 10%. (b) Air leakage testing on interior low-E panels installed in a New York City multifamily building over windows with and without AC units showed that the effective leakage area of the windows was reduced by 77-95%. (c) To study the use of low-E storm windows in a warmer mixed climate with a balance of both heating and cooling, 10 older homes near Atlanta with single pane windows were tested with three types of exterior storm windows: clear glass, low-E glass with high solar heat gain, and low-E glass with lower solar heat gain. The storm windows significantly reduced the overall home air leakage by an average of 17%, or 3.7 ACH50. Considerably high variability in the data made it difficult to draw strong conclusions about the overall energy usage, but for heating periods, the low-E storm windows showed approximately 15% heating energy savings, whereas clear storm windows were neutral in performance. For cooling periods, the low-E storm windows showed a wide range of performance from 2% to over 30% cooling energy savings. Overall, the study showed the potential for significantly more energy savings from using low-E glass versus no storm window or clear glass storm windows in warmer mixed climates, but it is difficult to conclusively say whether one type of low-E performed better than the other. COMMERCIAL CASE STUDIES: (a) A 12-story office building in Philadelphia was retrofitted by adding a double-pane low-E insulating glass unit to the existing single pane windows, to create a triple glazed low-E system. A detailed side-by-side comparison in two pairs of perimeter offices facing north and east showed a 39-60% reduction in heating energy use, a 9-36% reduction in cooling energy use, and a 10% reduction in peak electrical cooling demand. An analysis of utility bills estimated the whole building heating and cooling energy use was reduced by over 25%. Additionally, the retrofit window temperatures were commonly 20 degrees warmer on winter days, and 10-20 degrees cooler on summer days, leading to increased occupant comfort. (b) Two large 4-story office buildings in New Jersey were retrofitted with a similar system, but using two low-E coatings in the retrofit system. The energy savings are being monitored by a separate GPIC project; this work quantified the changes in glass surface temperatures, thermal comfort, and potential glass thermal stress. The low-E retrofit panels greatly reduced daily variations in the interior window surface temperatures, lowering the maximum temperature and raising the minimum temperature by over 20F compared to the original single pane windows with window film. The number of hours of potential thermal discomfort, as measured by deviation between mean radiant temperature and ambient air temperature by more than 3F, were reduced by 93 percent on the south orientation and over two-thirds on the west orientation. Overall, the low-E retrofit led to substantially improved occupant comfort with less periods of both overheating and feeling cold. (c) No significant thermal stress was observed in the New Jersey office building test window when using the low-E retrofit system over a variety of weather conditions. The surface temperature difference only exceeded 10F (500 psi thermal stress) for less than 1.5% of the monitored time, and in all cases, the maximum surface temperature difference never exceeded 35F (1,750 psi thermal stress). LOW-E STORM WINDOW OUTREACH AND EDUCATION PROGRAM: (a) The project team assisted the State of Pennsylvania in adding low-E storm windows as a cost effective weatherization measure on its priority list for the state weatherization assistance program. (b) No technical barriers that could hinder widespread application were identified in the case studies. However, educational barriers have been identified, in that weatherization personnel commonly misunderstand how the application of low-E storm windows is very different than much more expensive full window replacement. (c) A package of educational materials was developed to help communicate the benefits of low-E storm windows and retrofits as a cost effective tool for weatherization personnel. (d) Using detailed thermal simulations, more accurate U-factor and solar heat gain coefficient (SHGC) values were determined for low-E storm windows installed over different primary windows. IN SUMMARY, this work confirmed the potential for low-E storm windows, panels, and retrofit systems to provide significant energy savings, reductions in air leakage, and improvements in thermal comfort in both residential and commercial existing buildings.« less

Reduction of lighting energy consumption in office buildings through improved daylight design

NASA Astrophysics Data System (ADS)

Papadouri, Maria Violeta Prado

This study aims to investigate the lighting energy consumption in office buildings and the options for its reduction. One way to reduce lighting energy consumption is by improving the daylight design. A better use of daylight in buildings might be an outcome from the effort made in different directions. Like the improvement of a building's fabric and layout, the materials, even the furniture in a space influences the daylight quality considerably. Also very important role in lighting energy consumption has the development of more efficient lighting technology like the electric lighting control systems, such as photo sensors and occupancy sensors. Both systems are responsible so that the electric light is not used without reason. As the focusing area of this study, is to find ways to improve the daylight use in buildings, a consequent question is which are the methods provided in order to achieve this The accuracy of the methodology used is also an important issue in order to achieve reliable results. The methodology applied in this study includes the analysis of a case study by taking field measurements and computer simulations. The first stage included gathering information about the lighting design of the building and monitoring the light levels, both from natural and from the electric lighting. The second stage involved testing with computer simulations, different parameters that were expected to improve the daylight exploitation of the specific area. The results of the field measurements showed that the main problems of the space were the low natural light levels and the poor daylight distribution. The annual electric lighting energy consumption, as it was calculated with the use of computer simulations, represented the annual energy consumption of a typical air-conditioned prestige office building (energy consumption guide 19, for energy use in offices, 2000). After several computer simulations, the results showed that initial design parameters of the building can affect the lighting energy consumption of the space significantly. On the other hand, relatively small changes, like changing the reflectance of the surfaces and the lighting control systems can make even more difference to the light quality of the space and the reduction of lighting energy consumption.

Chemistry of fast electrons

PubMed Central

Maximoff, Sergey N.; Head-Gordon, Martin P.

2009-01-01

A chemicurrent is a flux of fast (kinetic energy ≳ 0.5−1.3 eV) metal electrons caused by moderately exothermic (1−3 eV) chemical reactions over high work function (4−6 eV) metal surfaces. In this report, the relation between chemicurrent and surface chemistry is elucidated with a combination of top-down phenomenology and bottom-up atomic-scale modeling. Examination of catalytic CO oxidation, an example which exhibits a chemicurrent, reveals 3 constituents of this relation: The localization of some conduction electrons to the surface via a reduction reaction, 0.5 O2 + δe− → Oδ− (Red); the delocalization of some surface electrons into a conduction band in an oxidation reaction, Oδ− + CO → CO2δ− → CO2 + δe− (Ox); and relaxation without charge transfer (Rel). Juxtaposition of Red, Ox, and Rel produces a daunting variety of metal electronic excitations, but only those that originate from CO2 reactive desorption are long-range and fast enough to dominate the chemicurrent. The chemicurrent yield depends on the universality class of the desorption process and the distribution of the desorption thresholds. This analysis implies a power-law relation with exponent 2.66 between the chemicurrent and the heat of adsorption, which is consistent with experimental findings for a range of systems. This picture also applies to other oxidation-reduction reactions over high work function metal surfaces. PMID:19561296

A Mechanistic Study of CO 2 Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy

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

Flynn, Kristen

2015-08-18

Carbon dioxide (CO 2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO 2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO 2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played duringmore » the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO 2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO 2 catalysis.« less

A Mechanistic Study of CO 2 Reduction at the Interface of a Gallium Phosphide (GaP) Surface using Core-level Spectroscopy - Oral Presentation

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

Flynn, Kristen

2015-08-19

Carbon dioxide (CO 2) emission into the atmosphere has increased tremendously through burning of fossil fuels, forestry, etc.. The increased concentration has made CO 2 reductions very attractive though the reaction is considered uphill. Utilizing the sun as a potential energy source, CO 2 has the possibility to undergo six electron and four proton transfers to produce methanol, a useable resource. This reaction has been shown to occur selectively in an aqueous pyridinium solution with a gallium phosphide (GaP) electrode. Though this reaction has a high faradaic efficiency, it was unclear as to what role the GaP surface played duringmore » the reaction. In this work, we aim to address the fundamental role of GaP during the catalytic conversion, by investigating the interaction between a clean GaP surface with the reactants, products, and intermediates of this reaction using X-ray photoelectron spectroscopy. We have determined a procedure to prepare atomically clean GaP and our initial CO 2 adsorption studies have shown that there is evidence of chemisorption and reaction to form carbonate on the clean surface at LN2 temperatures (80K), in contrast to previous theoretical calculations. These findings will enable future studies on CO 2 catalysis.« less

Surface chemical analysis and ab initio investigations of CsI coated C fiber cathodes for high power microwave sources

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios; Morgan, Dane; LaCour, Matthew; Golby, Ken; Shiffler, Don; Booske, John H.

2010-02-01

CsI coated C fiber cathodes are promising electron emitters utilized in field emission applications. Ab initio calculations, in conjunction with experimental investigations on CsI-spray coated C fiber cathodes, were performed in order to better understand the origin of the low turn-on E-field obtained, as compared to uncoated C fibers. One possible mechanism for lowering the turn-on E-field is surface dipole layers reducing the work function. Ab initio modeling revealed that surface monolayers of Cs, CsI, Cs2O, and CsO are all capable of producing low work function C fiber cathodes (1 eV<Φ<1.5 eV), yielding a reduction in the turn-on E-field by as much as ten times, when compared to the bare fiber. Although a CsI-containing aqueous solution is spray deposited on the C fiber surface, energy dispersive x-ray spectroscopy and scanning auger microscopy measurements show coabsorption of Cs and I into the fiber interior and Cs and O on the fiber surface, with no surface I. It is therefore proposed that a cesium oxide (CsxOy) surface coating is responsible, at least in part, for the low turn E-field and superior emission characteristics of this type of fiber cathode. This CsxOy layer could be formed during preconditioning heating. CsxOy surface layers cannot only lower the fiber work function by the formation of surface dipoles (if they are thin enough) but may also enhance surface emission through their ability to emit secondary electrons due to a process of grazing electron impact. These multiple electron emission processes may explain the reported 10-100 fold reduction in the turn-on E-field of coated C fibers.

Laser polishing of 3D printed mesoscale components

NASA Astrophysics Data System (ADS)

Bhaduri, Debajyoti; Penchev, Pavel; Batal, Afif; Dimov, Stefan; Soo, Sein Leung; Sten, Stella; Harrysson, Urban; Zhang, Zhenxue; Dong, Hanshan

2017-05-01

Laser polishing of various engineered materials such as glass, silica, steel, nickel and titanium alloys, has attracted considerable interest in the last 20 years due to its superior flexibility, operating speed and capability for localised surface treatment compared to conventional mechanical based methods. The paper initially reports results from process optimisation experiments aimed at investigating the influence of laser fluence and pulse overlap parameters on resulting workpiece surface roughness following laser polishing of planar 3D printed stainless steel (SS316L) specimens. A maximum reduction in roughness of over 94% (from ∼3.8 to ∼0.2 μm Sa) was achieved at the optimised settings (fluence of 9 J/cm2 and overlap factors of 95% and 88-91% along beam scanning and step-over directions respectively). Subsequent analysis using both X-ray photoelectron spectroscopy (XPS) and glow discharge optical emission spectroscopy (GDOES) confirmed the presence of surface oxide layers (predominantly consisting of Fe and Cr phases) up to a depth of ∼0.5 μm when laser polishing was performed under normal atmospheric conditions. Conversely, formation of oxide layers was negligible when operating in an inert argon gas environment. The microhardness of the polished specimens was primarily influenced by the input thermal energy, with greater sub-surface hardness (up to ∼60%) recorded in the samples processed with higher energy density. Additionally, all of the polished surfaces were free of the scratch marks, pits, holes, lumps and irregularities that were prevalent on the as-received stainless steel samples. The optimised laser polishing technology was consequently implemented for serial finishing of structured 3D printed mesoscale SS316L components. This led to substantial reductions in areal Sa and St parameters by 75% (0.489-0.126 μm) and 90% (17.71-1.21 μm) respectively, without compromising the geometrical accuracy of the native 3D printed samples.

A Holistic Multi Evidence Approach to Study the Fragmentation Behaviour of Crystalline Mannitol

PubMed Central

Koner, Jasdip S.; Rajabi-Siahboomi, Ali; Bowen, James; Perrie, Yvonne; Kirby, Daniel; Mohammed, Afzal R.

2015-01-01

Mannitol is an essential excipient employed in orally disintegrating tablets due to its high palatability. However its fundamental disadvantage is its fragmentation during direct compression, producing mechanically weak tablets. The primary aim of this study was to assess the fracture behaviour of crystalline mannitol in relation to the energy input during direct compression, utilising ball milling as the method of energy input, whilst assessing tablet characteristics of post-milled powders. Results indicated that crystalline mannitol fractured at the hydrophilic (011) plane, as observed through SEM, alongside a reduction in dispersive surface energy. Disintegration times of post-milled tablets were reduced due to the exposure of the hydrophilic plane, whilst more robust tablets were produced. This was shown through higher tablet hardness and increased plastic deformation profiles of the post-milled powders, as observed with a lower yield pressure through an out-of-die Heckel analysis. Evaluation of crystal state using x-ray diffraction/differential scanning calorimetry showed that mannitol predominantly retained the β-polymorph; however x-ray diffraction provided a novel method to calculate energy input into the powders during ball milling. It can be concluded that particle size reduction is a pragmatic strategy to overcome the current limitation of mannitol fragmentation and provide improvements in tablet properties. PMID:26553127

A Holistic Multi Evidence Approach to Study the Fragmentation Behaviour of Crystalline Mannitol

NASA Astrophysics Data System (ADS)

Koner, Jasdip S.; Rajabi-Siahboomi, Ali; Bowen, James; Perrie, Yvonne; Kirby, Daniel; Mohammed, Afzal R.

2015-11-01

Mannitol is an essential excipient employed in orally disintegrating tablets due to its high palatability. However its fundamental disadvantage is its fragmentation during direct compression, producing mechanically weak tablets. The primary aim of this study was to assess the fracture behaviour of crystalline mannitol in relation to the energy input during direct compression, utilising ball milling as the method of energy input, whilst assessing tablet characteristics of post-milled powders. Results indicated that crystalline mannitol fractured at the hydrophilic (011) plane, as observed through SEM, alongside a reduction in dispersive surface energy. Disintegration times of post-milled tablets were reduced due to the exposure of the hydrophilic plane, whilst more robust tablets were produced. This was shown through higher tablet hardness and increased plastic deformation profiles of the post-milled powders, as observed with a lower yield pressure through an out-of-die Heckel analysis. Evaluation of crystal state using x-ray diffraction/differential scanning calorimetry showed that mannitol predominantly retained the β-polymorph however x-ray diffraction provided a novel method to calculate energy input into the powders during ball milling. It can be concluded that particle size reduction is a pragmatic strategy to overcome the current limitation of mannitol fragmentation and provide improvements in tablet properties.

DFT Study of the Oxygen Reduction Reaction Activity on Fe−N4-Patched Carbon Nanotubes: The Influence of the Diameter and Length

PubMed Central

Chen, Xin; Hu, Rui; Bai, Fan

2017-01-01

The influences of diameter and length of the Fe−N4-patched carbon nanotubes (Fe−N4/CNTs) on oxygen reduction reaction (ORR) activity were investigated by density functional theory method using the BLYP/DZP basis set. The results indicate that the stability of the Fe−N4 catalytic site in Fe−N4/CNTs will be enhanced with a larger tube diameter, but reduced with shorter tube length. A tube with too small a diameter makes a Fe−N4 site unstable in acid medium since Fe−N and C−N bonds must be significantly bent at smaller diameters due to hoop strain. The adsorption energy of the ORR intermediates, especially of the OH group, becomes weaker with the increase of the tube diameter. The OH adsorption energy of Fe−N4/CNT with the largest tube diameter is close to that on Pt(111) surface, indicating that its catalytic property is similar to Pt. Electronic structure analysis shows that the OH adsorption energy is mainly controlled by the energy levels of Fe 3d orbital. The calculation results uncover that Fe−N4/CNTs with larger tube diameters and shorter lengths will exhibit better ORR activity and stability. PMID:28772903

Surfactant effects on alpha factors in full-scale wastewater aeration systems.

PubMed

Rosso, D; Larson, L E; Stenstrom, M K

2006-01-01

Aeration is an essential process in the majority of wastewater treatment processes, and accounts for the largest fraction of plant energy costs. Aeration systems can achieve wastewater oxygenation by shearing the surface (surface aerators) or releasing bubbles at the bottom of the tank (coarse- or fine-bubble aerators). Surfactants accumulate on gas-liquid interfaces and reduce mass transfer rates. This reduction in general is larger for fine-bubble aerators. This study was conducted to evaluate mass transfer effects on the characterization and specification of aeration systems in clean and process water conditions. Tests at different interfacial turbulence regimes were analysed, showing higher gas transfer depression for lower turbulence regimes. Higher turbulence regimes can offset contamination effects, at the expense of operating efficiency. This phenomenon is characteristic of surface aerators and coarse bubble diffusers and is here discussed. The results explain the variability of alpha factors measured at small scale, due to uncontrolled energy density. Results are also reported in dimensionless empirical correlations that describe mass transfer as a function of physiochemical and geometrical characteristics of the aeration process.

In situ fabrication of green reduced graphene-based biocompatible anode for efficient energy recycle.

PubMed

Cheng, Ying; Mallavarapu, Megharaj; Naidu, Ravi; Chen, Zuliang

2018-02-01

Improving the anode configuration to enhance biocompatibility and accelerate electron shuttling is critical for efficient energy recovery in microbial fuel cells (MFCs). In this paper, green reduced graphene nanocomposite was successfully coated using layer-by-layer assembly technique onto carbon brush anode. The modified anode achieved a 3.2-fold higher power density of 33.7 W m -3 at a current density of 69.4 A m -3 with a 75% shorter start period. As revealed in the characterization, the green synthesized nanocomposite film affords larger surface roughness for microbial colonization. Besides, gold nanoparticles, which anchored on graphene sheets, promise the relatively high electroactive sites and facilitate electron transfer from electricigens to the anode. The reduction-oxidation peaks in cyclic voltammograms indicated the mechanism of surface cytochromes facilitated current generation while the electrochemical impedance spectroscopy confirmed the enhanced electron transfer from surface cytochrome to electrode. The green synthesis process has the potential to generate a high performing anode in further applications of MFCs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Optimization of dual-energy subtraction chest radiography by use of a direct-conversion flat-panel detector system.

PubMed

Fukao, Mari; Kawamoto, Kiyosumi; Matsuzawa, Hiroaki; Honda, Osamu; Iwaki, Takeshi; Doi, Tsukasa

2015-01-01

We aimed to optimize the exposure conditions in the acquisition of soft-tissue images using dual-energy subtraction chest radiography with a direct-conversion flat-panel detector system. Two separate chest images were acquired at high- and low-energy exposures with standard or thick chest phantoms. The high-energy exposure was fixed at 120 kVp with the use of an auto-exposure control technique. For the low-energy exposure, the tube voltages and entrance surface doses ranged 40-80 kVp and 20-100 % of the dose required for high-energy exposure, respectively. Further, a repetitive processing algorithm was used for reduction of the image noise generated by the subtraction process. Seven radiology technicians ranked soft-tissue images, and these results were analyzed using the normalized-rank method. Images acquired at 60 kVp were of acceptable quality regardless of the entrance surface dose and phantom size. Using a repetitive processing algorithm, the minimum acceptable doses were reduced from 75 to 40 % for the standard phantom and to 50 % for the thick phantom. We determined that the optimum low-energy exposure was 60 kVp at 50 % of the dose required for the high-energy exposure. This allowed the simultaneous acquisition of standard radiographs and soft-tissue images at 1.5 times the dose required for a standard radiograph, which is significantly lower than the values reported previously.

Lost in transition? An exploration of attempts to reduce energy consumption by UK households

NASA Astrophysics Data System (ADS)

Kukla, Christopher

As significant energy consumers, UK households need to reduce their energy use if the UK is to achieve its greenhouse gas reduction targets. Low levels of engagement and adoption rates of energy curtailment measures need to be overcome. Policies perceived as ‘fair’ can increase levels of engagement and acceptability. This thesis explores how households approach reducing their own energy use, the reductions they can achieve and any existing barriers. Households’ perception of what is ‘fair’ in the context of energy reductions is explored based on households' own experiences of energy reduction. Households recruited from the South East of England participated in a mixed-methods study attempting to reduce their energy use over a 12-month period. Provided with estimates of their carbon footprints and a comparison to the UK average, the participants discussed their energy use, reductions and perceptions of how reductions could be encouraged fairly. Participants’ energy use was something of an enigma, as were the associated GHG emissions. However, its use was protected and seen as ‘acceptable’ and ‘necessary’ for them to be comfortable in their day-to-day lives. Reducing their energy use was seen as possible and acceptable in areas of energy use viewed as ‘wasteful’ or ‘unnecessary’. While seen as possible, these targets were not necessarily achievable, with 50 per cent of the participants making measurable reductions, and 50 per cent unable to. Energy reductions of ten per cent were seen as possible, even by those unable to reduce, with little scope to move beyond this as participants did not know what they should or could do next. To move forward participants viewed fairness as important, citing energy reductions needing to be a valid, legitimate aim of society; with required reductions being achievable, supported by information, and placing the burden of responsibility on those who use the most.

CO2 electroreduction characteristics of Pt-Ru/C powder and Pt-Ru sputtered electrodes under acidic condition

NASA Astrophysics Data System (ADS)

Furukawa, Hiroto; Matsuda, Shofu; Tanaka, Shoji; Shironita, Sayoko; Umeda, Minoru

2018-03-01

The objective of this study was to overcome the issue about the underpotential adsorption of the CO2 electroreductant on the surface of the Pt electrocatalyst under acidic conditions by the alloying of Pt and Ru. As evaluation parameters, the CO2 reduction onset potential and CO2-reductant reoxidation onset potential were employed. We prepared a porous microelectrode filled with Pt-Ru/C powder and a Pt-Ru sputtered electrode. For the Pt-Ru/C powder electrocatalyst, the CO2 reduction onset potential as well as the CO2-reductant reoxidation onset potential shifted in the direction of the CO2/CO2-reductant standard redox potential dependent on the Ru content, which is indicative of a decrease in the underpotential-adsorption energy of the CO2 reductant. For the Pt-Ru sputtered electrode, only the CO2 reduction onset potential shifted in the direction of the redox potential. Consequently, we demonstrated that the Pt-Ru/C powder electrode improved the reactivity of the CO2/CO2-reductant when discussing the relationship between the CO2 reduction onset potential and the CO2-reductant reoxidation onset potential. Based on our findings, the Pt-Ru/C (1:9) powder is the most effective electrocatalyst for the CO2 reduction, which could minimize the underpotential adsorption.

Drastic reduction in the growth temperature of graphene on copper via enhanced London dispersion force

PubMed Central

Choi, Jin-Ho; Li, Zhancheng; Cui, Ping; Fan, Xiaodong; Zhang, Hui; Zeng, Changgan; Zhang, Zhenyu

2013-01-01

London dispersion force is ubiquitous in nature, and is increasingly recognized to be an important factor in a variety of surface processes. Here we demonstrate unambiguously the decisive role of London dispersion force in non-equilibrium growth of ordered nanostructures on metal substrates using aromatic source molecules. Our first-principles based multi-scale modeling shows that a drastic reduction in the growth temperature, from ~1000°C to ~300°C, can be achieved in graphene growth on Cu(111) when the typical carbon source of methane is replaced by benzene or p-Terphenyl. The London dispersion force enhances their adsorption energies by about (0.5–1.8) eV, thereby preventing their easy desorption, facilitating dehydrogenation, and promoting graphene growth at much lower temperatures. These quantitative predictions are validated in our experimental tests, showing convincing demonstration of monolayer graphene growth using the p-Terphenyl source. The general trends established are also more broadly applicable in molecular synthesis of surface-based nanostructures. PMID:23722566

Green synthesis of size controllable gold nanoparticles

NASA Astrophysics Data System (ADS)

Mohan Kumar, Kesarla; Mandal, Badal Kumar; Kiran Kumar, Hoskote A.; Maddinedi, Sireesh Babu

2013-12-01

A facile rapid green eco-friendly method to synthesize gold nanoparticles (Au NPs) of tunable size using aqueous Terminalia arjuna fruit extracts has been demonstrated herein. Formation of Au NPs was confirmed by Surface Plasmon Resonance (SPR) study at 528 nm using UV-visible spectrophotometer. The time of reduction, size and morphological variations of Au NPs were studied with varying quantities of T. arjuna fruit aqueous extracts. Synthesized Au NPs were characterized using UV-visible spectroscopy, Fourier transformed infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and Energy dispersive X-ray spectroscopy (EDAX). Polyphenols responsible for reduction of Au3+ to Au0 were identified using High Performance Liquid Chromatography (HPLC) as ascorbic acid, gallic acid and pyrogallol. The oxidized forms of polyphenols formed coordination with surface of Au NPs which protected their further growth and aggregation. We also propose a plausible mechanism how to tune size and shape of Au NPs by varying the quantity of extracts. Thus obtained Au NPs were stable for more than four months.

Silver Nanoparticle Impregnated Bio-Based Activated Carbon with Enhanced Antimicrobial Activity

NASA Astrophysics Data System (ADS)

Selvakumar, R.; Suriyaraj, S. P.; Jayavignesh, V.; Swaminathan, K.

2013-08-01

The present study involves the production of silver nanoparticles using a novel yeast strain Saccharomyces cerevisiae BU-MBT CY-1 isolated from coconut cell sap. The biological reduction of silver nitrate by the isolate was deducted at various time intervals. The yeast cells after biological silver reduction were harvested and subjected to carbonization at 400°C for 1 h and its properties were analyzed using Fourier transform infra-red spectroscopy, X-ray diffraction, scanning electron microscope attached with energy dispersive spectroscopy and transmission electron microscopy. The average size of the silver nanoparticles present on the surface of the carbonized silver containing yeast cells (CSY) was 19 ± 9 nm. The carbonized control yeast cells (CCY) did not contain any particles on its surface. The carbonized silver nanoparticles containing yeast cells (CSY) were made into bioactive emulsion and tested for its efficacy against various pathogenic Gram positive and Gram negative bacteria. The antimicrobial activity studies indicated that CSY bioactive nanoemulsion was effective against Gram negative organisms than Gram positive organism.

Adsorption, folding, and packing of an amphiphilic peptide at the air/water interface.

PubMed

Engin, Ozge; Sayar, Mehmet

2012-02-23

Peptide oligomers play an essential role as model compounds for identifying key motifs in protein structure formation and protein aggregation. Here, we present our results, based on extensive molecular dynamics simulations, on adsorption, folding, and packing within a surface monolayer of an amphiphilic peptide at the air/water interface. Experimental results suggest that these molecules spontaneously form ordered monolayers at the interface, adopting a β-hairpin-like structure within the surface layer. Our results reveal that the β-hairpin structure can be observed both in bulk and at the air/water interface. However, the presence of an interface leads to ideal partitioning of the hydrophobic and hydrophilic residues, and therefore reduces the conformational space for the molecule and increases the stability of the hairpin structure. We obtained the adsorption free energy of a single β-hairpin at the air/water interface, and analyzed the enthalpic and entropic contributions. The adsorption process is favored by two main factors: (1) Free-energy reduction due to desolvation of the hydrophobic side chains of the peptide and release of the water molecules which form a cage around these hydrophobic groups in bulk water. (2) Reduction of the total air/water contact area at the interface upon adsorption of the peptide amphiphile. By performing mutations on the original molecule, we demonstrated the relative role of key design features of the peptide. Finally, by analyzing the potential of mean force among two peptides at the interface, we investigated possible packing mechanisms for these molecules within the surface monolayer. © 2012 American Chemical Society

An energetic perspective on hydrological cycle changes in the Geoengineering Model Intercomparison Project

NASA Astrophysics Data System (ADS)

Kravitz, Ben; Rasch, Philip J.; Forster, Piers M.; Andrews, Timothy; Cole, Jason N. S.; Irvine, Peter J.; Ji, Duoying; Kristjánsson, Jón Egill; Moore, John C.; Muri, Helene; Niemeier, Ulrike; Robock, Alan; Singh, Balwinder; Tilmes, Simone; Watanabe, Shingo; Yoon, Jin-Ho

2013-12-01

of surface and atmospheric energy budget responses to CO2 and solar forcings can be used to reveal mechanisms of change in the hydrological cycle. We apply this energetic perspective to output from 11 fully coupled atmosphere-ocean general circulation models simulating experiment G1 of the Geoengineering Model Intercomparison Project (GeoMIP), which achieves top-of-atmosphere energy balance between an abrupt quadrupling of CO2 from preindustrial levels (abrupt4xCO2) and uniform solar irradiance reduction. We divide the climate system response into a rapid adjustment, in which climate response is due to adjustment of the atmosphere and land surface on short time scales, and a feedback response, in which the climate response is predominantly due to feedback related to global mean temperature changes. Global mean temperature change is small in G1, so the feedback response is also small. G1 shows a smaller magnitude of land sensible heat flux rapid adjustment than in abrupt4xCO2 and a larger magnitude of latent heat flux adjustment, indicating a greater reduction of evaporation and less land temperature increase than abrupt4xCO2. The sum of surface flux changes in G1 is small, indicating little ocean heat uptake. Using an energetic perspective to assess precipitation changes, abrupt4xCO2 shows decreased mean evaporative moisture flux and increased moisture convergence, particularly over land. However, most changes in precipitation in G1 are in mean evaporative flux, suggesting that changes in mean circulation are small.

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

PubMed

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

Evidence for age-related performance degradation of (241)Am foil sources commonly used in UK schools.

PubMed

Whitcher, R; Page, R D; Cole, P R

2014-06-01

The characteristics of alpha radiation have for decades been demonstrated in UK schools using small sealed (241)Am sources. There is a small but steady number of schools who report a considerable reduction in the alpha count rate detected by an end-window GM detector compared with when the source was new. This cannot be explained by incorrect apparatus or set-up, foil surface contamination, or degradation of the GM detector. The University of Liverpool and CLEAPSS collaborated to research the cause of this performance degradation. The aim was to find what was causing the performance degradation and the ramifications for both the useful and safe service life of the sources. The research shows that these foil sources have greater energy straggling with a corresponding reduction in spectral peak energy. A likely cause for this increase in straggling is a significant diffusion of the metals over time. There was no evidence to suggest the foils have become unsafe, but precautionary checks should be made on old sources.

Simplifying the representation of complex free-energy landscapes using sketch-map

PubMed Central

Ceriotti, Michele; Tribello, Gareth A.; Parrinello, Michele

2011-01-01

A new scheme, sketch-map, for obtaining a low-dimensional representation of the region of phase space explored during an enhanced dynamics simulation is proposed. We show evidence, from an examination of the distribution of pairwise distances between frames, that some features of the free-energy surface are inherently high-dimensional. This makes dimensionality reduction problematic because the data does not satisfy the assumptions made in conventional manifold learning algorithms We therefore propose that when dimensionality reduction is performed on trajectory data one should think of the resultant embedding as a quickly sketched set of directions rather than a road map. In other words, the embedding tells one about the connectivity between states but does not provide the vectors that correspond to the slow degrees of freedom. This realization informs the development of sketch-map, which endeavors to reproduce the proximity information from the high-dimensionality description in a space of lower dimensionality even when a faithful embedding is not possible. PMID:21730167

Electron-stimulated reactions in layered CO/H2O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Low-energy (100 eV) electron-stimulated reactions in layered H2O/CO/H2O ices are investigated. For CO trapped within approximately 50 ML of the vacuum interface in the amorphous solid water (ASW) films, both oxidation and reduction reactions are observed. However for CO buried more deeply in the film, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in region from ~10 – 40 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried COmore » layers, the CO reduction reactions quickly increase with temperature above ~60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol that accounts for the observations.« less

Reduction reactions and densification during in situ TEM heating of iron oxide nanochains

NASA Astrophysics Data System (ADS)

Bonifacio, Cecile S.; Das, Gautom; Kennedy, Ian M.; van Benthem, Klaus

2017-12-01

The reduction reactions and densification of nanochains assembled from γ-Fe2O3 nanoparticles were investigated using in situ transmission electron microscopy (TEM). Morphological changes and reduction of the metal oxide nanochains were observed during in situ TEM annealing through simultaneous imaging and quantitative analysis of the near-edge fine structures of Fe L2,3 absorption edges acquired by spatially resolved electron energy loss spectroscopy. A change in the oxidation states during annealing of the iron oxide nanochains was observed with phase transformations due to continuous reduction from Fe2O3 over Fe3O4, FeO to metallic Fe. Phase transitions during the in situ heating experiments were accompanied with morphological changes in the nanochains, specifically rough-to-smooth surface transitions below 500 °C, neck formation between adjacent particles around 500 °C, and subsequent neck growth. At higher temperatures, coalescence of FeO particles was observed, representing densification.

Microscopic Study of Carbon Surfaces Interacting with High Carbon Ferromanganese Slag

NASA Astrophysics Data System (ADS)

Safarian, Jafar; Kolbeinsen, Leiv

2015-02-01

The interaction of carbon materials with molten slags occurs in many pyro-metallurgical processes. In the production of high carbon ferromanganese in submerged arc furnace, the carbothermic reduction of MnO-containing silicate slags yields the metal product. In order to study the interaction of carbon with MnO-containing slags, sessile drop wettability technique is employed in this study to reduce MnO from a molten slag drop by carbon substrates. The interfacial area on the carbon substrate before and after reaction with slag is studied by scanning electron microscope. It is indicated that no Mn metal particles are found at the interface through the reduction of the MnO slag. Moreover, the reduction of MnO occurs through the contribution of Boudouard reaction and it causes carbon consumption in particular active sites at the interface, which generate carbon degradation and open pore growth at the interface. It is shown that the slag is fragmented to many micro-droplets at the reaction interface, potentially due to the effect on the interfacial energies of a provisional liquid Mn thin film. The rapid reduction of these slag micro-droplets affects the carbon surface with making deep micro-pores. A mechanism for the formation of slag micro-droplets is proposed, which is based on the formation of provisional micro thin films of liquid Mn at the interface.

In-situ Production of High Density Polyethylene and Other Useful Materials on Mars

NASA Technical Reports Server (NTRS)

Flynn, Michael

2005-01-01

This paper describes a revolutionary materials structure and power storage concept based on the in-situ production of abiotic carbon 4 compounds. One of the largest single mass penalties required to support the human exploration of Mars is the surface habitat. This proposal will use physical chemical technologies to produce high density polyethylene (HDPE) inflatable structures and construction materials from Mars atmospheric CO2. The formation of polyethylene from Mars CO2 is based on the use of the Sabatier and modified Fischer Tropsch reactions. The proposed system will fully integrate with existing in-situ propellant production concepts. The technology will also be capable of supplementing human caloric requirements, providing solid and liquid fuels for energy storage, and providing significant reduction in mission risk. The NASA Mars Reference Mission Definition Team estimated that a conventional Mars surface habitat structure would weigh 10 tonnes. It is estimated that this technology could reduce this mass by 80%. This reduction in mass will significantly contribute to the reduction in total mission cost need to make a Mars mission a reality. In addition the potential reduction of risk provided by the ability to produce C4 and potentially higher carbon based materials in-situ on Mars is significant. Food, fuel, and shelter are only three of many requirements that would be impacted by this research.

The effect of breast support on upper body muscle activity during 5 km treadmill running.

PubMed

Milligan, Alexandra; Mills, Chris; Scurr, Joanna

2014-12-01

Breast support has previously been shown to influence surface EMG of the pectoralis major during running. Reductions in muscle activity have previously been associated with a reduction in energy cost, which may be advantageous for female runners. Ten female participants performed two self-paced (average pace 9 km h(-1)) 5 km treadmill runs under two breast support conditions (low and high); an additional bare-breasted 2 min run was also conducted. Surface EMG electrodes were positioned on the pectoralis major, anterior deltoid, medial deltoid, and upper trapezius, with data collected during the first 2 min of running and each kilometer interval thereafter. Reductions in peak EMG of the pectoralis major, anterior and medial deltoid were reported when participants ran in the high breast support during the initial intervals of the run (up to the second kilometer). The increased activation in the pectoralis major, anterior and medial deltoid in the low breast support may be due to increased tension within these muscles, induced by the greater breast pain experienced in the low breast support. This may be a strategy to reduce the independent breast movement causing the pain through increased muscular activation. This study further promotes the use of a high breast support during running with potential benefits for treadmill running associated with reductions in muscular demand during a 5 km run. Copyright © 2014 Elsevier B.V. All rights reserved.

Liquid metal actuator driven by electrochemical manipulation of surface tension

NASA Astrophysics Data System (ADS)

Russell, Loren; Wissman, James; Majidi, Carmel

2017-12-01

We examine the electrocapillary properties of a fluidic actuator composed of a liquid metal droplet that is submerged in electrolytic solution and attached to an elastic beam. The beam deflection is controlled by electrochemically driven changes in the surface energy of the droplet. The metal is a eutectic gallium-indium alloy that is liquid at room temperature and forms an nm-thin Ga2O3 skin when oxidized. The effective surface tension of the droplet changes dramatically with oxidation and reduction, which are reversibly controlled by applying low voltage to the electrolytic bath. Wetting the droplet to two copper pads allows for a controllable tensile force to be developed between the opposing surfaces. We demonstrate the ability to reliably control force by changing the applied oxidizing voltage. Actuator forces and droplet geometries are also examined by performing a computational fluid mechanics simulation using Surface Evolver. The theoretical predictions are in qualitative agreement with the experimental measurements and provide additional confirmation that actuation is driven by surface tension.

Surface hardness evaluation of different composite resin materials: influence of sports and energy drinks immersion after a short-term period

PubMed Central

ERDEMİR, Ugur; YİLDİZ, Esra; EREN, Meltem Mert; OZEL, Sevda

2013-01-01

Objectives: This study evaluated the effect of sports and energy drinks on the surface hardness of different composite resin restorative materials over a 1-month period. Material and Methods: A total of 168 specimens: Compoglass F, Filtek Z250, Filtek Supreme, and Premise were prepared using a customized cylindrical metal mould and they were divided into six groups (N=42; n=7 per group). For the control groups, the specimens were stored in distilled water for 24 hours at 37º C and the water was renewed daily. For the experimental groups, the specimens were immersed in 5 mL of one of the following test solutions: Powerade, Gatorade, X-IR, Burn, and Red Bull, for two minutes daily for up to a 1-month test period and all the solutions were refreshed daily. Surface hardness was measured using a Vickers hardness measuring instrument at baseline, after 1-week and 1-month. Data were statistically analyzed using Multivariate repeated measure ANOVA and Bonferroni's multiple comparison tests (α=0.05). Results: Multivariate repeated measures ANOVA revealed that there were statistically significant differences in the hardness of the restorative materials in different immersion times (p<0.001) in different solutions (p<0.001). The effect of different solutions on the surface hardness values of the restorative materials was tested using Bonferroni's multiple comparison tests, and it was observed that specimens stored in distilled water demonstrated statistically significant lower mean surface hardness reductions when compared to the specimens immersed in sports and energy drinks after a 1-month evaluation period (p<0.001). The compomer was the most affected by an acidic environment, whereas the composite resin materials were the least affected materials. Conclusions: The effect of sports and energy drinks on the surface hardness of a restorative material depends on the duration of exposure time, and the composition of the material. PMID:23739850

Changing surface-atmosphere energy exchange and refreezing capacity of the lower accumulation area, West Greenland

NASA Astrophysics Data System (ADS)

Charalampidis, C.; van As, D.; Box, J. E.; van den Broeke, M. R.; Colgan, W. T.; Doyle, S. H.; Hubbard, A. L.; MacFerrin, M.; Machguth, H.; Smeets, C. J. P. P.

2015-11-01

We present 5 years (2009-2013) of automatic weather station measurements from the lower accumulation area (1840 m a.s.l. - above sea level) of the Greenland ice sheet in the Kangerlussuaq region. Here, the summers of 2010 and 2012 were both exceptionally warm, but only 2012 resulted in a strongly negative surface mass budget (SMB) and surface meltwater run-off. The observed run-off was due to a large ice fraction in the upper 10 m of firn that prevented meltwater from percolating to available pore volume below. Analysis reveals an anomalously low 2012 summer-averaged albedo of 0.71 (typically ~ 0.78), as meltwater was present at the ice sheet surface. Consequently, during the 2012 melt season, the ice sheet surface absorbed 28 % (213 MJ m-2) more solar radiation than the average of all other years. A surface energy balance model is used to evaluate the seasonal and interannual variability of all surface energy fluxes. The model reproduces the observed melt rates as well as the SMB for each season. A sensitivity analysis reveals that 71 % of the additional solar radiation in 2012 was used for melt, corresponding to 36 % (0.64 m) of the 2012 surface lowering. The remaining 64 % (1.14 m) of surface lowering resulted from high atmospheric temperatures, up to a +2.6 °C daily average, indicating that 2012 would have been a negative SMB year at this site even without the melt-albedo feedback. Longer time series of SMB, regional temperature, and remotely sensed albedo (MODIS) show that 2012 was the first strongly negative SMB year, with the lowest albedo, at this elevation on record. The warm conditions of recent years have resulted in enhanced melt and reduction of the refreezing capacity in the lower accumulation area. If high temperatures continue, the current lower accumulation area will turn into a region with superimposed ice in coming years.

Streptococcus mutans forms xylitol-resistant biofilm on excess adhesive flash in novel ex-vivo orthodontic bracket model.

PubMed

Ho, Cindy S F; Ming, Yue; Foong, Kelvin W C; Rosa, Vinicius; Thuyen, Truong; Seneviratne, Chaminda J

2017-04-01

During orthodontic bonding procedures, excess adhesive is invariably left on the tooth surface at the interface between the bracket and the enamel junction; it is called excess adhesive flash (EAF). We comparatively evaluated the biofilm formation of Streptococcus mutans on EAF produced by 2 adhesives and examined the therapeutic efficacy of xylitol on S mutans formed on EAF. First, we investigated the biofilm formation of S mutans on 3 orthodontic bracket types: stainless steel preadjusted edgewise, ceramic preadjusted edgewise, and stainless steel self-ligating. Subsequently, tooth-colored Transbond XT (3M Unitek, Monrovia, Calif) and green Grengloo (Ormco, Glendora, Calif) adhesives were used for bonding ceramic brackets to extracted teeth. S mutans biofilms on EAF produced by the adhesives were studied using the crystal violet assay and scanning electron microscopy. Surface roughness and surface energy of the EAF were examined. The therapeutic efficacies of different concentrations of xylitol were tested on S mutans biofilms. Significantly higher biofilms were formed on the ceramic preadjusted edgewise brackets (P = 0.003). Transbond XT had significantly higher S mutans biofilms compared with Grengloo surfaces (P = 0.007). There was no significant difference in surface roughness between Transbond XT and Grengloo surfaces (P >0.05). Surface energy of Transbond XT had a considerably smaller contact angle than did Grengloo, suggesting that Transbond XT is a more hydrophilic material. Xylitol at low concentrations had no significant effect on the reduction of S mutans biofilms on orthodontic adhesives (P = 0.016). Transbond XT orthodontic adhesive resulted in more S mutans biofilm compared with Grengloo adhesive on ceramic brackets. Surface energy seemed to play a more important role than surface roughness for the formation of S mutans biofilm on EAF. Xylitol does not appear to have a therapeutic effect on mature S mutans biofilm. Copyright © 2017 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.

Impact of Sustainable Cool Roof Technology on Building Energy Consumption

NASA Astrophysics Data System (ADS)

Vuppuluri, Prem Kiran

Highly reflective roofing systems have been analyzed over several decades to evaluate their ability to meet sustainability goals, including reducing building energy consumption and mitigating the urban heat island. Studies have isolated and evaluated the effects of climate, surface reflectivity, and roof insulation on energy savings, thermal load mitigation and also ameliorating the urban heat island. Other sustainable roofing systems, like green-roofs and solar panels have been similarly evaluated. The motivation for the present study is twofold: the first goal is to present a method for simultaneous evaluation and inter-comparison of multiple roofing systems, and the second goal is to quantitatively evaluate the realized heating and cooling energy savings associated with a white roof system compared to the reduction in roof-top heat flux. To address the first research goal a field experiment was conducted at the International Harvester Building located in Portland, OR. Thermal data was collected for a white roof, vegetated roof, and a solar panel shaded vegetated roof, and the heat flux through these roofing systems was compared against a control patch of conventional dark roof membrane. The second research goal was accomplished using a building energy simulation program to determine the impact of roof area and roof insulation on the savings from a white roof, in both Portland and Phoenix. The ratio of cooling energy savings to roof heat flux reduction from replacing a dark roof with a white roof was 1:4 for the month of July, and 1:5 annually in Portland. The COP of the associated chillers ranges from 2.8-4.2, indicating that the ratio of cooling energy savings to heat flux reduction is not accounted for solely by the COP of the chillers. The results of the building simulation indicate that based on energy savings alone, white roofs are not an optimal choice for Portland. The benefits associated with cooling energy savings relative to a black roof are offset by the winter-time penalty, and the net benefit from adopting white roof technology in Portland is small. That said, there are other potential benefits of white roofing such as impact on urban heat islands and roof life that must also be considered.

Hybrid-Particle-In-Cell Simulation of Backsputtered Carbon Transport in the Near-Field Plume of a Hall Thruster

NASA Technical Reports Server (NTRS)

Choi, Maria; Yim, John T.; Williams, George J.; Herman, Daniel A.; Gilland, James H.

2018-01-01

Magnetic shielding has eliminated boron nitride erosion as the life limiting mechanism in a Hall thruster but has resulted in erosion of the front magnetic field pole pieces. Recent experiments show that the erosion of graphite pole covers, which are added to protect the magnetic field pole pieces, causes carbon to redeposit on other surfaces, such as boron nitride discharge channel and cathode keeper surfaces. As a part of the risk-reduction activities for Advanced Electric Propulsion System thruster development, this study models transport of backsputtered carbon from the graphite front pole covers and vacuum facility walls. Fluxes, energy distributions, and redeposition rates of backsputtered carbon on the anode, discharge channel, and graphite cathode keeper surfaces are predicted.

Electroless silver plating on PET fabric initiated by in situ reduction of polyaniline

NASA Astrophysics Data System (ADS)

Mu, Shipeng; Xie, Huayang; Wang, Wei; Yu, Dan

2015-10-01

Novel electroless silver plating poly(ethylene terephthalate) (PET) fabric was prepared by a two-step procedure. In the first step, the in situ polymerized polyaniline (PANI) occurred on the fabric surface in the presence of ammonium persulfate (APS). Then, Ag(0) species reduced from silver nitrate (AgNO3) by in situ reduction of PANI were used as catalyst to initiate electroless silver plating. Hence, this composite material was prepared by conductive polymer combined with electroless plating. The silver layer on PET fabric surface was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive spectroscopy (EDX) as well as X-ray photoelectron spectroscopy (XPS). The results showed that the silver layer was plated uniformly and compactly with surface resistance about 0.1 Ω/sq on average. The shielding effectiveness (SE) of silver-plated PET fabric was around 50-90 dB, which was considered to have potential applications in electromagnetic shielding materials. Thermogravimetric (TG) analysis was carried out to study thermal stability. The antibacterial tests demonstrated that the silver-plated fabric exhibited excellent antibacterial activity against Staphylococcus aureus and Escherichia coli both with 100%.

Deposition of thin Si and Ge films by ballistic hot electron reduction in a solution-dripping mode and its application to the growth of thin SiGe films

NASA Astrophysics Data System (ADS)

Suda, Ryutaro; Yagi, Mamiko; Kojima, Akira; Mentek, Romain; Mori, Nobuya; Shirakashi, Jun-ichi; Koshida, Nobuyoshi

2015-04-01

To enhance the usefulness of ballistic hot electron injection into solutions for depositing thin group-IV films, a dripping scheme is proposed. A very small amount of SiCl4 or GeCl4 solution was dripped onto the surface of a nanocrystalline Si (nc-Si) electron emitter, and then the emitter is driven without using any counter electrodes. It is shown that thin Si and Ge films are deposited onto the emitting surface. Spectroscopic surface and compositional analyses showed no extrinsic carbon contaminations in deposited thin films, in contrast to the results of a previous study using the dipping scheme. The availability of this technique for depositing thin SiGe films is also demonstrated using a mixture SiCl4+GeCl4 solution. Ballistic hot electrons injected into solutions with appropriate kinetic energies promote preferential reduction of target ions with no by-products leading to nuclei formation for the thin film growth. Specific advantageous features of this clean, room-temperature, and power-effective process is discussed in comparison with the conventional dry and wet processes.

New pathway to prepare gold nanoparticles and their applications in catalysis and surface-enhanced Raman scattering.

PubMed

Chang, Chun-Chao; Yang, Kuang-Hsuan; Liu, Yu-Chuan; Hsu, Ting-Chu

2012-05-01

As shown in the literature, additional energies are necessary for the reduction of positively charged noble metal ions to prepare metal nanoparticles (NPs). In this work, we report a new green pathway to prepare Au NPs in neutral 0.1M NaCl aqueous solutions from bulk Au substrates without addition of any stabilizer and reductant just via aid of natural chitosan (Ch) at room temperature. Au- and Ch-containing complexes in aqueous solution were electrochemically prepared. The role of Ch is just an intermediate to perform electron transfer with Au NPs. The stability of these prepared Au NPs is well maintained by Au NPs themselves with slightly positively charged Au remained on the surface of Au NPs. The particle size of prepared spherical Au (111) NPs is ca. 15 nm in diameter. Moreover, increasing the pH of preparation solutions can be contributive to preparing concentrated Au NPs in solutions. The prepared Au NPs are surface-enhanced Raman scattering (SERS)-active for probe molecules of Rhodamine 6G. They also demonstrate significantly catalytic activity for decomposition of acetaldehyde in rice wine. Copyright © 2012 Elsevier B.V. All rights reserved.

Variability of albedo and utility of the MODIS albedo product in forested wetlands

USGS Publications Warehouse

Sumner, David M.; Wu, Qinglong; Pathak, Chandra S.

2011-01-01

Albedo was monitored over a two-year period (beginning April 2008) at three forested wetland sites in Florida, USA using up- and down-ward facing pyranometers. Water level, above and below land surface, is the primary control on the temporal variability of daily albedo. Relatively low reflectivity of water accounts for the observed reductions in albedo with increased inundation of the forest floor. Enhanced canopy shading of the forest floor was responsible for lower sensitivity of albedo to water level at the most dense forest site. At one site, the most dramatic reduction in daily albedo was observed during the inundation of a highly-reflective, calcareous periphyton-covered land surface. Satellite-based Moderate-Resolution Imaging Spectroradiometer (MODIS) estimates of albedo compare favorably with measured albedo. Use of MODIS albedo values in net radiation computations introduced a root mean squared error of less than 4.7 W/m2 and a mean, annual bias of less than 2.3 W/m2 (1.7%). These results suggest that MODIS-estimated albedo values can reliably be used to capture areal and temporal variations in albedo that are important to the surface energy balance.

Relevance of impacter shape to nonvisible damage and residual tensile strength of a thick graphite/epoxy laminate

NASA Technical Reports Server (NTRS)

Poe, C. C., Jr.

1990-01-01

A study was made to determine the relevance of impacter shape to nonvisible damage and tensile residual strength of a 36 mm (1.4 in.) thick graphite/epoxy motor case. The shapes of the impacters were as follows: 12.7 mm (0.5 in.) and 25.4 mm (1.0 in.) diameter hemispheres, a sharp corner, and a 6.3 mm (0.25 in.) diameter bolt-like rod. The investigation revealed that damage initiated when the contact pressure exceeded a critical level. However, the damage was not visible on the surface until an even higher pressure was exceeded. The damage on the surface consisted of a crater shaped like the impacter, and the damage below the surface consisted of broken fibers. The impact energy to initiate damage or cause visible damage on the surface increased approximately with impacter diameter to the third power. The reduction in strength for nonvisible damage increased with increasing diameter, 9 and 30 percent for the 12.7 mm (0.5 in.) and 25.4 mm (1.0 in.) diameter hemispheres, respectively. The corner impacter made visible damage on the surface for even the smallest impact energy. The rod impacter acted like a punch and sliced through the composite. Even so, the critical level of pressure to initiate damage was the same for the rod and hemispherical impacters. Factors of safety for nonvisible damage increased with increasing kinetic energy of impact. The effects of impacter shape on impact force, damage size, damage visibility, and residual tensile strength were predicted quite well assuming Hertzian contact and using maximum stress criteria and a surface crack analysis.

TiO2-NT electrodes modified with Ag and diamond like carbon (DLC) for hydrogen production by alkaline water electrolysis

NASA Astrophysics Data System (ADS)

Baran, Evrim; Baz, Zeynep; Esen, Ramazan; Yazici Devrim, Birgül

2017-10-01

In present work, the two-step anodization technique was applied for synthesis of TiO2 nanotube (NT). Silver and diamond like carbon (DLC) were coated on the surface of as prepared TiO2-NT using chemical reduction method and MW ECR plasma system. The morphology, composition and structure of the electrodes were examined by field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). The results showed that Ag nanoparticles, having size in the range of 48-115 nm, are evenly distributed on the top, inside and outside surface of TiO2-NT and when DLC was coated on the surface of TiO2-NT and TiO2-NT-Ag, the top of nanotubes were partially open and the pore diameter of hexagonal structure decreased from 165 nm to of 38-80 nm. On the other hand, the microhardness test and contact angle measurements revealed that additions of Ag and diamond like carbon have a positive effect on the mechanical properties of TiO2-NT film. The electrocatalytic properties of the electrodes towards the hydrogen evolution reaction (HER) were investigated by the electrochemical measurements recorded in 1 M KOH solution. In addition, long-term durability of electrodes towards HER and the energy consumption of alkaline electrolysis were investigated. The energy requirement showed that while the deposition of silver provides approximately 14.95% savings of the energy consumption, the DLC coating causes increase in energy consumption.

Improving model biases in an ESM with an isopycnic ocean component by accounting for wind work on oceanic near-inertial motions.

NASA Astrophysics Data System (ADS)

de Wet, P. D.; Bentsen, M.; Bethke, I.

2016-02-01

It is well-known that, when comparing climatological parameters such as ocean temperature and salinity to the output of an Earth System Model (ESM), the model exhibits biases. In ESMs with an isopycnic ocean component, such as NorESM, insufficient vertical mixing is thought to be one of the causes of such differences between observational and model data. However, enhancing the vertical mixing of the model's ocean component not only requires increasing the energy input, but also sound physical reasoning for doing so. Various authors have shown that the action of atmospheric winds on the ocean's surface is a major source of energy input into the upper ocean. However, due to model and computational constraints, oceanic processes linked to surface winds are incompletely accounted for. Consequently, despite significantly contributing to the energy required to maintain ocean stratification, most ESMs do not directly make provision for this energy. In this study we investigate the implementation of a routine in which the energy from work done on oceanic near-inertial motions is calculated in an offline slab model. The slab model, which has been well-documented in the literature, runs parallel to but independently from the ESM's ocean component. It receives wind fields with a frequency higher than that of the coupling frequency, allowing it to capture the fluctuations in the winds on shorter time scales. The additional energy calculated thus is then passed to the ocean component, avoiding the need for increased coupling between the components of the ESM. Results show localised reduction in, amongst others, the salinity and temperature biases of NorESM, confirming model sensitivity to wind-forcing and points to the need for better representation of surface processes in ESMs.

Computational evaluation of sub-nanometer cluster activity of singly exposed copper atom with various coordinative environment in catalytic CO2 transformation

NASA Astrophysics Data System (ADS)

Shanmugam, Ramasamy; Thamaraichelvan, Arunachalam; Ganesan, Tharumeya Kuppusamy; Viswanathan, Balasubramanian

2017-02-01

Metal cluster, at sub-nanometer level has a unique property in the activation of small molecules, in contrast to that of bulk surface. In the present work, singly exposed active site of copper metal cluster at sub-nanometer level was designed to arrive at the energy minimised configurations, binding energy, electrostatic potential map, frontier molecular orbitals and partial density of states. The ab initio molecular dynamics was carried out to probe the catalytic nature of the cluster. Further, the stability of the metal cluster and its catalytic activity in the electrochemical reduction of CO2 to CO were evaluated by means of computational hydrogen electrode via calculation of the free energy profile using DFT/B3LYP level of theory in vacuum. The activity of the cluster is ascertained from the fact that the copper atom, present in a two coordinative environment, performs a more selective conversion of CO2 to CO at an applied potential of -0.35 V which is comparatively lower than that of higher coordinative sites. The present study helps to design any sub-nano level metal catalyst for electrochemical reduction of CO2 to various value added chemicals.

Paper-Based Analytical Devices Relying on Visible-Light-Enhanced Glucose/Air Biofuel Cells.

PubMed

Wu, Kaiqing; Zhang, Yan; Wang, Yanhu; Ge, Shenguang; Yan, Mei; Yu, Jinghua; Song, Xianrang

2015-11-04

A strategy that combines visible-light-enhanced biofuel cells (BFCs) and electrochemical immunosensor into paper-based analytical devices was proposed for sensitive detection of the carbohydrate antigen 15-3 (CA15-3). The gold nanoparticle modified paper electrode with large surface area and good conductibility was applied as an effective matrix for primary antibodies. The glucose dehydrogenase (GDH) modified gold-silver bimetallic nanoparticles were used as bioanodic biocatalyst and signal magnification label. Poly(terthiophene) (pTTh), a photoresponsive conducting polymer, served as catalyst in cathode for the reduction of oxygen upon illumination by visible light. In the bioanode, electrons were generated through the oxidation of glucose catalyzed by GDH. The amount of electrons is determined by the amount of GDH, which finally depended on the amount of CA15-3. In the cathode, electrons from the bioanode could combine with the generated holes in the HOMO energy level of cathode catalysts pTTh. Meanwhile, the high energy level photoexcited electrons were generated in the LUMO energy level and involved in the oxygen reduction reaction, finally resulting in an increasing current and a decreasing overpotential. According to the current signal, simple and efficient detection of CA15-3 was achieved.

Hydrogen-vacancy-dislocation interactions in α-Fe

NASA Astrophysics Data System (ADS)

Tehranchi, A.; Zhang, X.; Lu, G.; Curtin, W. A.

2017-02-01

Atomistic simulations of the interactions between dislocations, hydrogen atoms, and vacancies are studied to assess the viability of a recently proposed mechanism for the formation of nanoscale voids in Fe-based steels in the presence of hydrogen. Quantum-mechanics/molecular-mechanics method calculations confirm molecular statics simulations based on embedded atom method (EAM) potential showing that individual vacancies on the compressive side of an edge dislocation can be transported with the dislocation as it glides. Molecular dynamics simulations based on EAM potential then show, however, that vacancy clusters in the glide plane of an approaching dislocation are annihilated or reduced in size by the creation of a double-jog/climb process that is driven by the huge reduction in energy accompanying vacancy annihilation. The effectiveness of annihilation/reduction processes is not reduced by the presence of hydrogen in the vacancy clusters because typical V-H cluster binding energies are much lower than the vacancy formation energy, except at very high hydrogen content in the cluster. Analysis of a range of configurations indicates that hydrogen plays no special role in stabilizing nanovoids against jog formation processes that shrink voids. Experimental observations of nanovoids on the fracture surfaces of steels must be due to as-yet undetermined processes.

Analysis of cutting force signals by wavelet packet transform for surface roughness monitoring in CNC turning

NASA Astrophysics Data System (ADS)

García Plaza, E.; Núñez López, P. J.

2018-01-01

On-line monitoring of surface finish in machining processes has proven to be a substantial advancement over traditional post-process quality control techniques by reducing inspection times and costs and by avoiding the manufacture of defective products. This study applied techniques for processing cutting force signals based on the wavelet packet transform (WPT) method for the monitoring of surface finish in computer numerical control (CNC) turning operations. The behaviour of 40 mother wavelets was analysed using three techniques: global packet analysis (G-WPT), and the application of two packet reduction criteria: maximum energy (E-WPT) and maximum entropy (SE-WPT). The optimum signal decomposition level (Lj) was determined to eliminate noise and to obtain information correlated to surface finish. The results obtained with the G-WPT method provided an in-depth analysis of cutting force signals, and frequency ranges and signal characteristics were correlated to surface finish with excellent results in the accuracy and reliability of the predictive models. The radial and tangential cutting force components at low frequency provided most of the information for the monitoring of surface finish. The E-WPT and SE-WPT packet reduction criteria substantially reduced signal processing time, but at the expense of discarding packets with relevant information, which impoverished the results. The G-WPT method was observed to be an ideal procedure for processing cutting force signals applied to the real-time monitoring of surface finish, and was estimated to be highly accurate and reliable at a low analytical-computational cost.

10 CFR 490.804 - Eligible reductions in petroleum consumption.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 10 Energy 3 2013-01-01 2013-01-01 false Eligible reductions in petroleum consumption. 490.804 Section 490.804 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.804 Eligible reductions in petroleum consumption. (a) Motor vehicles...

10 CFR 490.804 - Eligible reductions in petroleum consumption.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 10 Energy 3 2014-01-01 2014-01-01 false Eligible reductions in petroleum consumption. 490.804 Section 490.804 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.804 Eligible reductions in petroleum consumption. (a) Motor vehicles...

10 CFR 490.804 - Eligible reductions in petroleum consumption.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 3 2011-01-01 2011-01-01 false Eligible reductions in petroleum consumption. 490.804 Section 490.804 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.804 Eligible reductions in petroleum consumption. (a) Motor vehicles...

10 CFR 490.804 - Eligible reductions in petroleum consumption.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 10 Energy 3 2010-01-01 2010-01-01 false Eligible reductions in petroleum consumption. 490.804 Section 490.804 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.804 Eligible reductions in petroleum consumption. (a) Motor vehicles...

10 CFR 490.804 - Eligible reductions in petroleum consumption.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 10 Energy 3 2012-01-01 2012-01-01 false Eligible reductions in petroleum consumption. 490.804 Section 490.804 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.804 Eligible reductions in petroleum consumption. (a) Motor vehicles...

Impact behaviour of auxetic Kevlar®/ epoxy composites

NASA Astrophysics Data System (ADS)

Yang, S.; Chalivendra, V. B.; Kim, Y. K.

2017-10-01

Experimental study was performed to investigate fracture and impact properties of novel Auxetic Kevlar® laminated composites. For comparison, standard Kevlar® woven composites with and without polyurethane surface treatment were also considered in this study. For these three composites, short nylon fibers of two different fiber lengths and three different fiber densities were flocked between laminates. Vacuum infusion process along with optimized compaction was employed to fabricate composites. The double cantilever beam configuration was used to investigate the fracture properties. The Auxetic Kevlar® composites showed a significant improvement of 225% in fracture toughness compared to regular woven Kevlar® composites. Furthermore, the initiation toughness was increased by 577% with the application of flocking in Auxetic Kevlar®. During impact testing, the Auxetic Kevlar® reinforced composites showed a significant reduction in damaged area compared to woven counterpart. On the other hand, the reduction in damaged area influenced the reduction in impact energy absorption.

Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction

PubMed Central

2017-01-01

Conversion of carbon monoxide (CO), a major one-carbon product of carbon dioxide (CO2) reduction, into value-added multicarbon species is a challenge to addressing global energy demands and climate change. Here we report a modular synthetic approach for aqueous electrochemical CO reduction to carbon–carbon coupled products via self-assembly of supramolecular cages at molecular–materials interfaces. Heterobimetallic cavities formed by face-to-face coordination of thiol-terminated metalloporphyrins to copper electrodes through varying organic struts convert CO to C2 products with high faradaic efficiency (FE = 83% total with 57% to ethanol) and current density (1.34 mA/cm2) at a potential of −0.40 V vs RHE. The cage-functionalized electrodes offer an order of magnitude improvement in both selectivity and activity for electrocatalytic carbon fixation compared to parent copper surfaces or copper functionalized with porphyrins in an edge-on orientation. PMID:28979945

Theoretical Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2012-10-10

We use density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5- 1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, nonhollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity towards the oxygen reduction reaction of platinum nanowires was addressed by studying the change in the chemisorption energies of oxygen and hydroxyl groups, inducedmore » by inserting the inner chain of platinum atoms into the hollow nanotubes. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Nanotubes with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Density Functional Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2013-03-14

We used density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5–1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, non-hollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity toward the oxygen reduction reaction of platinum nanowires was assessed by studying the change in the chemisorption energies of oxygen, hydroxyl, and hydroperoxyl groups, inducedmore » by converting the nanotube models to nanowires. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Single-wall nanotubes and platinum nanowires with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Increasing the Energy Efficiency of Aluminum-Reduction Cells Using Modified Cathodes

NASA Astrophysics Data System (ADS)

Jianping, Peng; Yang, Song; Yuezhong, Di; Yaowu, Wang; Naixiang, Feng

2017-10-01

A cathode with an inclined surface (5°) and increased bar collector height (230 mm high) was incorporated into two 300-kA industrial aluminum-reduction cells. The voltage of the cells with the modified cathode was reduced by approximately 200 mV when compared with that of a conventional cell with a flat cathode. Through the use of simulations, the reduction in the cell voltage was attributed to the cathode modification (40 mV) and a reduced electrolyte level of 0.5 cm (160 mV). As a result of reduced anode cathode distance (ACD), the ledge toe was extended to the anode shadow by 12 cm. This caused a large inverted horizontal current and a velocity increase. The ledge profile returned to the desired position when the cells were insulated more effectively, and the metal velocity and metal crest in the modified cells were reduced accordingly.

Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction

DOE PAGES

Gong, Ming; Cao, Zhi; Liu, Wei; ...

2017-09-13

Conversion of carbon monoxide (CO), a major one-carbon product of carbon dioxide (CO 2) reduction, into value-added multicarbon species is a challenge to addressing global energy demands and climate change. Here in this paper, we report a modular synthetic approach for aqueous electrochemical CO reduction to carbon-carbon coupled products via self-assembly of supramolecular cages at molecular-materials interfaces. Heterobimetallic cavities formed by face-to-face coordination of thiol-terminated metalloporphyrins to copper electrodes through varying organic struts convert CO to C2 products with high faradaic efficiency (FE = 83% total with 57% to ethanol) and current density (1.34 mA/cm 2) at a potential ofmore » -0.40 V vs RHE. The cage-functionalized electrodes offer an order of magnitude improvement in both selectivity and activity for electrocatalytic carbon fixation compared to parent copper surfaces or copper functionalized with porphyrins in an edge-on orientation.« less

The membrane biofilm reactor: the natural partnership of membranes and biofilm.

PubMed

Rittmann, B E

2006-01-01

Many exciting new technologies for water-quality control combine microbiological processes with adsorption, advanced oxidation, a membrane or an electrode to improve performance, address emerging contaminants or capture renewable energy. An excellent example is the H2-based membrane biofilm reactor (MBfR), which delivers H2 gas to a biofilm that naturally accumulates on the outer surface of a bubbleless membrane. Autotrophic bacteria in the biofilm oxidise the H2 and use the electrons to reduce NO3-, CIO4- and other oxidised contaminants. This natural partnership of membranes and biofilm makes it possible to gain many cost, performance and simplicity advantages from using H2 as the electron donor for microbially catalysed reductions. The MBfR has been demonstrated for denitrification in drinking water; reduction of perchlorate in groundwater; reduction of selenate, chromate, trichloroethene and other emerging contaminants; advanced N removal in wastewater treatment and autotrophic total-N removal.

[Efficiency of industrial energy conservation and carbon emission reduction in Liaoning Pro-vince based on data envelopment analysis (DEA)method.

PubMed

Wang, Li; Xi, Feng Ming; Li, Jin Xin; Liu, Li Li

2016-09-01

Taking 39 industries as independent decision-making units in Liaoning Province from 2003 to 2012 and considering the benefits of energy, economy and environment, we combined direction distance function and radial DEA method to estimate and decompose the energy conservation and carbon emissions reduction efficiency of the industries. Carbon emission of each industry was calculated and defined as an undesirable output into the model of energy saving and carbon emission reduction efficiency. The results showed that energy saving and carbon emission reduction efficiency of industries had obvious heterogeneity in Liaoning Province. The whole energy conservation and carbon emissions reduction efficiency in each industry of Liaoning Province was not high, but it presented a rising trend. Improvements of pure technical efficiency and scale efficiency were the main measures to enhance energy saving and carbon emission reduction efficiency, especially scale efficiency improvement. In order to improve the energy saving and carbon emission reduction efficiency of each industry in Liaoning Province, we put forward that Liaoning Province should adjust industry structure, encourage the development of low carbon high benefit industries, improve scientific and technological level and adjust the industry scale reasonably, meanwhile, optimize energy structure, and develop renewable and clean energy.

Critical heat flux maxima during boiling crisis on textured surfaces

PubMed Central

Dhillon, Navdeep Singh; Buongiorno, Jacopo; Varanasi, Kripa K.

2015-01-01

Enhancing the critical heat flux (CHF) of industrial boilers by surface texturing can lead to substantial energy savings and global reduction in greenhouse gas emissions, but fundamentally this phenomenon is not well understood. Prior studies on boiling crisis indicate that CHF monotonically increases with increasing texture density. Here we report on the existence of maxima in CHF enhancement at intermediate texture density using measurements on parametrically designed plain and nano-textured micropillar surfaces. Using high-speed optical and infrared imaging, we study the dynamics of dry spot heating and rewetting phenomena and reveal that the dry spot heating timescale is of the same order as that of the gravity and liquid imbibition-induced dry spot rewetting timescale. Based on these insights, we develop a coupled thermal-hydraulic model that relates CHF enhancement to rewetting of a hot dry spot on the boiling surface, thereby revealing the mechanism governing the hitherto unknown CHF enhancement maxima. PMID:26346098

Electromagnetic studies of redox systems for energy storage

NASA Technical Reports Server (NTRS)

Wu, C. D.; Scherson, D.; Yeager, E.

1981-01-01

Both chromium and iron couples were studied on various electrode surfaces in acidic perchlorate solution by using rotating ring-disk techniques. It was found that chloride which forms inner sphere coordination complexes with the redox species enhances the electrode kinetics dramatically. The effects of lead underpotential deposition and surface alloy formation on the kinetics of the chromium couple on gold were studied using both linear sweep voltammetry and potential step techniques. The lad underpotential deposition was found to slow down the kinetics of the reduction of the Cr species on gold surfaces although increase the hydrogen overvoltage. The effect on the chromium kinetics can be explained in terms of principally a double layer effect. The underpotential deposition lead species with its positive charge results in a decrease in the concentration of the Cr species at the electrode surface. Similar phenomena were also observed with bismuth underpotential deposition on gold for the iron couple.

Structural Evolution of Nanoscale Zero-Valent Iron (nZVI) in Anoxic Co2+Soultion : Interactional Performance and Mechanism

NASA Astrophysics Data System (ADS)

Dai, C.; Zhang, Y.

2015-12-01

The nanoscale particle and low oxidation reduction potential make nano zero-valent iron (nZVI) an efficient sorbent and reductant for treating many kinds of organic contaminants and heavy metals.The structures of nanoscale zero-valent iron (nZVI) particles are evolving in reactions, and the reactions are influenced by the evolved structures. In order to understand the detail removal process, it is important to investigate the interactions between reactions and structural evolution. In this work, reactions between nZVI and Co2+ at different initial concentrations in anoxic aqueous solutions (to eliminate the effects of O2) were tracked for 10 days using a variety of methods including inductively coupled plasma optical emission spectrometry (ICP-OES), high resolution-transmission electron microscopy (HR-TEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM). Continuous removal and reduction of Co2+ by nZVI caused by structural evolution were revealed in reaction processes. The system pH (pH measured in mixture), which controls the stability of coprecipitation and the corrosion rate of nZVI, was deemed as the determining factors of structural evolutions. X-ray photoelectron spectroscopy (XPS) results showed that the formation and dissolution of sheet structure impacts on the ratio of Fe (0) on nZVI's surface and the surface reduction of Co2+. The cavity structure provides the possibility of Co migrating from surface to inside of nZVI leading a continuous removal. A subacidity condition could accelerate the evolution to improve the removal of Co2+ and the results of structural controlled reactions further indicated that the removal was suspended by sheet structure and enhanced by cavity structure. The results in this study revealed "structural influence" for fully and dynamically understanding nZVI's reactions.

Oxygen reduction reaction (orr) on bimetallic AuPt and AuPd(1 0 0)-electrodes: Effects of the heteroatomic junction on the reaction paths

NASA Astrophysics Data System (ADS)

Schulte, E.; Belletti, G.; Arce, M.; Quaino, P.

2018-05-01

The seek for materials to enhance the oxygen reduction reaction (orr) rate is a highly relevant topic due to its implication in fuel cell devices. Herein, the orr on bimetallic electrocatalysts based on Au-M (M = Pt, Pd) has been studied computationally, by performing density functional theory calculations. Bimetallic (1 0 0) electrode surfaces with two different Au:M ratios were proposed, and two possible pathways, associative and dissociative, were considered for the orr. Changes in the electronic properties of these materials with respect to the pure metals were acknowledged to gain understanding in the overall reactivity trend. The effect of the bimetallic junction on the stability of the intermediates O2 and OOH was also evaluated by means of geometrical and energetic parameters; being the intermediates preferably adsorbed on Pt/Pd atoms, but presenting in some cases higher adsorption energies compared with bare metals. Finally, the kinetics of the Osbnd O bond breaking in O2∗ and OOH∗ adsorbed intermediates in the bimetallic materials and the influence of the Au-M junction were studied by means of the nudge elastic-band method. A barrierless process for the scission of O2∗ was found in Au-M for the higher M ratios. Surprisingly, for Au-M with lower M ratios, the barriers were much lower than for pure Au surfaces, suggesting a highly reactive surface towards the orr. The Osbnd O scission of the OOH∗ was found to be a barrierless process in Ausbnd Pt systems and nearly barrierless in all Ausbnd Pd systems, implying that the reduction ofO2 in these systems proceeds via the full reduction of O2 to H2O , avoiding H2O2 formation.

Global health benefits of mitigating ozone pollution with methane emission controls.

PubMed

West, J Jason; Fiore, Arlene M; Horowitz, Larry W; Mauzerall, Denise L

2006-03-14

Methane (CH(4)) contributes to the growing global background concentration of tropospheric ozone (O(3)), an air pollutant associated with premature mortality. Methane and ozone are also important greenhouse gases. Reducing methane emissions therefore decreases surface ozone everywhere while slowing climate warming, but although methane mitigation has been considered to address climate change, it has not for air quality. Here we show that global decreases in surface ozone concentrations, due to methane mitigation, result in substantial and widespread decreases in premature human mortality. Reducing global anthropogenic methane emissions by 20% beginning in 2010 would decrease the average daily maximum 8-h surface ozone by approximately 1 part per billion by volume globally. By using epidemiologic ozone-mortality relationships, this ozone reduction is estimated to prevent approximately 30,000 premature all-cause mortalities globally in 2030, and approximately 370,000 between 2010 and 2030. If only cardiovascular and respiratory mortalities are considered, approximately 17,000 global mortalities can be avoided in 2030. The marginal cost-effectiveness of this 20% methane reduction is estimated to be approximately 420,000 US dollars per avoided mortality. If avoided mortalities are valued at 1 US dollars million each, the benefit is approximately 240 US dollars per tone of CH(4) ( approximately 12 US dollars per tone of CO(2) equivalent), which exceeds the marginal cost of the methane reduction. These estimated air pollution ancillary benefits of climate-motivated methane emission reductions are comparable with those estimated previously for CO(2). Methane mitigation offers a unique opportunity to improve air quality globally and can be a cost-effective component of international ozone management, bringing multiple benefits for air quality, public health, agriculture, climate, and energy.

Nested high-resolution modeling of the impact of urbanization on regional climate in three vast urban agglomerations in China

NASA Astrophysics Data System (ADS)

Wang, Jun; Feng, Jinming; Yan, Zhongwei; Hu, Yonghong; Jia, Gensuo

2012-11-01

In this paper, the Weather Research and Forecasting Model, coupled to the Urban Canopy Model, is employed to simulate the impact of urbanization on the regional climate over three vast city agglomerations in China. Based on high-resolution land use and land cover data, two scenarios are designed to represent the nonurban and current urban land use distributions. By comparing the results of two nested, high-resolution numerical experiments, the spatial and temporal changes on surface air temperature, heat stress index, surface energy budget, and precipitation due to urbanization are analyzed and quantified. Urban expansion increases the surface air temperature in urban areas by about 1°C, and this climatic forcing of urbanization on temperature is more pronounced in summer and nighttime than other seasons and daytime. The heat stress intensity, which reflects the combined effects of temperature and humidity, is enhanced by about 0.5 units in urban areas. The regional incoming solar radiation increases after urban expansion, which may be caused by the reduction of cloud fraction. The increased temperature and roughness of the urban surface lead to enhanced convergence. Meanwhile, the planetary boundary layer is deepened, and water vapor is mixed more evenly in the lower atmosphere. The deficit of water vapor leads to less convective available potential energy and more convective inhibition energy. Finally, these combined effects may reduce the rainfall amount over urban areas, mainly in summer, and change the regional precipitation pattern to a certain extent.

Nested High Resolution Modeling of the Impact of Urbanization on Regional Climate in Three Vast Urban Agglomerations in China

NASA Astrophysics Data System (ADS)

Wang, Jun; Feng, Jinming; Yan, Zhongwei; Hu, Yonghong; Jia, Gensuo

2013-04-01

In this paper, the Weather Research and Forecasting (WRF) model coupled to the Urban Canopy Model (UCM) is employed to simulate the impact of urbanization on the regional climate over three vast city agglomerations in China. Based on high resolution land use and land cover data, two scenarios are designed to represent the non-urban and current urban land use distributions. By comparing the results of two nested, high resolution numerical experiments, the spatial and temporal changes on surface air temperature, heat stress index, surface energy budget and precipitation due to urbanization are analyzed and quantified. Urban expansion increases the surface air temperature in urban areas by about 1? and this climatic forcing of urbanization on temperature is more pronounced in summer and nighttime than other seasons and daytime. The heat stress intensity, which reflects the combined effects of temperature and humidity, is enhanced by about 0.5 units in urban areas. The regional incoming solar radiation increases after urban expansion, which may be caused by the reduction of cloud fraction. The increased temperature and roughness of the urban surface lead to enhanced convergence. Meanwhile, the planetary boundary layer is deepened and water vapor is mixed more evenly in the lower atmosphere. The deficit of water vapor leads to less convective available potential energy and more convective inhibition energy. Finally, these combined effects may reduce the rainfall amount over urban area mainly in summer and change the regional precipitation pattern to a certain extent.

Summary of SLAC's SEY Measurement On Flat Accelerator Wall Materials

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

Le Pimpec, F.; /PSI, Villigen /SLAC

The electron cloud effect (ECE) causes beam instabilities in accelerator structures with intense positively charged bunched beams. Reduction of the secondary electron yield (SEY) of the beam pipe inner wall is effective in controlling cloud formation. We summarize SEY results obtained from flat TiN, TiZrV and Al surfaces carried out in a laboratory environment. SEY was measured after thermal conditioning, as well as after low energy, less than 300 eV, particle exposure.

An Investigation of the Effectiveness of Solar Power on Navy Surface Combatants

DTIC Science & Technology

2013-09-01

addition , this could cause a measureable reduction in the Navy’s environmental impact, especially since solar power can be generated both when the ships...that a relatively small addition in overall ship’s displacement would be required to implement a solar power system. Additionally, the solar cells...as a source of pulse power for large electrical loads such as high - energy weapons or radars. Both these applications are well within the current

Emission dynamics of hybrid plasmonic gold/organic GaN nanorods

NASA Astrophysics Data System (ADS)

Mohammadi, F.; Schmitzer, H.; Kunert, G.; Hommel, D.; Ge, J.; Duscher, G.; Langbein, W.; Wagner, H. P.

2017-12-01

We studied the emission of bare and aluminum quinoline (Alq3)/gold coated wurtzite GaN nanorods by temperature- and intensity-dependent time-integrated and time-resolved photoluminescence (PL). The GaN nanorods of ˜1.5 μm length and ˜250 nm diameter were grown by plasma-assisted molecular beam epitaxy. Gold/Alq3 coated GaN nanorods were synthesized by organic molecular beam deposition. The near band-edge and donor-acceptor pair luminescence was investigated in bare GaN nanorods and compared with multilevel model calculations providing the dynamical parameters for electron-hole pairs, excitons, impurity bound excitons, donors and acceptors. Subsequently, the influence of a 10 nm gold coating without and with an Alq3 spacer layer was studied and the experimental results were analyzed with the multilevel model. Without a spacer layer, a significant PL quenching and lifetime reduction of the near band-edge emission is found. The behavior is attributed to surface band-bending and Förster energy transfer from excitons to surface plasmons in the gold layer. Inserting a 5 nm Alq3 spacer layer reduces the PL quenching and lifetime reduction which is consistent with a reduced band-bending and Förster energy transfer. Increasing the spacer layer to 30 nm results in lifetimes which are similar to uncoated structures, showing a significantly decreased influence of the gold coating on the excitonic dynamics.

Emission dynamics of hybrid plasmonic gold/organic GaN nanorods.

PubMed

Mohammadi, F; Schmitzer, H; Kunert, G; Hommel, D; Ge, J; Duscher, G; Langbein, W; Wagner, H P

2017-12-15

We studied the emission of bare and aluminum quinoline (Alq 3 )/gold coated wurtzite GaN nanorods by temperature- and intensity-dependent time-integrated and time-resolved photoluminescence (PL). The GaN nanorods of ∼1.5 μm length and ∼250 nm diameter were grown by plasma-assisted molecular beam epitaxy. Gold/Alq 3 coated GaN nanorods were synthesized by organic molecular beam deposition. The near band-edge and donor-acceptor pair luminescence was investigated in bare GaN nanorods and compared with multilevel model calculations providing the dynamical parameters for electron-hole pairs, excitons, impurity bound excitons, donors and acceptors. Subsequently, the influence of a 10 nm gold coating without and with an Alq 3 spacer layer was studied and the experimental results were analyzed with the multilevel model. Without a spacer layer, a significant PL quenching and lifetime reduction of the near band-edge emission is found. The behavior is attributed to surface band-bending and Förster energy transfer from excitons to surface plasmons in the gold layer. Inserting a 5 nm Alq 3 spacer layer reduces the PL quenching and lifetime reduction which is consistent with a reduced band-bending and Förster energy transfer. Increasing the spacer layer to 30 nm results in lifetimes which are similar to uncoated structures, showing a significantly decreased influence of the gold coating on the excitonic dynamics.

Single-Crystal Antimonene Films Prepared by Molecular Beam Epitaxy: Selective Growth and Contact Resistance Reduction of the 2D Material Heterostructure.

PubMed

Chen, Hsuan-An; Sun, Hsu; Wu, Chong-Rong; Wang, Yu-Xuan; Lee, Po-Hsiang; Pao, Chun-Wei; Lin, Shih-Yen

2018-05-02

Single-crystal antimonene flakes are observed on sapphire substrates after the postgrowth annealing procedure of amorphous antimony (Sb) droplets prepared by using molecular beam epitaxy at room temperature. The large wetting angles of the antimonene flakes to the sapphire substrate suggest that an alternate substrate should be adopted to obtain a continuous antimonene film. By using a bilayer MoS 2 /sapphire sample as the new substrate, a continuous and single-crystal antimonene film is obtained at a low growth temperature of 200 °C. The results are consistent with the theoretical prediction of the lower interface energy between antimonene and MoS 2 . The different interface energies of antimonene between sapphire and MoS 2 surfaces lead to the selective growth of antimonene only atop MoS 2 surfaces on a prepatterned MoS 2 /sapphire substrate. With similar sheet resistance to graphene, it is possible to use antimonene as the contact metal of 2D material devices. Compared with Au/Ti electrodes, a specific contact resistance reduction up to 3 orders of magnitude is observed by using the multilayer antimonene as the contact metal to MoS 2 . The lower contact resistance, the lower growth temperature, and the preferential growth to other 2D materials have made antimonene a promising candidate as the contact metal for 2D material devices.

Simulation on a car interior aerodynamic noise control based on statistical energy analysis

NASA Astrophysics Data System (ADS)

Chen, Xin; Wang, Dengfeng; Ma, Zhengdong

2012-09-01

How to simulate interior aerodynamic noise accurately is an important question of a car interior noise reduction. The unsteady aerodynamic pressure on body surfaces is proved to be the key effect factor of car interior aerodynamic noise control in high frequency on high speed. In this paper, a detail statistical energy analysis (SEA) model is built. And the vibra-acoustic power inputs are loaded on the model for the valid result of car interior noise analysis. The model is the solid foundation for further optimization on car interior noise control. After the most sensitive subsystems for the power contribution to car interior noise are pointed by SEA comprehensive analysis, the sound pressure level of car interior aerodynamic noise can be reduced by improving their sound and damping characteristics. The further vehicle testing results show that it is available to improve the interior acoustic performance by using detailed SEA model, which comprised by more than 80 subsystems, with the unsteady aerodynamic pressure calculation on body surfaces and the materials improvement of sound/damping properties. It is able to acquire more than 2 dB reduction on the central frequency in the spectrum over 800 Hz. The proposed optimization method can be looked as a reference of car interior aerodynamic noise control by the detail SEA model integrated unsteady computational fluid dynamics (CFD) and sensitivity analysis of acoustic contribution.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE PAGES

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.; ...

2018-01-19

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Climate change mitigation by recovery of energy from the water cycle: a new challenge for water management.

PubMed

van der Hoek, J P

2012-01-01

Waternet is responsible for drinking water treatment and distribution, wastewater collection and treatment, and surface water management and control (quality and quantity) in and around Amsterdam. Waternet has the ambition to operate climate neutral in 2020. To realise this ambition, measures are required to compensate for the emission of 53,000 ton CO(2)-eq/year. Energy recovery from the water cycle looks very promising. First, calculations reveal that energy recovery from the water cycle in and around Amsterdam may contribute to a total reduction in greenhouse gas emissions up to 148,000 ton CO(2)-eq/year. The challenge for the coming years is to choose combinations of all the possibilities to fulfil the energy demand as much as possible. Only then the use of fossil fuel can be minimized and inevitable greenhouse gas emissions can be compensated, supporting the target to operate climate neutral in 2020.

Effect of laser energy on the SPR and size of silver nanoparticles synthesized by pulsed laser ablation in distilled water

NASA Astrophysics Data System (ADS)

Baruah, Prahlad K.; Sharma, Ashwini K.; Khare, Alika

2018-04-01

The effect of incident laser energy on the surface plasmon resonance (SPR) and size of silver nanoparticles synthesized via pulsed laser ablation of silver immersed in distilled water is reported in this paper. The broadening in the plasmonic bandwidth of the synthesized nanoparticles with the increase in the laser energy incident onto the silver target indicates the reduction in size of the nanoparticles. This is confirmed by the transmission electron microscope (TEM) images which show a decrease in the average particle size of the nanoparticles from approximately 15 to 10 nm with the increase in incident laser energy from 30 to 70 mJ, respectively. The structural features as revealed by the selected area electron diffraction and ultra-high resolution TEM studies confirmed the formation of both silver as well as silver oxide nanoparticles.

Relative complexation energies for Li(+) ion in solution: molecular level solvation versus polarizable continuum model study.

PubMed

Eilmes, Andrzej; Kubisiak, Piotr

2010-01-21

Relative complexation energies for the lithium cation in acetonitrile and diethyl ether have been studied. Quantum-chemical calculations explicitly describing the solvation of Li(+) have been performed based on structures obtained from molecular dynamics simulations. The effect of an increasing number of solvent molecules beyond the first solvation shell has been found to consist in reduction of the differences in complexation energies for different coordination numbers. Explicit-solvation data have served as a benchmark to the results of polarizable continuum model (PCM) calculations. It has been demonstrated that the PCM approach can yield relative complexation energies comparable to the predictions based on molecular-level solvation, but at significantly lower computational cost. The best agreement between the explicit-solvation and the PCM results has been obtained when the van der Waals surface was adopted to build the molecular cavity.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

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

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Exceptionally High Efficient Co-Co2P@N, P-Codoped Carbon Hybrid Catalyst for Visible Light-Driven CO2-to-CO Conversion.

PubMed

Fu, Wen Gan

2018-05-02

Artificial photosynthesis has attracted wide attention, particularly the development of efficient solar light-driven methods to reduce CO2 to form energy-rich carbon-based products. Because CO2 reduction is an uphill process with a large energy barrier, suitable catalysts are necessary to achieve this transformation. In addition, CO2 adsorption on a catalyst and proton transfer to CO2 are two important factors for the conversion reaction，and catalysts with high surface area and more active sites are required to improve the efficiency of CO2 reduction. Here, we report a visible light-driven system for CO2-to-CO conversion that consists of a heterogeneous hybrid catalyst of Co and Co2P nanoparticles embedded in carbon nanolayers codoped with N and P (Co-Co2P@NPC) and a homogeneous Ru(II)-based complex photosensitizer. The average generation rate of CO of the system was up to 35,000 μmol h-1 g-1 with selectivity of 79.1% in 3 h. Linear CO production at an exceptionally high rate of 63,000 μmol h-1 g-1 was observed in the first hour of reaction. Inspired by this highly active catalyst, we also synthesized Co@NC and Co2P@NPC materials and explored their structure, morphology, and catalytic properties for CO2 photoreduction. The results showed that the nanoparticle size, partially adsorbed H2O molecules on the catalyst surface, and the hybrid nature of the systems influenced their photocatalytic CO2 reduction performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold nanorod embedded reduction responsive block copolymer micelle-triggered drug delivery combined with photothermal ablation for targeted cancer therapy.

PubMed

Parida, Sheetal; Maiti, Chiranjit; Rajesh, Y; Dey, Kaushik K; Pal, Ipsita; Parekh, Aditya; Patra, Rusha; Dhara, Dibakar; Dutta, Pranab Kumar; Mandal, Mahitosh

2017-01-01

Gold nanorods, by virtue of surface plasmon resonance, convert incident light energy (NIR) into heat energy which induces hyperthermia. We designed unique, multifunctional, gold nanorod embedded block copolymer micelle loaded with GW627368X for targeted drug delivery and photothermal therapy. Glutathione responsive diblock co-polymer was synthesized by RAFT process forming self-assembled micelle on gold nanorods prepared by seed mediated method and GW627368X was loaded on to the reduction responsive gold nanorod embedded micelle. Photothermal therapy was administered using cwNIR laser (808nm; 4W/cm 2 ). Efficacy of nanoformulated GW627368X, photothermal therapy and combination of both were evaluated in vitro and in vivo. In response to photothermal treatment, cells undergo regulated, patterned cell death by necroptosis. Combining GW627368X with photothermal treatment using single nanoparticle enhanced therapeutic outcome. In addition, these nanoparticles are effective X-ray CT contrast agents, thus, can help in monitoring treatment. Reduction responsive nanorod embedded micelle containing folic acid and lipoic acid when treated on cervical cancer cells or tumour bearing mice, aggregate in and around cancer cells. Due to high glutathione concentration, micelles degrade releasing drug which binds surface receptors inducing apoptosis. When incident with 808nm cwNIR lasers, gold nanorods bring about photothermal effect leading to hyperthermic cell death by necroptosis. Combination of the two modalities enhances therapeutic efficacy by inducing both forms of cell death. Our proposed treatment strategy achieves photothermal therapy and targeted drug delivery simultaneously. It can prove useful in overcoming general toxicities associated with chemotherapeutics and intrinsic/acquired resistance to chemo and radiotherapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Heterojunction-Assisted Co3 S4 @Co3 O4 Core-Shell Octahedrons for Supercapacitors and Both Oxygen and Carbon Dioxide Reduction Reactions.

PubMed

Yan, Yibo; Li, Kaixin; Chen, Xiaoping; Yang, Yanhui; Lee, Jong-Min

2017-12-01

Expedition of electron transfer efficiency and optimization of surface reactant adsorption products desorption processes are two main challenges for developing non-noble catalysts in the oxygen reduction reaction (ORR) and CO 2 reduction reaction (CRR). A heterojunction prototype on Co 3 S 4 @Co 3 O 4 core-shell octahedron structure is established via hydrothermal lattice anion exchange protocol to implement the electroreduction of oxygen and carbon dioxide with high performance. The synergistic bifunctional catalyst consists of p-type Co 3 O 4 core and n-type Co 3 S 4 shell, which afford high surface electron density along with high capacitance without sacrificing mechanical robustness. A four electron ORR process, identical to the Pt catalyzed ORR, is validated using the core-shell octahedron catalyst. The synergistic interaction between cobalt sulfide and cobalt oxide bicatalyst reduces the activation energy to convert CO 2 into adsorbed intermediates and hereby enables CRR to run at a low overpotential, with formate as the highly selective main product at a high faraday efficiency of 85.3%. The remarkable performance can be ascribed to the synergistic coupling effect of the structured co-catalysts; heterojunction structure expedites the electron transfer efficiency and optimizes surface reactant adsorption product desorption processes, which also provide theoretical and pragmatic guideline for catalyst development and mechanism explorations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

10 CFR 490.808 - Use of credits to offset petroleum reduction shortfall.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 10 Energy 3 2012-01-01 2012-01-01 false Use of credits to offset petroleum reduction shortfall. 490.808 Section 490.808 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.808 Use of credits to offset petroleum reduction shortfall...

10 CFR 490.808 - Use of credits to offset petroleum reduction shortfall.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 10 Energy 3 2010-01-01 2010-01-01 false Use of credits to offset petroleum reduction shortfall. 490.808 Section 490.808 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.808 Use of credits to offset petroleum reduction shortfall...

10 CFR 490.808 - Use of credits to offset petroleum reduction shortfall.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 10 Energy 3 2013-01-01 2013-01-01 false Use of credits to offset petroleum reduction shortfall. 490.808 Section 490.808 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.808 Use of credits to offset petroleum reduction shortfall...

10 CFR 490.808 - Use of credits to offset petroleum reduction shortfall.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 10 Energy 3 2014-01-01 2014-01-01 false Use of credits to offset petroleum reduction shortfall. 490.808 Section 490.808 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.808 Use of credits to offset petroleum reduction shortfall...

10 CFR 490.808 - Use of credits to offset petroleum reduction shortfall.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 3 2011-01-01 2011-01-01 false Use of credits to offset petroleum reduction shortfall. 490.808 Section 490.808 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ALTERNATIVE FUEL TRANSPORTATION PROGRAM Alternative Compliance § 490.808 Use of credits to offset petroleum reduction shortfall...

Energy Cost Reduction for Automotive Service Facilities.

ERIC Educational Resources Information Center

Federal Energy Administration, Washington, DC.

This handbook on energy cost reduction for automotive service facilities consists of four sections. The importance and economic benefits of energy conservation are discussed in the first section. In the second section six energy cost reduction measures are discussed: relamping interior areas; relamping and reducing interior lighting; setting back…

Measured impacts of supermarket humidity level on defrost performance and refrigerating system energy use

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

Henderson, H.I.; Khattar, M.

This paper presents field-monitor data from two supermarkets where the impact of space humidity on refrigerating system energy use was evaluated. Direct digital control (DDC) systems were used at both stores to collect 15-minute monitored data. At Store A in Minneapolis, the DDC system was used to monitor system performance as well as to implement temperature-terminated control in place of time-terminated control on 16 refrigerated zones using hot gas defrost. At Store B in Indianapolis, the DDC system was used to quantify the performance trends for the single compressor rack system with electric defrost. The results at Store B showedmore » that refrigerating system energy use decreases by nearly 10 kWh/day for each 1% drop in space relative humidity, or about 0.4% of average annual system energy use. This value includes the impact of reduced latent loads, the reduction in direct energy use and imposed load from reduced electric defrost heater operation, and the smaller imposed load from reduced anti-sweat heater energy use. The measured reductions agree well with the impact predicted using the calculation methods developed by Howell (1933b) in ASHRAE Research Project 596. At Store A, the measured data show that implementing temperature-terminated defrost reduced refrigerating system energy use by nearly 70 kWh/day over the winter period when the average space humidity was 22% RH. The savings from temperature-terminated defrost increase by 4 kWh/day per each 1% drop in relative humidity. At both stores, the same type of mechanical controls were used to duty cycle the anti-sweat heaters based on store dew point. Anti-sweat heater electricity use was observed to decrease by 4.6 kWh/day at Store B and 3.4 kWh/day at Store A for each 1% drop in relative humidity. At Store A, a more aggressive control scheme was implemented with the DDC system that reduced anti-sweat heater energy use by 7.8 kWh/day per % RH. The more aggressive control approach was reported to properly control fogging and condensation on display case surfaces. The overall energy reduction factor at the two stores was 12 kWh/day per % RH at Store A and 15 kWh/day per % RH at Store B. With more aggressive anti-sweat heater control, reduction factors as high as 20 kWh/day per % RH appear to be possible.« less

Design and Implementation of a Thermal Load Reduction System for a Hyundai Sonata PHEV for Improved Range

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

Rugh, John P; Kreutzer, Cory J; Scott, Matthew

Increased adoption of electric-drive vehicles requires overcoming hurdles including limited vehicle range. Vehicle cabin heating and cooling demand for occupant climate control requires energy from the main battery and has been shown to significantly degrade vehicle range. During peak cooling and heating conditions, climate control can require as much as or more energy than propulsion. As part of an ongoing project, the National Renewable Energy Laboratory and project partners Hyundai America Technical Center, Inc., Gentherm, Pittsburgh Glass Works, PPG Industries, Sekisui, 3 M, and Hanon Systems developed a thermal load reduction system to reduce the range penalty associated with electricmore » vehicle climate control. Solar reflective paint, solar control glass, heated and cooled/ventilated seats, heated surfaces, and a heated windshield with door demisters were integrated into a Hyundai Sonata plug-in hybrid electric vehicle. Cold weather field-testing was conducted in Fairbanks, Alaska, and warm weather testing was conducted in Death Valley, California, to assess the system performance in comparison to the baseline production vehicle. In addition, environmental chamber testing at peak heating and cooling conditions was performed to assess the performance of the system in standardized conditions compared to the baseline. Experimental results are presented in this paper, providing quantitative data to automobile manufacturers on the impact of climate control thermal load reduction technologies to increase the advanced thermal technology adoption and market penetration of electric drive vehicles.« less

Kinetics of the solid-state carbothermic reduction of wessel manganese ores

NASA Astrophysics Data System (ADS)

Akdogan, Guven; Eric, R. Hurman

1995-02-01

Reduction of manganese ores from the Wessel mine of South Africa has been investigated in the temperature range 1100 °C to 1350 °C with pure graphite as the reductant under argon atmosphere. The rate and degree of reduction were found to increase with increasing temperature and decreasing particle sizes of both the ore and the graphite. The reduction was found to occur in two stages: (1) The first stage includes the rapid reduction of higher oxides of manganese and iron to MnO and FeO. The rate control appears to be mixed, both inward diffusion of CO and outward diffusion of CO2 across the porous product layer, and the reaction of carbon monoxide on the pore walls of the oxide phase play important roles. The values of effective CO-CO2 diffusivities generated by the mathematical model are in the range from 2.15 x 10-5 to 6.17 X 10-5 cm2.s-1 for different ores at 1300 °C. Apparent activation energies range from 81. 3 to 94.6 kJ/kg/mol. (2) The second stage is slower during which MnO and FeO are reduced to mixed carbide of iron and manganese. The chemical reaction between the manganous oxide and carbon dissolved in the metal phase or metal carbide seems to be the rate-controlling process The rate constant of chemical reaction between MnO and carbide on the surface of the impervious core was found to lie in the range from 1.53 x 10-8 to 1.32 x 10-7 mol . s-1 . cm-2. Apparent activation energies calculated are in the range from 102.1 to 141.7 kJ/kg/mol.

Monostable superrepellent materials

NASA Astrophysics Data System (ADS)

Li, Yanshen; Quéré, David; Lv, Cunjing; Zheng, Quanshui

2017-03-01

Superrepellency is an extreme situation where liquids stay at the tops of rough surfaces, in the so-called Cassie state. Owing to the dramatic reduction of solid/liquid contact, such states lead to many applications, such as antifouling, droplet manipulation, hydrodynamic slip, and self-cleaning. However, superrepellency is often destroyed by impalement transitions triggered by environmental disturbances whereas inverse transitions are not observed without energy input. Here we show through controlled experiments the existence of a “monostable” region in the phase space of surface chemistry and roughness, where transitions from Cassie to (impaled) Wenzel states become spontaneously reversible. We establish the condition for observing monostability, which might guide further design and engineering of robust superrepellent materials.

Effects of Small Oscillations on the Effective Area

NASA Astrophysics Data System (ADS)

Cotroneo, V.; Conconi, P.; Cusumano, G.; Pareschi, G.; Spiga, D.; Tagliaferri, G.

2009-05-01

We analyze the effective area of the Simbol-X mirrors as a function of the off-axis angle for small oscillations. A reduction is expected due to: 1) geometrical effects, because some of the photons miss the secondary mirror surface; 2) reflectivity effects, caused by the variation of the coating reflectivity with the incidence angle. The former are related to the length of the two mirror surfaces, and can be reduced by making the secondary mirror longer. The second ones are energy-dependent, and strongly related to the characteristics of the reflecting coating. These effects are analyzed by means of ray-tracing simulations in order to optimize the mirror and coating design, aiming to improve the effective area stability.