Jumping liquid metal droplet in electrolyte triggered by solid metal particles

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

Tang, Jianbo; University of Chinese Academy of Sciences, Beijing 100049; Wang, Junjie

2016-05-30

We report the electron discharge effect due to point contact between liquid metal and solid metal particles in electrolyte. Adding nickel particles induces drastic hydrogen generating and intermittent jumping of a sub-millimeter EGaIn droplet in NaOH solution. Observations from different orientations disclose that such jumping behavior is triggered by pressurized bubbles under the assistance of interfacial interactions. Hydrogen evolution around particles provides clear evidence that such electric instability originates from the varied electric potential and morphology between the two metallic materials. The point-contact-induced charge concentration significantly enhances the near-surface electric field intensity at the particle tips and thus causes electricmore » breakdown of the electrolyte.« less

Metal-dielectric interactions

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1979-01-01

Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.

Liquid metal actuation by electrical control of interfacial tension

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

Eaker, Collin B.; Dickey, Michael D., E-mail: michael-dickey@ncsu.edu

2016-09-15

By combining metallic electrical conductivity with low viscosity, liquid metals and liquid metal alloys offer new and exciting opportunities to serve as reconfigurable components of electronic, microfluidic, and electromagnetic devices. Here, we review the physics and applications of techniques that utilize voltage to manipulate the interfacial tension of liquid metals; such techniques include electrocapillarity, continuous electrowetting, electrowetting-on-dielectric, and electrochemistry. These techniques lower the interfacial tension between liquid metals and a surrounding electrolyte by driving charged species (or in the case of electrochemistry, chemical species) to the interface. The techniques are useful for manipulating and actuating liquid metals at sub-mm lengthmore » scales where interfacial forces dominate. We focus on metals and alloys that are liquid near or below room temperature (mercury, gallium, and gallium-based alloys). The review includes discussion of mercury—despite its toxicity—because it has been utilized in numerous applications and it offers a way of introducing several phenomena without the complications associated with the oxide layer that forms on gallium and its alloys. The review focuses on the advantages, applications, opportunities, challenges, and limitations of utilizing voltage to control interfacial tension as a method to manipulate liquid metals.« less

Reduced quenching effects of organic gain media with metallic electrodes via introducing a conjugated macroelectrolyte interlayer

NASA Astrophysics Data System (ADS)

Yi, Jianpeng; Huang, Jinjin; Liu, Chengfang; Lai, Wen-Yong; Huang, Wei

2017-01-01

We have demonstrated amplified spontaneous emission (ASE) restoration and threshold reduction by introducing a novel water/alcohol soluble conjugated macroelectrolyte, tris(4-(7-(9,9-di(hexyl-1-N,N-diethanolamino)-9H-fluoren-2-yl)-9,9-di(hexyl-1-N,N-diethanolamino)-9H-fluoren-2-yl)phenyl)amine (TPAOH), serving as an interfacial layer between the gain media layer, dioctyl substituted polyfluorene (PFO), and the Ag electrode layer. By optimizing the film thickness of TPAOH, enhanced ASE performance has been achieved with the lowest threshold of 21 μJ/cm2, demonstrating 3.5-fold reduction from 74 μJ/cm2. Atomic force microscopy results showed good compatibility between the TPAOH film and the PFO layer. The results suggest a facile and low-cost solution-processing interfacial technique to construct efficient organic semiconductor lasers in the presence of metallic electrodes.

Oxidation-Mediated Fingering in Liquid Metals

NASA Astrophysics Data System (ADS)

Eaker, Collin B.; Hight, David C.; O'Regan, John D.; Dickey, Michael D.; Daniels, Karen E.

2017-10-01

We identify and characterize a new class of fingering instabilities in liquid metals; these instabilities are unexpected due to the large interfacial tension of metals. Electrochemical oxidation lowers the effective interfacial tension of a gallium-based liquid metal alloy to values approaching zero, thereby inducing drastic shape changes, including the formation of fractals. The measured fractal dimension (D =1.3 ±0.05 ) places the instability in a different universality class than other fingering instabilities. By characterizing changes in morphology and dynamics as a function of droplet volume and applied electric potential, we identify the three main forces involved in this process: interfacial tension, gravity, and oxidative stress. Importantly, we find that electrochemical oxidation can generate compressive interfacial forces that oppose the tensile forces at a liquid interface. The surface oxide layer ultimately provides a physical and electrochemical barrier that halts the instabilities at larger positive potentials. Controlling the competition between interfacial tension and oxidative (compressive) stresses at the interface is important for the development of reconfigurable electronic, electromagnetic, and optical devices that take advantage of the metallic properties of liquid metals.

Nanoparticle Decoration of Carbon Nanotubes by Sputtering

DTIC Science & Technology

2013-02-01

subsequent coalescence as the mechanism of growth, but focused on per- formance of the metallized arrays rather than processing- structure relationships...dictates its wet- ting behavior; if the interfacial energy is comparable to the surface energy, the metal will avoid contact with the sub- strate and...form an isolated island to minimize interfacial en- ergy. Significantly lower interfacial energy values will drive the metal to spread on the surface—for

Spontaneous interfacial reaction between metallic copper and PBS to form cupric phosphate nanoflower and its enzyme hybrid with enhanced activity.

PubMed

He, Guangli; Hu, Weihua; Li, Chang Ming

2015-11-01

We herein report the spontaneous interfacial reaction between copper foil with 0.01 M phosphate buffered saline (PBS) to form free-standing cupric phosphate (Cu3(PO4)2) nanoflowers at ambient temperature. The underlying chemistry was thoroughly investigated and it is found that the formation of nanoflower is synergistically caused by dissolved oxygen, chlorine ions and phosphate ions. Enzyme-Cu3(PO4)2 hybrid nanoflower was further prepared successfully by using an enzyme-dissolving PBS solution and the enzymes in the hybrid exhibit enhanced biological activity. This work provides a facile route for large-scale synthesis of hierarchical inorganic and functional protein-inorganic hybrid architectures via a simple one-step solution-immersion reaction without using either template or surfactant, thus offering great potential for biosensing application among others. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of Organic Matter - Mineral Interfacial Reactions on Metal(loid) Speciation and Bioaccessibility

NASA Astrophysics Data System (ADS)

Chorover, J.; Kong, S.; Root, R. A.; Thomas, A.

2015-12-01

Bioaccessibility of contaminant metals in geomedia is often measured on the basis of kinetic release to solution during in vitro reaction with biofluid simulants. We postulate that development of a predictive-mechanistic understanding of bioaccessibility requires knowledge of metal(loid) molecular speciation upon sample introduction, as well as its change over the course of the in vitro reaction. Our results - including data from batch, column, mesocosm and field studies pertaining to arsenic, lead, and zinc contaminated materials - indicate the strong influence of organic matter and associated biological activity on metal(loid) speciation in mine tailings and related model systems. Furthermore, presence/absence of organic matter during bioassays affects the kinetics of metal(loid) release into biofluid simulants through multiple mechanisms.

Molecular-Scale Investigation of Heavy Metal Ions at a Charged Langmuir Monolayer

NASA Astrophysics Data System (ADS)

Rock, William; Qiao, Baofu; Uysal, Ahmet; Bu, Wei; Lin, Binhua

Solvent extraction - the surfactant-aided preferential transfer of a species from an aqueous to an organic phase - is an important technique used in heavy and precious metal refining and reprocessing. Solvent extraction requires transfer through an oil/water interface, and interfacial interactions are expected to control transfer kinetics and phase stability, yet these key interactions are poorly understood. Langmuir monolayers with charged headgroups atop concentrated salt solutions containing heavy metal ions act as a model of solvent extraction interfaces; studies of ions at a charged surface are also fundamentally important to many other phenomena including protein solvation, mineral surface chemistry, and electrochemistry. We probe these charged interfaces using a variety of surface-sensitive techniques - vibrational sum frequency generation (VSFG) spectroscopy, x-ray reflectivity (XRR), x-ray fluorescence near total reflection (XFNTR), and grazing incidence diffraction (GID). We integrate experiments with Molecular Dynamics (MD) simulations to uncover the molecular-level interfacial structure. This work is supported by the U.S. DOE, BES, Contract DE-AC02-06CH11357. ChemMatCARS is supported by NSF/CHE-1346572.

Collaborative Research and Development (CR&D) III Task Order 0077: Fundamental Studies of Plasticity, Interfacial Boundaries and Liquid Metals

DTIC Science & Technology

2013-06-01

Interfacial Boundaries and Liquid Metals Dallas Trinkle Independent Contractor JUNE 2013 Final Report Approved for public...SIGNATURE//_________________ CHRISTOPHER WOODWARD, Project Engineer DANIEL EVANS, Chief Metals Branch Metals Branch Structural ...Materials Division Structural Materials Division ____//SIGNATURE//___________________ ROBERT T. MARSHALL, Deputy Chief

Project Description and Publications List for UAH CMMR

NASA Technical Reports Server (NTRS)

Kaukler, William F.

1999-01-01

This research combines a state of the art X-ray Transmission Microscope, XTM, with a specially designed x-ray transparent horizontal Bridgman furnace to image (with resolutions up to 3 micrometers) the solidification of metal alloys in real-time. The objective is to obtain real-time dynamic data to provide direct measure of the solute profile in the liquid, phase coalescence and growth in the liquid, and the detailed interface morphology (e,g., dendrites and cells) during solidification. We are also enhancing the XTM data with precise solid-liquid interfacial temperature and the thermal gradient measurement techniques, and working on the application of this technology to the study of the fundamentals of solidification in microgravity. Over the last several years we have successfully imaged in real-time: interfacial-morphologies, phase growth, coalescence, incorporation of phases into the growing interface, and the solute boundary layer in the liquid at the solid-liquid interface. We have also measured true local growth rates and can evaluate segregation structures in the solid. Interfacial undercoolings are being measured either with a special Seebeck furnace or with micro-thermocouple arrays we are developing. These later techniques are presently being incorporated with the XTM furnace. This last year emphasized the investigation of the solute layer in the melt during solidification. Methods were developed to quantify the solute concentrations using x-ray absorption and to compare to predictions from simulations. In addition, work is being completed on a brass-board portable XTM that incorporates a vertical Bridgman furnace.

Determination of interfacial adhesion strength between oxide scale and substrate for metallic SOFC interconnects

NASA Astrophysics Data System (ADS)

Sun, X.; Liu, W. N.; Stephens, E.; Khaleel, M. A.

The interfacial adhesion strength between the oxide scale and the substrate is crucial to the reliability and durability of metallic interconnects in solid oxide fuel cell (SOFC) operating environments. It is necessary, therefore, to establish a methodology to quantify the interfacial adhesion strength between the oxide scale and the metallic interconnect substrate, and furthermore to design and optimize the interconnect material as well as the coating materials to meet the design life of an SOFC system. In this paper, we present an integrated experimental/analytical methodology for quantifying the interfacial adhesion strength between the oxide scale and a ferritic stainless steel interconnect. Stair-stepping indentation tests are used in conjunction with subsequent finite element analyses to predict the interfacial strength between the oxide scale and Crofer 22 APU substrate.

What Can Interfacial Water Molecules Tell Us About Solute Structure?

NASA Astrophysics Data System (ADS)

Willard, Adam

The molecular structure of bulk liquid water reflects a molecular tendency to engage in tetrahedrally coordinated hydrogen bonding. At a solute interface waters preferred three-dimensional hydrogen bonding network must conform to a locally anisotropy interfacial environment. Interfacial water molecules adopt configurations that balance water-solute and water-water interactions. The arrangements of interfacial water molecules, therefore encode information about the effective solute-water interactions. This solute-specific information is difficult to extract, however, because interfacial structure also reflects waters collective response to an anisotropic hydrogen bonding environment. Here I present a methodology for characterizing the molecular-level structure of liquid water interface from simulation data. This method can be used to explore waters static and/or dynamic response to a wide range of chemically and topologically heterogeneous solutes such as proteins.

Smooth Interfacial Scavenging for Resistive Switching Oxide via the Formation of Highly Uniform Layers of Amorphous TaOx.

PubMed

Tsurumaki-Fukuchi, Atsushi; Nakagawa, Ryosuke; Arita, Masashi; Takahashi, Yasuo

2018-02-14

We demonstrate that the inclusion of a Ta interfacial layer is a remarkably effective strategy for forming interfacial oxygen defects at metal/oxide junctions. The insertion of an interfacial layer of a reactive metal, that is, a "scavenging" layer, has been recently proposed as a way to create a high concentration of oxygen defects at an interface in redox-based resistive switching devices, and growing interest has been given to the underlying mechanism. Through structural and chemical analyses of Pt/metal/SrTiO 3 /Pt structures, we reveal that the rate and amount of oxygen scavenging are not directly determined by the formation free energies in the oxidation reactions of the scavenging metal and unveil the important roles of oxygen diffusibility. Active oxygen scavenging and highly uniform oxidation via scavenging are revealed for a Ta interfacial layer with high oxygen diffusibility. In addition, the Ta scavenging layer is shown to exhibit a highly uniform structure and to form a very flat interface with SrTiO 3 , which are advantageous for the fabrication of a steep metal/oxide contact.

The Emergence of Atomic-Level Structural Information for Ordered Metal-Solution Interfaces: Some Recent Contributions from In-Situ Infrared Spectroscopy and Scanning Tunneling Microscopy

DTIC Science & Technology

1992-02-28

Distribution/ Availabilit Codes jAval’ an~d/or Dist Speoial (19. cont.) reconstruction at gold-aqueous interfaces. All three low-index gold surfaces are...uncharged (vide supra). This difference may well be due to the influence of the interfacial water , or conceivably to adsorbed perchlorate anions. Both Au

Dependence of interfacial Dzyaloshinskii-Moriya interaction and perpendicular magnetic anisotropy on the thickness of the heavy-metal layer

NASA Astrophysics Data System (ADS)

Kim, Nam-Hui; Han, Dong-Soo; Jung, Jinyong; Park, Kwonjin; Swagten, Henk J. M.; Kim, June-Seo; You, Chun-Yeol

2017-10-01

The interfacial Dzyaloshinskii-Moriya interaction (iDMI) and the interfacial perpendicular magnetic anisotropy (iPMA) between a heavy metal and ferromagnet are investigated by employing Brillouin light scattering. With increasing thickness of the heavy-metal (Pt) layer, the iDMI and iPMA energy densities are rapidly enhanced and they saturate for a Pt thickness of 2.4 nm. Since these two individual magnetic properties show the same Pt thickness dependence, this is evidence that the iDMI and iPMA at the interface between the heavy metal and ferromagnet, the physical origin of these phenomena, are effectively enhanced upon increasing the thickness of the heavy-metal layer.

Optimization of Residual Stresses in MMC's Using Compensating/Compliant Interfacial Layers. Part 2: OPTCOMP User's Guide

NASA Technical Reports Server (NTRS)

Pindera, Marek-Jerzy; Salzar, Robert S.; Williams, Todd O.

1994-01-01

A user's guide for the computer program OPTCOMP is presented in this report. This program provides a capability to optimize the fabrication or service-induced residual stresses in uni-directional metal matrix composites subjected to combined thermo-mechanical axisymmetric loading using compensating or compliant layers at the fiber/matrix interface. The user specifies the architecture and the initial material parameters of the interfacial region, which can be either elastic or elastoplastic, and defines the design variables, together with the objective function, the associated constraints and the loading history through a user-friendly data input interface. The optimization procedure is based on an efficient solution methodology for the elastoplastic response of an arbitrarily layered multiple concentric cylinder model that is coupled to the commercial optimization package DOT. The solution methodology for the arbitrarily layered cylinder is based on the local-global stiffness matrix formulation and Mendelson's iterative technique of successive elastic solutions developed for elastoplastic boundary-value problems. The optimization algorithm employed in DOT is based on the method of feasible directions.

Synthesis of colloidal metal nanocrystals in droplet reactors: the pros and cons of interfacial adsorption.

PubMed

Zhang, Lei; Wang, Yi; Tong, Limin; Xia, Younan

2014-07-09

Droplet reactors have received considerable attention in recent years as an alternative route to the synthesis and potentially high-volume production of colloidal metal nanocrystals. Interfacial adsorption will immediately become an important issue to address when one seeks to translate a nanocrystal synthesis from batch reactors to droplet reactors due to the involvement of higher surface-to-volume ratios for the droplets and the fact that nanocrystals tend to be concentrated at the water-oil interface. Here we report a systematic study to compare the pros and cons of interfacial adsorption of metal nanocrystals during their synthesis in droplet reactors. On the one hand, interfacial adsorption can be used to generate nanocrystals with asymmetric shapes or structures, including one-sixth-truncated Ag octahedra and Au-Ag nanocups. On the other hand, interfacial adsorption has to be mitigated to obtain nanocrystals with uniform sizes and controlled shapes. We confirmed that Triton X-100, a nonionic surfactant, could effectively alleviate interfacial adsorption while imposing no impact on the capping agent typically needed for a shape-controlled synthesis. With the introduction of a proper surfactant, droplet reactors offer an attractive platform for the continuous production of colloidal metal nanocrystals.

A Method to Manipulate Surface Tension of a Liquid Metal via Surface Oxidation and Reduction

PubMed Central

Dickey, Michael D.

2016-01-01

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where interfacial tension is a dominant force. A variety of methods exist for controlling the interfacial tension of aqueous and organic liquids on this scale; however, these techniques have limited utility for liquid metals due to their large interfacial tension. Liquid metals can form soft, stretchable, and shape-reconfigurable components in electronic and electromagnetic devices. Although it is possible to manipulate these fluids via mechanical methods (e.g., pumping), electrical methods are easier to miniaturize, control, and implement. However, most electrical techniques have their own constraints: electrowetting-on-dielectric requires large (kV) potentials for modest actuation, electrocapillarity can affect relatively small changes in the interfacial tension, and continuous electrowetting is limited to plugs of the liquid metal in capillaries. Here, we present a method for actuating gallium and gallium-based liquid metal alloys via an electrochemical surface reaction. Controlling the electrochemical potential on the surface of the liquid metal in electrolyte rapidly and reversibly changes the interfacial tension by over two orders of magnitude (~500 mN/m to near zero). Furthermore, this method requires only a very modest potential (< 1 V) applied relative to a counter electrode. The resulting change in tension is due primarily to the electrochemical deposition of a surface oxide layer, which acts as a surfactant; removal of the oxide increases the interfacial tension, and vice versa. This technique can be applied in a wide variety of electrolytes and is independent of the substrate on which it rests. PMID:26863045

Metal/oxide interfacial effects on the selective oxidation of primary alcohols

PubMed Central

Zhao, Guofeng; Yang, Fan; Chen, Zongjia; Liu, Qingfei; Ji, Yongjun; Zhang, Yi; Niu, Zhiqiang; Mao, Junjie; Bao, Xinhe; Hu, Peijun; Li, Yadong

2017-01-01

A main obstacle in the rational development of heterogeneous catalysts is the difficulty in identifying active sites. Here we show metal/oxide interfacial sites are highly active for the oxidation of benzyl alcohol and other industrially important primary alcohols on a range of metals and oxides combinations. Scanning tunnelling microscopy together with density functional theory calculations on FeO/Pt(111) reveals that benzyl alcohol enriches preferentially at the oxygen-terminated FeO/Pt(111) interface and undergoes readily O–H and C–H dissociations with the aid of interfacial oxygen, which is also validated in the model study of Cu2O/Ag(111). We demonstrate that the interfacial effects are independent of metal or oxide sizes and the way by which the interfaces were constructed. It inspires us to inversely support nano-oxides on micro-metals to make the structure more stable against sintering while the number of active sites is not sacrificed. The catalyst lifetime, by taking the inverse design, is thereby significantly prolonged. PMID:28098146

Hydrophobic Materials Based on Salts of Di(2-ethylhexyl)phosphoric Acid

NASA Astrophysics Data System (ADS)

Kizim, N. F.; Golubina, E. N.

2018-03-01

Interfacial formations of material based on metals di(2-ethylhexyl)phosphates of various metals exhibit hydrophobic properties. The contact angle of the surface, modified by the interfacial formations materials, could reach up to 140° depending on the nature of the solvent, the metal salt, the number of applications.

Effective NiMn Nanoparticles-Functionalized Carbon Felt as an Effective Anode for Direct Urea Fuel Cells.

PubMed

Barakat, Nasser A M; Alajami, Mohannad; Ghouri, Zafar Khan; Al-Meer, Saeed

2018-05-16

The internal resistances of fuel cells strongly affect the generated power. Basically, in the fuel cell, the anode can be prepared by deposition of a film from the functional electrocatalyst on a proper gas diffusion layer. Accordingly, an interfacial resistance for the electron transport is created between the two layers. Electrocatalyst-functionalized gas diffusion layer (GDL) can distinctly reduce the interfacial resistance between the catalyst layer and the GDL. In this study, NiMn nanoparticles-decorated carbon felt is introduced as functionalized GDL to be exploited as a ready-made anode in a direct urea fuel cell. The proposed treated GDL was prepared by calcination of nickel acetate/manganese acetate-loaded carbon felt under an argon atmosphere at 850 °C. The physiochemical characterizations confirmed complete reduction for the utilized precursors and deposition of pristine NiMn nanoparticles on the carbon felt fiber. In passive direct urea fuel cells, investigation the performance of the functionalized GDLs indicated that the composition of the metal nanoparticles has to be optimized as the GDL obtained from 40 wt % manganese acetate reveals the maximum generated power density; 36 mW/m² at room temperature and 0.5 M urea solution. Moreover, the electrochemical measurements proved that low urea solution concentration is preferred as utilizing 0.5 M solution resulted into generating higher power compared to 1.0 and 2.0 M solution. Overall, this study opens a new avenue toward functionalization of the GDL as a novel strategy to overcome the interfacial resistance between the electrocatalyst and the GDL.

Effective NiMn Nanoparticles-Functionalized Carbon Felt as an Effective Anode for Direct Urea Fuel Cells

PubMed Central

Barakat, Nasser A. M.; Alajami, Mohannad; Ghouri, Zafar Khan; Al-Meer, Saeed

2018-01-01

The internal resistances of fuel cells strongly affect the generated power. Basically, in the fuel cell, the anode can be prepared by deposition of a film from the functional electrocatalyst on a proper gas diffusion layer. Accordingly, an interfacial resistance for the electron transport is created between the two layers. Electrocatalyst-functionalized gas diffusion layer (GDL) can distinctly reduce the interfacial resistance between the catalyst layer and the GDL. In this study, NiMn nanoparticles-decorated carbon felt is introduced as functionalized GDL to be exploited as a ready-made anode in a direct urea fuel cell. The proposed treated GDL was prepared by calcination of nickel acetate/manganese acetate-loaded carbon felt under an argon atmosphere at 850 °C. The physiochemical characterizations confirmed complete reduction for the utilized precursors and deposition of pristine NiMn nanoparticles on the carbon felt fiber. In passive direct urea fuel cells, investigation the performance of the functionalized GDLs indicated that the composition of the metal nanoparticles has to be optimized as the GDL obtained from 40 wt % manganese acetate reveals the maximum generated power density; 36 mW/m2 at room temperature and 0.5 M urea solution. Moreover, the electrochemical measurements proved that low urea solution concentration is preferred as utilizing 0.5 M solution resulted into generating higher power compared to 1.0 and 2.0 M solution. Overall, this study opens a new avenue toward functionalization of the GDL as a novel strategy to overcome the interfacial resistance between the electrocatalyst and the GDL. PMID:29772710

Seamless growth of a supramolecular carpet

PubMed Central

Kim, Ju-Hyung; Ribierre, Jean-Charles; Yang, Yu Seok; Adachi, Chihaya; Kawai, Maki; Jung, Jaehoon; Fukushima, Takanori; Kim, Yousoo

2016-01-01

Organic/metal interfaces play crucial roles in the formation of intermolecular networks on metal surfaces and the performance of organic devices. Although their purity and uniformity have profound effects on the operation of organic devices, the formation of organic thin films with high interfacial uniformity on metal surfaces has suffered from the intrinsic limitation of molecular ordering imposed by irregular surface structures. Here we demonstrate a supramolecular carpet with widely uniform interfacial structure and high adaptability on a metal surface via a one-step process. The high uniformity is achieved with well-balanced interfacial interactions and site-specific molecular rearrangements, even on a pre-annealed amorphous gold surface. Co-existing electronic structures show selective availability corresponding to the energy region and the local position of the system. These findings provide not only a deeper insight into organic thin films with high structural integrity, but also a new way to tailor interfacial geometric and electronic structures. PMID:26839053

Effects of Interfacial Fluorination on Performance Enhancement of High-k-Based Charge Trap Flash Memory

NASA Astrophysics Data System (ADS)

Wang, Chenjie; Huo, Zongliang; Liu, Ziyu; Liu, Yu; Cui, Yanxiang; Wang, Yumei; Li, Fanghua; Liu, Ming

2013-07-01

The effects of interfacial fluorination on the metal/Al2O3/HfO2/SiO2/Si (MAHOS) memory structure have been investigated. By comparing MAHOS memories with and without interfacial fluorination, it was identified that the deterioration of the performance and reliability of MAHOS memories is mainly due to the formation of an interfacial layer that generates excess oxygen vacancies at the interface. Interfacial fluorination suppresses the growth of the interfacial layer, which is confirmed by X-ray photoelectron spectroscopy depth profile analysis, increases enhanced program/erase efficiency, and improves data retention characteristics. Moreover, it was observed that fluorination at the SiO-HfO interface achieves a more effective performance enhancement than that at the HfO-AlO interface.

Interfacial behaviours between lithium ion conductors and electrode materials in various battery systems

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

Wu, Bingbin; Wang, Shanyu; Evans IV, Willie J.

In recent years room temperature Li+ ion conductors have been intensively revisited in order to develop safe lithium ion (Li-ion) batteries and beyond that can be deployed in the electrical vehicles. Through careful modification on materials synthesis, promising solid Li+ conductors with high ionic conductivity, competitve with liquid electrolytes, have been demonstrated. However, the integration of those highly conductive solid electrolytes into the whole system is still very challenging mainly due to the high impedance existing in the different interfaces throughout the entire battery structure. Herein , this review paper focuses on the overview of the interfacial behaviors between Li+more » conductors and cathode/anode materials. The origin, evolution and potential solutions to reuce these interfacial impedances are reviewed for various battery systems spanning from Li-ion, lithium sulfur (Li-S), lithium oxygen (Li-O2) batteries to lithium metal protection. The predicted gravimetric and volumetric energy densities at different scenarios are also discussed along with the prospectives for further development of solid state batteries.« less

Fast Synthesis of Pt Nanocrystals and Pt/Microporous La2O3 Materials Using Acoustic Levitation.

PubMed

Yu, Yinkai; Qu, Shaohua; Zang, Duyang; Wang, Liuding; Wu, Hongjing

2018-02-13

Usually, we must use an appropriate support material to keep the metal species stable and finely dispersed as supported metal nanoparticles for industry application. Therefore, the choice of support material is a key factor in determining the dispersion and particle size of the noble metal species. Here, we report the synthesis of a single-atom Pt material in the solution and supported Pt nanoclusters on microporous La 2 O 3 by a one-step acoustic levitation method without any pretreatment/modification of raw oxide. We have strongly contributed to the synthetic methodology of the surface/interfacial heterogeneous catalysts in this study, and this finding could open another door for synthesis of supported metal nanoparticles on porous materials for environmental catalysis.

Fast Synthesis of Pt Nanocrystals and Pt/Microporous La2O3 Materials Using Acoustic Levitation

NASA Astrophysics Data System (ADS)

Yu, Yinkai; Qu, Shaohua; Zang, Duyang; Wang, Liuding; Wu, Hongjing

2018-02-01

Usually, we must use an appropriate support material to keep the metal species stable and finely dispersed as supported metal nanoparticles for industry application. Therefore, the choice of support material is a key factor in determining the dispersion and particle size of the noble metal species. Here, we report the synthesis of a single-atom Pt material in the solution and supported Pt nanoclusters on microporous La2O3 by a one-step acoustic levitation method without any pretreatment/modification of raw oxide. We have strongly contributed to the synthetic methodology of the surface/interfacial heterogeneous catalysts in this study, and this finding could open another door for synthesis of supported metal nanoparticles on porous materials for environmental catalysis.

Water/alcohol soluble conjugated polymers as highly efficient electron transporting/injection layer in optoelectronic devices.

PubMed

Huang, Fei; Wu, Hongbin; Cao, Yong

2010-07-01

Water/alcohol soluble conjugated polymers (WSCPs) can be processed from water or other polar solvents, which offer good opportunities to avoid interfacial mixing upon fabrication of multilayer polymer optoelectronic devices by solution processing, and can dramatically improve charge injection from high work-function metal cathode resulting in greatly enhancement of the device performance. In this critical review, the authors provide a brief review of recent developments in this field, including the materials design, functional principles, and their unique applications as interface modification layer in solution-processable multilayer optoelectronic devices (135 references).

Fundamental insights into interfacial catalysis.

PubMed

Gong, Jinlong; Bao, Xinhe

2017-04-03

Surface and interfacial catalysis plays a vital role in chemical industries, electrochemistry and photochemical reactions. The challenges of modern chemistry are to optimize the chemical reaction processes and understand the detailed mechanism of chemical reactions. Since the early 1960s, the foundation of surface science systems has allowed the study of surface and interfacial phenomena on atomic/molecular level, and thus brought a number of significant developments to fundamental and technological processes, such as catalysis, material science and biochemistry, just to name a few. This themed issue describes the recent advances and developments in the fundamental understanding of surface and interfacial catalysis, encompassing areas of knowledge from metal to metal oxide, carbide, graphene, hexagonal boron nitride, and transition metal dichalcogenides under ultrahigh vacuum conditions, as well as under realistic reaction conditions.

Using Grand Canonical Monte Carlo Simulations to Understand the Role of Interfacial Fluctuations on Solvation at the Water-Vapor Interface.

PubMed

Rane, Kaustubh; van der Vegt, Nico F A

2016-09-15

The present work investigates the effect of interfacial fluctuations (predominantly capillary wave-like fluctuations) on the solvation free energy (Δμ) of a monatomic solute at the water-vapor interface. We introduce a grand-canonical-ensemble-based simulation approach that quantifies the contribution of interfacial fluctuations to Δμ. This approach is used to understand how the above contribution depends on the strength of dispersive and electrostatic solute-water interactions at the temperature of 400 K. At this temperature, we observe that interfacial fluctuations do play a role in the variation of Δμ with the strength of the electrostatic solute-water interaction. We also use grand canonical simulations to further investigate how interfacial fluctuations affect the propensity of the solute toward the water-vapor interface. To this end, we track a quantity called the interface potential (surface excess free energy) with the number of water molecules. With increasing number of water molecules, the liquid-vapor interface moves across a solute, which is kept at a fixed position in the simulation. Hence, the dependence of the interface potential on the number of waters models the process of moving the solute through the water-vapor interface. We analyze the change of the interface potential with the number of water molecules to explain that solute-induced changes in the interfacial fluctuations, like the pinning of capillary-wave-like undulations, do not play any role in the propensity of solutes toward water-vapor interfaces. The above analysis also shows that the dampening of interfacial fluctuations accompanies the adsorption of any solute at the liquid-vapor interface, irrespective of the chemical nature of the solute and solvent. However, such a correlation does not imply that dampening of fluctuations causes adsorption.

Interfacial engineering of solution-processed Ni nanochain-SiO x (x< 2) cermets towards thermodynamically stable, anti-oxidation solar selective absorbers

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

Yu, Xiaobai; Wang, Xiaoxin; Zhang, Qinglin

Here, cermet solar thermal selective absorber coatings are an important component of high-efficiency concentrated solar power (CSP) receivers. The oxidation of the metal nanoparticles in cermet solar absorbers is a great challenge for vacuum-free operation. Recently, we have demonstrated that oxidation is kinetically retarded in solution processed, high-optical-performance Ni nanochain-SiO x cermet system compared to conventional Ni-Al 2O 3 system when annealed in air at 450–600 °C for several hours. However, for long-term, high-temperature applications in CSP systems, thermodynamically stable antioxidation behavior is highly desirable, which requires new mechanisms beyond kinetically reducing the oxidation rate. Towards this goal, in thismore » paper, we demonstrate that pre-operation annealing of Ni nanochain-SiO x cermets at 900 °C in N 2 forms the thermodynamically stable orthorhombic phase of NiSi at the Ni/SiO x interfaces, leading to self-terminated oxidation at 550 °C in air due to this interfacial engineering. In contrast, pre-operation annealing at a lower temperature of 750 °C in N 2 (as conducted in our previous work) cannot achieve interfacial NiSi formation directly, and further annealing in air at 450–600 °C for >4 h only leads to the formation of the less stable (metastable) hexagonal phase of NiSi. Therefore, the high-temperature pre-operation annealing is critical to form the desirable orthorhombic phase of NiSi at Ni/SiO x interfaces towards thermodynamically stable antioxidation behavior. Remarkably, with this improved interfacial engineering, the oxidation of 80-nm-diameter Ni nanochain-SiO x saturates after annealing at 550 °C in air for 12 h. Additional annealing at 550 °C in air for as long as 20 h (i.e., 32 h air annealing at >550 °C in total) has almost no further impact on the structural or optical properties of the coatings, the latter being very sensitive to any interfacial changes due to the localized surface plasmon resonances of the metal nanostructures. This phenomenon holds true for Ni nanoparticle diameter down to 40 nm in Ni-SiO x system, where the optical response remains stable for 53 h at 550 °C in air. The oxidation vs. time curve also shows saturation behavior deviating from the kinetic Deal-Grove oxidation model. These results strongly suggest a promising approach to thermodynamically stable, anti-oxidation Ni/SiO x cermet absorbers via interfacial engineering.« less

Interfacial engineering of solution-processed Ni nanochain-SiO x (x< 2) cermets towards thermodynamically stable, anti-oxidation solar selective absorbers

DOE PAGES

Yu, Xiaobai; Wang, Xiaoxin; Zhang, Qinglin; ...

2016-04-01

Here, cermet solar thermal selective absorber coatings are an important component of high-efficiency concentrated solar power (CSP) receivers. The oxidation of the metal nanoparticles in cermet solar absorbers is a great challenge for vacuum-free operation. Recently, we have demonstrated that oxidation is kinetically retarded in solution processed, high-optical-performance Ni nanochain-SiO x cermet system compared to conventional Ni-Al 2O 3 system when annealed in air at 450–600 °C for several hours. However, for long-term, high-temperature applications in CSP systems, thermodynamically stable antioxidation behavior is highly desirable, which requires new mechanisms beyond kinetically reducing the oxidation rate. Towards this goal, in thismore » paper, we demonstrate that pre-operation annealing of Ni nanochain-SiO x cermets at 900 °C in N 2 forms the thermodynamically stable orthorhombic phase of NiSi at the Ni/SiO x interfaces, leading to self-terminated oxidation at 550 °C in air due to this interfacial engineering. In contrast, pre-operation annealing at a lower temperature of 750 °C in N 2 (as conducted in our previous work) cannot achieve interfacial NiSi formation directly, and further annealing in air at 450–600 °C for >4 h only leads to the formation of the less stable (metastable) hexagonal phase of NiSi. Therefore, the high-temperature pre-operation annealing is critical to form the desirable orthorhombic phase of NiSi at Ni/SiO x interfaces towards thermodynamically stable antioxidation behavior. Remarkably, with this improved interfacial engineering, the oxidation of 80-nm-diameter Ni nanochain-SiO x saturates after annealing at 550 °C in air for 12 h. Additional annealing at 550 °C in air for as long as 20 h (i.e., 32 h air annealing at >550 °C in total) has almost no further impact on the structural or optical properties of the coatings, the latter being very sensitive to any interfacial changes due to the localized surface plasmon resonances of the metal nanostructures. This phenomenon holds true for Ni nanoparticle diameter down to 40 nm in Ni-SiO x system, where the optical response remains stable for 53 h at 550 °C in air. The oxidation vs. time curve also shows saturation behavior deviating from the kinetic Deal-Grove oxidation model. These results strongly suggest a promising approach to thermodynamically stable, anti-oxidation Ni/SiO x cermet absorbers via interfacial engineering.« less

The role of interfacial metal silicates on the magnetism in FeCo/SiO 2 and Fe 49% Co 49% V 2% /SiO 2 core/shell nanoparticles

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

Desautels, R. D.; Freeland, J. W.; Rowe, M. P.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO2 and Fe49%Co49%V2%/SiO2 core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, and vanadium silicates. Magnetometry experiments havemore » shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO2-based interfacial shell.« less

Oxidized film structure and method of making epitaxial metal oxide structure

DOEpatents

Gan, Shupan [Richland, WA; Liang, Yong [Richland, WA

2003-02-25

A stable oxidized structure and an improved method of making such a structure, including an improved method of making an interfacial template for growing a crystalline metal oxide structure, are disclosed. The improved method comprises the steps of providing a substrate with a clean surface and depositing a metal on the surface at a high temperature under a vacuum to form a metal-substrate compound layer on the surface with a thickness of less than one monolayer. The compound layer is then oxidized by exposing the compound layer to essentially oxygen at a low partial pressure and low temperature. The method may further comprise the step of annealing the surface while under a vacuum to further stabilize the oxidized film structure. A crystalline metal oxide structure may be subsequently epitaxially grown by using the oxidized film structure as an interfacial template and depositing on the interfacial template at least one layer of a crystalline metal oxide.

Core–Shell Nanoparticle Coating as an Interfacial Layer for Dendrite-Free Lithium Metal Anodes

DOE PAGES

Liu, Wei; Li, Weiyang; Zhuo, Denys; ...

2017-02-08

Lithium metal based batteries represent a major challenge and opportunity in enabling a variety of devices requiring high-energy-density storage. However, dendritic lithium growth has limited the practical application of lithium metal anodes. Here we report a nanoporous, flexible and electrochemically stable coating of silica@poly(methyl methacrylate) (SiO 2@PMMA) core–shell nanospheres as an interfacial layer on lithium metal anode. This interfacial layer is capable of inhibiting Li dendrite growth while sustaining ionic flux through it, which is attributed to the nanoscaled pores formed among the nanospheres. Lastly, enhanced Coulombic efficiencies during lithium charge/discharge cycles have been achieved at various current densities andmore » areal capacities.« less

Core–Shell Nanoparticle Coating as an Interfacial Layer for Dendrite-Free Lithium Metal Anodes

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

Liu, Wei; Li, Weiyang; Zhuo, Denys

Lithium metal based batteries represent a major challenge and opportunity in enabling a variety of devices requiring high-energy-density storage. However, dendritic lithium growth has limited the practical application of lithium metal anodes. Here we report a nanoporous, flexible and electrochemically stable coating of silica@poly(methyl methacrylate) (SiO 2@PMMA) core–shell nanospheres as an interfacial layer on lithium metal anode. This interfacial layer is capable of inhibiting Li dendrite growth while sustaining ionic flux through it, which is attributed to the nanoscaled pores formed among the nanospheres. Lastly, enhanced Coulombic efficiencies during lithium charge/discharge cycles have been achieved at various current densities andmore » areal capacities.« less

Solid/liquid interfacial free energies in binary systems

NASA Technical Reports Server (NTRS)

Nason, D.; Tiller, W. A.

1973-01-01

Description of a semiquantitative technique for predicting the segregation characteristics of smooth interfaces between binary solid and liquid solutions in terms of readily available thermodynamic parameters of the bulk solutions. A lattice-liquid interfacial model and a pair-bonded regular solution model are employed in the treatment with an accommodation for liquid interfacial entropy. The method is used to calculate the interfacial segregation and the free energy of segregation for solid-liquid interfaces between binary solutions for the (111) boundary of fcc crystals. The zone of compositional transition across the interface is shown to be on the order of a few atomic layers in width, being moderately narrower for ideal solutions. The free energy of the segregated interface depends primarily upon the solid composition and the heats of fusion of the component atoms, the composition difference of the solutions, and the difference of the heats of mixing of the solutions.

Effect of chemically converted graphene as an electrode interfacial modifier on device-performances of inverted organic photovoltaic cells

NASA Astrophysics Data System (ADS)

Kang, Tae-Woon; Noh, Yong-Jin; Yun, Jin-Mun; Yang, Si-Young; Yang, Yong-Eon; Lee, Hae-Seong; Na, Seok-In

2015-06-01

This study examined the effects of chemically converted graphene (CCG) materials as a metal electrode interfacial modifier on device-performances of inverted organic photovoltaic cells (OPVs). As CCG materials for interfacial layers, a conventional graphene oxide (GO) and reduced graphene oxide (rGO) were prepared, and their functions on OPV-performances were compared. The inverted OPVs with CCG materials showed all improved cell-efficiencies compared with the OPVs with no metal/bulk-heterojunction (BHJ) interlayers. In particular, the inverted OPVs with reduction form of GO showed better device-performances than those with GO and better device-stability than poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS)-based inverted solar cells, showing that the rGO can be more desirable as a metal/BHJ interfacial material for fabricating inverted-configuration OPVs.

Synthesis and Compatibility of Ionic Liquid Containing Rod-Coil Polyimide Gel Electrolytes with Lithium Metal Electrodes

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Palker, Allyson E.; Meador, Mary Ann B.; Bennett, William R.

2008-01-01

A highly cross-linked polyimide-polyethylene oxide copolymer has been synthesized that is capable of holding large volumes of liquid component, simultaneously maintaining good dimensional stability. An amine end capped oligomer was made that was imidized in solution, followed by reaction with a triisocyanate in the presence of desired additives at ambient temperature. Polymer films are able to hold over 4 times their weight in room temperature ionic liquid RTIL or carbonate solvent. Electrolytes were studied that contained varying amounts of RTIL, lithium trifluoromethanesulfonimide LiTFSi, and alumina nanoparticles. Electrochemical stability of these electrolytes with lithium metal electrodes was studied by galvanic cycling and impedance spectroscopy. Improved cycling stability and decreased interfacial resistance were observed when increasing amounts of RTIL and LiTFSi were added. The addition of small amounts of alumina further decreased interfacial resistance by nearly an order of magnitude. During the course of the study, cycling stability increased from less than 3 to greater than 1000 h at 60 C and 0.25 mA/cm2 current density.

Stacking fault energy of face-centered cubic metals: thermodynamic and ab initio approaches

NASA Astrophysics Data System (ADS)

Li, Ruihuan; Lu, Song; Kim, Dongyoo; Schönecker, Stephan; Zhao, Jijun; Kwon, Se Kyun; Vitos, Levente

2016-10-01

The formation energy of the interface between face-centered cubic (fcc) and hexagonal close packed (hcp) structures is a key parameter in determining the stacking fault energy (SFE) of fcc metals and alloys using thermodynamic calculations. It is often assumed that the contribution of the planar fault energy to the SFE has the same order of magnitude as the bulk part, and thus the lack of precise information about it can become the limiting factor in thermodynamic predictions. Here, we differentiate between the interfacial energy for the coherent fcc(1 1 1)/hcp(0 0 0 1) interface and the ‘pseudo-interfacial energy’ that enters the thermodynamic expression for the SFE. Using first-principles calculations, we determine the coherent and pseudo-interfacial energies for six elemental metals (Al, Ni, Cu, Ag, Pt, and Au) and three paramagnetic Fe-Cr-Ni alloys. Our results show that the two interfacial energies significantly differ from each other. We observe a strong chemistry dependence for both interfacial energies. The calculated pseudo-interfacial energies for the Fe-Cr-Ni steels agree well with the available literature data. We discuss the effects of strain on the description of planar faults via thermodynamic and ab initio approaches.

Stacking fault energy of face-centered cubic metals: thermodynamic and ab initio approaches.

PubMed

Li, Ruihuan; Lu, Song; Kim, Dongyoo; Schönecker, Stephan; Zhao, Jijun; Kwon, Se Kyun; Vitos, Levente

2016-10-05

The formation energy of the interface between face-centered cubic (fcc) and hexagonal close packed (hcp) structures is a key parameter in determining the stacking fault energy (SFE) of fcc metals and alloys using thermodynamic calculations. It is often assumed that the contribution of the planar fault energy to the SFE has the same order of magnitude as the bulk part, and thus the lack of precise information about it can become the limiting factor in thermodynamic predictions. Here, we differentiate between the interfacial energy for the coherent fcc(1 1 1)/hcp(0 0 0 1) interface and the 'pseudo-interfacial energy' that enters the thermodynamic expression for the SFE. Using first-principles calculations, we determine the coherent and pseudo-interfacial energies for six elemental metals (Al, Ni, Cu, Ag, Pt, and Au) and three paramagnetic Fe-Cr-Ni alloys. Our results show that the two interfacial energies significantly differ from each other. We observe a strong chemistry dependence for both interfacial energies. The calculated pseudo-interfacial energies for the Fe-Cr-Ni steels agree well with the available literature data. We discuss the effects of strain on the description of planar faults via thermodynamic and ab initio approaches.

Interfacial reactions between metal and gallium arsenide

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

Lin, J.C.; Schulz, K.J.; Hsieh, K.C.

1989-10-01

The phase formation sequence for GaAs/metal ternary diffusion couples is discussed. The diffusion path concept is introduced and is used with the phase diagram to understand interfacial reactions between GaAs and metal. The correlation between growth kinetics and interface morphology is discussed. Studies of bulk and thin film couples in two systems, GaAs/Pd and GaAs/Pt, are given to illustrate these concepts.

First principles modeling of the metal-electrolyte interface: A novel approach to the study of the electrochemical interface

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

Fernandez-Serra, Maria Victoria

2016-09-12

The research objective of this proposal is the computational modeling of the metal-electrolyte interface purely from first principles. The accurate calculation of the electrostatic potential at electrically biased metal-electrolyte interfaces is a current challenge for periodic “ab-initio” simulations. It is also an essential requisite for predicting the correspondence between the macroscopic voltage and the microscopic interfacial charge distribution in electrochemical fuel cells. This interfacial charge distribution is the result of the chemical bonding between solute and metal atoms, and therefore cannot be accurately calculated with the use of semi-empirical classical force fields. The project aims to study in detail themore » structure and dynamics of aqueous electrolytes at metallic interfaces taking into account the effect of the electrode potential. Another side of the project is to produce an accurate method to simulate the water/metal interface. While both experimental and theoretical surface scientists have made a lot of progress on the understanding and characterization of both atomistic structures and reactions at the solid/vacuum interface, the theoretical description of electrochemical interfaces is still lacking behind. A reason for this is that a complete and accurate first principles description of both the liquid and the metal interfaces is still computationally too expensive and complex, since their characteristics are governed by the explicit atomic and electronic structure built at the interface as a response to environmental conditions. This project will characterize in detail how different theoretical levels of modeling describer the metal/water interface. In particular the role of van der Waals interactions will be carefully analyzed and prescriptions to perform accurate simulations will be produced.« less

Enhancement in the interfacial perpendicular magnetic anisotropy and the voltage-controlled magnetic anisotropy by heavy metal doping at the Fe/MgO interface

NASA Astrophysics Data System (ADS)

Nozaki, Takayuki; Yamamoto, Tatsuya; Tamaru, Shingo; Kubota, Hitoshi; Fukushima, Akio; Suzuki, Yoshishige; Yuasa, Shinji

2018-02-01

We investigated the influence of heavy metal doping at the Fe/MgO interface on the interfacial perpendicular magnetic anisotropy (PMA) and the voltage-controlled magnetic anisotropy (VCMA) in magnetic tunnel junctions prepared by sputtering-based deposition. The interfacial PMA was increased by tungsten doping and a maximum intrinsic interfacial PMA energy, Ki,0 of 2.0 mJ/m2 was obtained. Ir doping led to a large increase in the VCMA coefficient by a factor of 4.7 compared with that for the standard Fe/MgO interface. The developed technique provides an effective approach to enhancing the interfacial PMA and VCMA properties in the development of voltage-controlled spintronic devices.

Interfacial charge transfer absorption: Application to metal molecule assemblies

NASA Astrophysics Data System (ADS)

Creutz, Carol; Brunschwig, Bruce S.; Sutin, Norman

2006-05-01

Optically induced charge transfer between adsorbed molecules and a metal electrode was predicted by Hush to lead to new electronic absorption features, but has been only rarely observed experimentally. Interfacial charge transfer absorption (IFCTA) provides information concerning the barriers to charge transfer between molecules and the metal/semiconductor and the magnitude of the electronic coupling and could thus provide a powerful tool for understanding interfacial charge-transfer kinetics. Here, we utilize a previously published model [C. Creutz, B.S. Brunschwig, N. Sutin, J. Phys. Chem. B 109 (2005) 10251] to predict IFCTA spectra of metal-molecule assemblies and compare the literature observations to these predictions. We conclude that, in general, the electronic coupling between molecular adsorbates and the metal levels is so small that IFCTA is not detectable. However, few experiments designed to detect IFCTA have been done. We suggest approaches to optimizing the conditions for observing the process.

The role of interfacial metal silicates on the magnetism in FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles

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

Desautels, R. D., E-mail: rddesautels@physics.umanitoba.ca; Toyota Research Institute of North America, Ann Arbor, Michigan 48169; Freeland, J. W.

2015-05-07

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, andmore » vanadium silicates. Magnetometry experiments have shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO{sub 2}-based interfacial shell.« less

Effect of metal surface topography on mechanical bonding at simulated total hip stem-cement interfaces.

PubMed

Chen, C Q; Scott, W; Barker, T M

1999-01-01

Bonding and loosening mechanisms between bone cement and joint prostheses have not been well identified. In this study, the effects of simulated hip stem surface topography on the interfacial shear strength were examined. Six different surface topographies were used. They were described by several surface characterization parameters that may directly relate to the interfacial bonding strength: average surface roughness R(a), root mean square slope R(Deltaq), correlation length beta, and fluid retention index R(ri). The shear strengths between Palacos E bone cement and stainless steel rods were measured using an Instron materials testing machine. We found that cement can "flow" into the surface microtopography and establish good contact with the metal surface. The results show that the interfacial strength increases monotonically with the increase of R(Deltaq) instead of with R(a). The relationship between interfacial strength and surface parameters shows that a metal stem with an isotropic surface texture, higher R(Deltaq), and greater R(ri) gives a higher interfacial strength. Copyright 1999 John Wiley & Sons, Inc.

Dynamic Impact of Electrode Materials on Interface of Single-Crystalline Methylammonium Lead Bromide Perovskite

DOE PAGES

Tisdale, Jeremy T.; Muckley, Eric; Ahmadi, Mahshid; ...

2018-06-19

One of the current challenges in methylammonium lead halide (MAPbX 3) perovskite application research is understanding contact formation and interfacial phenomena for highly efficient and stable device performance. For semiconductors, development of contact formation is inseparable from device performance and stability. Single–crystalline MAPbX3 has become of great interest for perovskite devices in photodetectors, light–emitting diodes, and more recently in high–energy radiation detection. Deeper research is required to understand interfacial interactions in single–crystalline MAPbX 3. This article focuses on the dynamic impact of electrode metal (Au and Cr) on methylammonium lead bromide (MAPbBr 3) single crystals. It is studied how chargemore » transport properties of single crystal MAPbBr 3 can be tuned via electrode material selection at the metal/MAPbBr 3 interface to improve device performance with proper contact formation. The ability to create an ohmic–like or nonohmic contact by switching the electrode metal from Cr to Au, respectively, is demonstrated. It is observed that the interfacial charge transfer resistance (recombination resistance) of the Cr/MAPbBr 3 interface is 1.79 × 10 9 Ω, compared to 1.32 × 10 7 Ω for the Au/MAPbBr 3. Cr contacts can reduce hysteretic behavior by reducing interfacial recombination and interfacial polarization. Furthermore, these studies provide insight to metal/MAPbX 3 interfacial interactions toward device engineering for hole transport layer–free MAPbX 3 device structures.« less

Dynamic Impact of Electrode Materials on Interface of Single-Crystalline Methylammonium Lead Bromide Perovskite

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

Tisdale, Jeremy T.; Muckley, Eric; Ahmadi, Mahshid

One of the current challenges in methylammonium lead halide (MAPbX 3) perovskite application research is understanding contact formation and interfacial phenomena for highly efficient and stable device performance. For semiconductors, development of contact formation is inseparable from device performance and stability. Single–crystalline MAPbX3 has become of great interest for perovskite devices in photodetectors, light–emitting diodes, and more recently in high–energy radiation detection. Deeper research is required to understand interfacial interactions in single–crystalline MAPbX 3. This article focuses on the dynamic impact of electrode metal (Au and Cr) on methylammonium lead bromide (MAPbBr 3) single crystals. It is studied how chargemore » transport properties of single crystal MAPbBr 3 can be tuned via electrode material selection at the metal/MAPbBr 3 interface to improve device performance with proper contact formation. The ability to create an ohmic–like or nonohmic contact by switching the electrode metal from Cr to Au, respectively, is demonstrated. It is observed that the interfacial charge transfer resistance (recombination resistance) of the Cr/MAPbBr 3 interface is 1.79 × 10 9 Ω, compared to 1.32 × 10 7 Ω for the Au/MAPbBr 3. Cr contacts can reduce hysteretic behavior by reducing interfacial recombination and interfacial polarization. Furthermore, these studies provide insight to metal/MAPbX 3 interfacial interactions toward device engineering for hole transport layer–free MAPbX 3 device structures.« less

Electrochemical performance and interfacial properties of Li-metal in lithium bis(fluorosulfonyl)imide based electrolytes.

PubMed

Younesi, Reza; Bardé, Fanny

2017-11-21

Successful usage of lithium metal as the negative electrode or anode in rechargeable batteries can be an important step to increase the energy density of lithium batteries. Performance of lithium metal in a relatively promising electrolyte solution composed of lithium bis(fluorosulfonyl)imide (LiN(SO 2 F) 2 ; LiFSI) salt dissolved in 1,2-dimethoxyethane (DME) is here studied. The influence of the concentration of the electrolyte salt -1 M or 4 M LiFSI- is investigated by varying important electrochemical parameters such as applied current density and plating capacity. X-ray photoelectron spectroscopy analysis as a surface sensitive technique is here used to analyze that how the composition of the solid electrolyte interphase varies with the salt concentration and with the number of cycles.

Emergent Interfacial Ferromagnetism in CaMnO3-based Superlattices

NASA Astrophysics Data System (ADS)

Grutter, Alexander

2014-03-01

Interfaces of complex oxide materials provide a rich playground not only for the exploration of properties not found in the bulk constituents but also for the development of functional interfaces to be incorporated in spintronic applications. Emergent interfacial magnetic phenomena have been of great interest but surprisingly there have been few examples of emergent interfacial ferromagnetism. In this talk, I will describe our recent work on the stabilization of ferromagnetism in CaMnO3-based superlattices. We have demonstrated ferromagnetism at the interface between the antiferromagnetic insulator CaMnO3 and a paramagnetic metallic layer, including CaRuO3 and LaNiO3. Theoretically the ferromagnetism has been attributed to an interfacial double exchange interaction among the interfacial Mn ions that is mediated by itinerant electrons from the paramagnetic metallic layer. Through polarized neutron reflectivity and observation of exchange bias, we have demonstrated that the ferromagnetism comes from Mn ions in a single unit cell at the interfaces just as theory has predicted. We have also demonstrated that the metallicity of the paramagnetic layer is critical in stabilizing ferromagnetism at the interface and that the interfacial ferromagnetism can be suppressed by suppressing the metallicity of the paramagnetic layer. Despite the agreement with theory, there remain open questions as to the magnetic interactions among the interfacial ferromagnetic layers. For example, the saturated magnetic moment modulates as a function of the thickness of both the CaMnO3 and paramagnetic metal layers. The origins of this oscillation are not well understood and may stem from either structural effects or long-range oscillatory magnetic coupling interactions reminiscent of RKKY interactions. Evidence of the doubling of the unit cell and long range antiferromagnetic correlations support these speculations. This work was supported by the U.S. Department of Energy, Office of Science, Division of Materials Sciences and Engineering, under Contract # DE-AC05-76RL01830 and DE-SC0008505.

Modulating DNA configuration by interfacial traction: an elastic rod model to characterize DNA folding and unfolding.

PubMed

Huang, Zaixing

2011-01-01

As a continuum model of DNA, a thin elastic rod subjected to interfacial interactions is used to investigate the equilibrium configuration of DNA in intracellular solution. The interfacial traction between the rod and the solution environment is derived in detail. Kirchhoff's theory of elastic rods is used to analyze the equilibrium configuration of a DNA segment under the action of the interfacial traction. The influences of the interfacial energy factor and bending stiffness on the toroidal spool formation of the DNA segment are discussed. The results show that the equilibrium configuration of DNA is mainly determined by competition between the interfacial energy and elastic strain energy of the DNA itself, and the interfacial traction is one of the forces that drives DNA folding and unfolding.

Interfacial behavior of polymer electrolytes

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

Kerr, John; Kerr, John B.; Han, Yong Bong

2003-06-03

Evidence is presented concerning the effect of surfaces on the segmental motion of PEO-based polymer electrolytes in lithium batteries. For dry systems with no moisture the effect of surfaces of nano-particle fillers is to inhibit the segmental motion and to reduce the lithium ion transport. These effects also occur at the surfaces in composite electrodes that contain considerable quantities of carbon black nano-particles for electronic connection. The problem of reduced polymer mobility is compounded by the generation of salt concentration gradients within the composite electrode. Highly concentrated polymer electrolytes have reduced transport properties due to the increased ionic cross-linking. Combinedmore » with the interfacial interactions this leads to the generation of low mobility electrolyte layers within the electrode and to loss of capacity and power capability. It is shown that even with planar lithium metal electrodes the concentration gradients can significantly impact the interfacial impedance. The interfacial impedance of lithium/PEO-LiTFSI cells varies depending upon the time elapsed since current was turned off after polarization. The behavior is consistent with relaxation of the salt concentration gradients and indicates that a portion of the interfacial impedance usually attributed to the SEI layer is due to concentrated salt solutions next to the electrode surfaces that are very resistive. These resistive layers may undergo actual phase changes in a non-uniform manner and the possible role of the reduced mobility polymer layers in dendrite initiation and growth is also explored. It is concluded that PEO and ethylene oxide-based polymers are less than ideal with respect to this interfacial behavior.« less

In situ measurement of contact angles and surface tensions of interfacial nanobubbles in ethanol aqueous solutions.

PubMed

Zhao, Binyu; Wang, Xingya; Wang, Shuo; Tai, Renzhong; Zhang, Lijuan; Hu, Jun

2016-04-14

The astonishing long lifetime and large contact angles of interfacial nanobubbles are still in hot debate despite numerous experimental and theoretical studies. One hypothesis to reconcile the two abnormalities of interfacial nanobubbles is that they have low surface tensions. However, few studies have been reported to measure the surface tensions of nanobubbles due to the lack of effective measurements. Herein, we investigate the in situ contact angles and surface tensions of individual interfacial nanobubbles immersed in different ethanol aqueous solutions using quantitative nanomechanical atomic force microscopy (AFM). The results showed that the contact angles of nanobubbles in the studied ethanol solutions were also much larger than the corresponding macroscopic counterparts on the same substrate, and they decreased with increasing ethanol concentrations. More significantly, the surface tensions calculated were much lower than those of the gas-liquid interfaces of the solutions at the macroscopic scale but have similar tendencies with increasing ethanol concentrations. Those results are expected to be helpful in further understanding the stability of interfacial nanobubbles in complex solutions.

Insight into induced charges at metal surfaces and biointerfaces using a polarizable Lennard-Jones potential.

PubMed

Geada, Isidro Lorenzo; Ramezani-Dakhel, Hadi; Jamil, Tariq; Sulpizi, Marialore; Heinz, Hendrik

2018-02-19

Metallic nanostructures have become popular for applications in therapeutics, catalysts, imaging, and gene delivery. Molecular dynamics simulations are gaining influence to predict nanostructure assembly and performance; however, instantaneous polarization effects due to induced charges in the free electron gas are not routinely included. Here we present a simple, compatible, and accurate polarizable potential for gold that consists of a Lennard-Jones potential and a harmonically coupled core-shell charge pair for every metal atom. The model reproduces the classical image potential of adsorbed ions as well as surface, bulk, and aqueous interfacial properties in excellent agreement with experiment. Induced charges affect the adsorption of ions onto gold surfaces in the gas phase at a strength similar to chemical bonds while ions and charged peptides in solution are influenced at a strength similar to intermolecular bonds. The proposed model can be applied to complex gold interfaces, electrode processes, and extended to other metals.

Interfacial engineering of solution-processed Ni nanochain-SiO{sub x} (x < 2) cermets towards thermodynamically stable, anti-oxidation solar selective absorbers

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

Yu, Xiaobai; Wang, Xiaoxin; Liu, Jifeng, E-mail: Jifeng.Liu@dartmouth.edu

Cermet solar thermal selective absorber coatings are an important component of high-efficiency concentrated solar power (CSP) receivers. The oxidation of the metal nanoparticles in cermet solar absorbers is a great challenge for vacuum-free operation. Recently, we have demonstrated that oxidation is kinetically retarded in solution processed, high-optical-performance Ni nanochain-SiO{sub x} cermet system compared to conventional Ni-Al{sub 2}O{sub 3} system when annealed in air at 450–600 °C for several hours. However, for long-term, high-temperature applications in CSP systems, thermodynamically stable antioxidation behavior is highly desirable, which requires new mechanisms beyond kinetically reducing the oxidation rate. Towards this goal, in this paper, wemore » demonstrate that pre-operation annealing of Ni nanochain-SiO{sub x} cermets at 900 °C in N{sub 2} forms the thermodynamically stable orthorhombic phase of NiSi at the Ni/SiO{sub x} interfaces, leading to self-terminated oxidation at 550 °C in air due to this interfacial engineering. In contrast, pre-operation annealing at a lower temperature of 750 °C in N{sub 2} (as conducted in our previous work) cannot achieve interfacial NiSi formation directly, and further annealing in air at 450–600 °C for >4 h only leads to the formation of the less stable (metastable) hexagonal phase of NiSi. Therefore, the high-temperature pre-operation annealing is critical to form the desirable orthorhombic phase of NiSi at Ni/SiO{sub x} interfaces towards thermodynamically stable antioxidation behavior. Remarkably, with this improved interfacial engineering, the oxidation of 80-nm-diameter Ni nanochain-SiO{sub x} saturates after annealing at 550 °C in air for 12 h. Additional annealing at 550 °C in air for as long as 20 h (i.e., 32 h air annealing at >550 °C in total) has almost no further impact on the structural or optical properties of the coatings, the latter being very sensitive to any interfacial changes due to the localized surface plasmon resonances of the metal nanostructures. This phenomenon holds true for Ni nanoparticle diameter down to 40 nm in Ni-SiO{sub x} system, where the optical response remains stable for 53 h at 550 °C in air. The oxidation vs. time curve also shows saturation behavior deviating from the kinetic Deal-Grove oxidation model. These results strongly suggest a promising approach to thermodynamically stable, anti-oxidation Ni/SiO{sub x} cermet absorbers via interfacial engineering.« less

Optimization of Residual Stresses in MMC's through Process Parameter Control and the use of Heterogeneous Compensating/Compliant Interfacial Layers. OPTCOMP2 User's Guide

NASA Technical Reports Server (NTRS)

Pindera, Marek-Jerzy; Salzar, Robert S.

1996-01-01

A user's guide for the computer program OPTCOMP2 is presented in this report. This program provides a capability to optimize the fabrication or service-induced residual stresses in unidirectional metal matrix composites subjected to combined thermomechanical axisymmetric loading by altering the processing history, as well as through the microstructural design of interfacial fiber coatings. The user specifies the initial architecture of the composite and the load history, with the constituent materials being elastic, plastic, viscoplastic, or as defined by the 'user-defined' constitutive model, in addition to the objective function and constraints, through a user-friendly data input interface. The optimization procedure is based on an efficient solution methodology for the inelastic response of a fiber/interface layer(s)/matrix concentric cylinder model where the interface layers can be either homogeneous or heterogeneous. The response of heterogeneous layers is modeled using Aboudi's three-dimensional method of cells micromechanics model. The commercial optimization package DOT is used for the nonlinear optimization problem. The solution methodology for the arbitrarily layered cylinder is based on the local-global stiffness matrix formulation and Mendelson's iterative technique of successive elastic solutions developed for elastoplastic boundary-value problems. The optimization algorithm employed in DOT is based on the method of feasible directions.

Combined Thermodynamic-Kinetic Analysis of the Interfacial Reactions between Ni Metallization and Various Lead-Free Solders

PubMed Central

Laurila, Tomi; Vuorinen, Vesa

2009-01-01

In this paper we will demonstrate how a thermodynamic-kinetic method can be utilized to rationalize a wide range of interfacial phenomena between Sn-based lead-free solders and Ni metallizations. First, the effect of P on the interfacial reactions, and thus on the reliability, between Sn-based solders and electroless Ni/immersion Au (ENIG) metallizations, will be discussed. Next, the effect of small amounts of Cu in Sn-based solders on the intermetallic compound (IMC), which forms first on top of Ni metallization, will be covered. With the help of thermodynamic arguments a so called critical Cu concentration for the formation of (Cu,Ni)6Sn5 can be determined as a function of temperature. Then the important phenomenon of redeposition of (Au,Ni)Sn4 layer on top of Ni3Sn4 IMC will be discussed in detail. The reasons leading to this behaviour will be rationalized with the help of thermodynamic information and an explanation of why this phenomenon does not occur when an appropriate amount of Cu is present in the soldering system will be given. Finally, interfacial reaction issues related to low temperature Sn-Zn and Sn-Bi based solders and Ni metallization will be discussed.

Nitride passivation reduces interfacial traps in atomic-layer-deposited Al2O3/GaAs (001) metal-oxide-semiconductor capacitors using atmospheric metal-organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Aoki, T.; Fukuhara, N.; Osada, T.; Sazawa, H.; Hata, M.; Inoue, T.

2014-07-01

Using an atmospheric metal-organic chemical vapor deposition system, we passivated GaAs with AlN prior to atomic layer deposition of Al2O3. This AlN passivation incorporated nitrogen at the Al2O3/GaAs interface, improving the capacitance-voltage (C-V) characteristics of the resultant metal-oxide-semiconductor capacitors (MOSCAPs). The C-V curves of these devices showed a remarkable reduction in the frequency dispersion of the accumulation capacitance. Using the conductance method at various temperatures, we extracted the interfacial density of states (Dit). The Dit was reduced over the entire GaAs band gap. In particular, these devices exhibited Dit around the midgap of less than 4 × 1012 cm-2eV-1, showing that AlN passivation effectively reduced interfacial traps in the MOS structure.

Interfacial Ordering and Accompanying Divergent Capacitance at Ionic Liquid-Metal Interfaces.

PubMed

Limmer, David T

2015-12-18

A theory is constructed for dense ionic solutions near charged planar walls that is valid for strong interionic correlations. This theory predicts a fluctuation-induced, first-order transition and spontaneous charge density ordering at the interface, in the presence of an otherwise disordered bulk solution. The surface ordering is driven by applied voltage and results in an anomalous differential capacitance, in agreement with recent simulation results and consistent with experimental observations of a wide array of systems. Explicit forms for the charge density profile and capacitance are given. The theory is compared with numerical results for the charge frustrated Ising model, which is also found to exhibit a voltage driven first-order transition.

Interfacial Ordering and Accompanying Divergent Capacitance at Ionic Liquid-Metal Interfaces

NASA Astrophysics Data System (ADS)

Limmer, David T.

2015-12-01

A theory is constructed for dense ionic solutions near charged planar walls that is valid for strong interionic correlations. This theory predicts a fluctuation-induced, first-order transition and spontaneous charge density ordering at the interface, in the presence of an otherwise disordered bulk solution. The surface ordering is driven by applied voltage and results in an anomalous differential capacitance, in agreement with recent simulation results and consistent with experimental observations of a wide array of systems. Explicit forms for the charge density profile and capacitance are given. The theory is compared with numerical results for the charge frustrated Ising model, which is also found to exhibit a voltage driven first-order transition.

The effect of solute on the homogeneous crystal nucleation frequency in metallic melts

NASA Technical Reports Server (NTRS)

Thompson, C. V.; Spaepen, F.

1982-01-01

A complete calculation that extends the classical theory for crystal nucleation in pure melts to binary alloys has been made. Using a regular solution model, approximate expressions have been developed for the free energy change upon crystallization as a function of solute concentration. They are used, together with model-based estimates of the interfacial tension, to calculate the nucleation frequency. The predictions of the theory for the maximum attainable undercooling are compared with existing experimental results for non-glass forming alloys. The theory is also applied to several easy glass-forming alloys (Pd-Si, Au-Si, Fe-B) for qualitative comparison with the present experimental experience on the ease of glass formation, and for assessment of the potential for formation of the glass in bulk.

Grain Size Modulation and Interfacial Engineering of CH3 NH3 PbBr3 Emitter Films through Incorporation of Tetraethylammonium Bromide.

PubMed

Jamaludin, Nur Fadilah; Yantara, Natalia; Ng, Yan Fong; Li, Mingjie; Goh, Teck Wee; Thirumal, Krishnamoorthy; Sum, Tze Chien; Mathews, Nripan; Soci, Cesare; Mhaisalkar, Subodh

2018-05-07

Metal halide perovskites have demonstrated breakthrough performances as absorber and emitter materials for photovoltaic and display applications respectively. However, despite the low manufacturing cost associated with solution-based processing, the propensity for defect formation with this technique has led to an increasing need for defect passivation. Here, we present an inexpensive and facile method to remedy surface defects through a postdeposition treatment process using branched alkylammonium cation species. The simultaneous realignment of interfacial energy levels upon incorporation of tetraethylammonium bromide onto the surface of CH 3 NH 3 PbBr 3 films contributes favorably toward the enhancement in overall light-emitting diode characteristics, achieving maximum luminance, current efficiency, and external quantum efficiency values of 11 000 cd m -2 , 0.68 cd A -1 , and 0.16 %, respectively. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Growth of MAPbBr3 perovskite crystals and its interfacial properties with Al and Ag contacts for perovskite solar cells

NASA Astrophysics Data System (ADS)

Najeeb, Mansoor Ani; Ahmad, Zubair; Shakoor, R. A.; Alashraf, Abdulla; Bhadra, Jolly; Al-Thani, N. J.; Al-Muhtaseb, Shaheen A.; Mohamed, A. M. A.

2017-11-01

In this work, the MAPbBr3 perovskite crystals were grown and the interfacial properties of the poly-crystalline MAPbBr3 with Aluminum (Al) and Silver (Ag) contacts has been investigated. MAPbBr3 crystals are turned into the poly-crystalline pellets (PCP) using compaction technique and the Al/PCP, Al/interface layer/PCP, Ag/PCP, and Ag/interface layer/PCP contacts were investigated. Scanning Electron Microscopic (SEM), Energy-dispersive X-ray spectroscopy (EDX) and current-voltage (I-V) characteristic technique were used to have an insight of the degradation mechanism happening at the Metal/perovskite interface. The Ag/PCP contact appears to be stable, whereas Al is found to be highly reactive with the MAPbBr3 perovskite crystals due to the infiltration setback of Al in to the perovskite crystals. The interface layer showed a slight effect on the penetration of Al in to the perovskite crystals however it does not seem to be an appropriate solution. It is noteworthy that the stability of the underlying metal/perovskite contact is very crucial towards the perovskite solar cells with extended device lifetime.

SERS and DFT study of water on metal cathodes of silver, gold and platinum nanoparticles.

PubMed

Li, Jian-Feng; Huang, Yi-Fan; Duan, Sai; Pang, Ran; Wu, De-Yin; Ren, Bin; Xu, Xin; Tian, Zhong-Qun

2010-03-14

The observed surface-enhanced Raman scattering (SERS) spectra of water adsorbed on metal film electrodes of silver, gold, and platinum nanoparticles were used to infer interfacial water structures on the basis of the change of the electrochemical vibrational Stark tuning rates and the relative Raman intensity of the stretching and bending modes. To explain the increase of the relative Raman intensity ratio of the bending and stretching vibrations at the very negative potential region, density functional theory calculations provide the conceptual model. The specific enhancement effect for the bending mode was closely associated with the water adsorption structure in a hydrogen bonded configuration through its H-end binding to surface sites with large polarizability due to strong cathodic polarization. The present results allow us to propose that interfacial water molecules exist on these metal cathodes with different hydrogen bonding interactions, i.e., the HO-HH-Pt dihydrogen bond for platinum and the HO-HAg(Au) for silver and gold. This dihydrogen bonding configuration on platinum is further supported from observation of the Pt-H stretching band. Furthermore, the influences of the pH effect on SERS intensity and vibrational Stark effect on the gold electrode indicate that the O-H stretching SERS signals are enhanced in the alkaline solutions because of the hydrated hydroxide surface species adsorbed on the gold cathode.

Effect of interfacial species on shear strength of metal-sapphire contacts

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1979-01-01

The interfacial shear strength of the metal-insulator system has been studied by means of the coefficient of static friction of copper, nickel, or gold contacts on sapphire in ultrahigh vacuum. The effect on contact strength of adsorbed oxygen, nitrogen, chlorine, and carbon monoxide on the metal surfaces is reported. It was found that exposures as low as 1 L of O2 on Ni produced observable increases in contact strength, whereas exposures of 3 L of Cl2 lead to a decrease in contact strength. These results imply that submonolayer concentrations of these species at the interface of a thin Ni film on Al2O3 should affect film adhesion similarly. The atomic mechanism by which these surface or interface phases affect interfacial strength is not yet understood.

Effect of Interfacial characteristics of metal clad polymeric substrates on electrical high frequency interconnection performance

NASA Technical Reports Server (NTRS)

Bhasin, K. B.; Romanofsky, R. R.; Ponchak, G. E.; Liu, D. C.

1984-01-01

Etched metallic conductor lines on metal clad polymeric substrates are used for electronic component interconnections. Significant signal losses are observed for microstrip conductor lines used for interconnecting high frequency devices. At these frequencies, the electronic signal travels closer to the metal-polymer interface due to the skin effect. Copper-teflon interfaces were characterized by scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to determine the interfacial properties. Data relating roughness of the copper film to signal losses was compared to theory. Films used to enhance adhesion are found, to contribute to these losses.

Fracture of coherent interfaces between an fcc metal matrix and the Cr23C6 carbide precipitate from first principles

NASA Astrophysics Data System (ADS)

Barbé, Elric; Fu, Chu-Chun; Sauzay, Maxime

2018-02-01

It is known that microcrack initiation in metallic alloys containing second-phase particles may be caused by either an interfacial or an intraprecipitate fracture. So far, the dependence of these features on properties of the precipitate and the interface is not clearly known. The present study aims to determine the key properties of carbide-metal interfaces controlling the energy and critical stress of fracture, based on density functional theory (DFT) calculations. We address coherent interfaces between a fcc iron or nickel matrix and a frequently observed carbide, the M23C6 , for which a simplified chemical composition Cr23C6 is assumed. The interfacial properties such as the formation and Griffith energies, and the effective Young's modulus are analyzed as functions of the magnetic state of the metal lattice, including the paramagnetic phase of iron. Interestingly, a simpler antiferromagnetic phase is found to exhibit similar interfacial mechanical behavior to the paramagnetic phase. A linear dependence is determined between the surface (and interface) energy and the variation of the number of chemical bonds weighted by the respective bond strength, which can be used to predict the relative formation energy for the surface and interface with various chemical terminations. Finally, the critical stresses of both intraprecipitate and interfacial fractures due to a tensile loading are estimated via the universal binding energy relation (UBER) model, parametrized on the DFT data. The validity of this model is verified in the case of intraprecipitate fracture, against results from DFT tensile test simulations. In agreement with experimental evidences, we predict a much stronger tendency for an interfacial fracture for this carbide. In addition, the calculated interfacial critical stresses are fully compatible with available experimental data in steels, where the interfacial carbide-matrix fracture is only observed at incoherent interfaces.

Adhesion, friction, and wear behavior of clean metal-ceramic couples

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa

1995-01-01

When a clean metal is brought into contact with a clean, harder ceramic in ultrahigh vacuum, strong bonds form between the two materials. The interfacial bond strength between the metal and ceramic surfaces in sliding contact is generally greater than the cohesive bond strength in the metal. Thus, fracture of the cohesive bonds in the metal results when shearing occurs. These strong interfacial bonds and the shearing fracture in the metal are the main causes of the observed wear behavior and the transfer of the metal to the ceramic. In the literature, the surface energy (bond energy) per unit area of the metal is shown to be related to the degree of interfacial bond strength per unit area. Because the two materials of a metal-ceramic couple have markedly different ductilities, contact can cause considerable plastic deformation of the softer metal. It is the ductility of the metal, then, that determines the real area of contact. In general, the less ductile the metal, the smaller the real area of contact. The coefficient of friction for clean surfaces of metal-ceramic couples correlates with the metals total surface energy in the real area of contact gamma A (which is the product of the surface energy per unit area of the metal gamma and the real area of contact (A)). The coefficient of friction increases as gamma A increases. Furthermore, gamma A is associated with the wear and transfer of the metal at the metal-ceramic interface: the higher the value of gamma A, the greater the wear and transfer of the metal.

Comparison of fluid-fluid interfacial areas measured with X-ray microtomography and interfacial partitioning tracer tests for the same samples: COMPARISON OF FLUID-FLUID INTERFACIAL AREAS

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

McDonald, Kieran; Carroll, Kenneth C.; Brusseau, Mark L.

2016-07-01

Two different methods are currently used for measuring interfacial areas between immiscible fluids within 3-D porous media, high-resolution microtomographic imaging and interfacial partitioning tracer tests (IPTT). Both methods were used in this study to measure nonwetting/wetting interfacial areas for a natural sand. The microtomographic imaging was conducted on the same packed columns that were used for the IPTTs. This is in contrast to prior studies comparing the two methods, for which in all cases different samples were used for the two methods. In addition, the columns were imaged before and after the IPTTs to evaluate the potential impacts of themore » tracer solution on fluid configuration and attendant interfacial area. The interfacial areas measured using IPTT are ~5 times larger than the microtomographic-measured values, which is consistent with previous work. Analysis of the image data revealed no significant impact of the tracer solution on NAPL configuration or interfacial area. Other potential sources of error were evaluated, and all were demonstrated to be insignificant. The disparity in measured interfacial areas between the two methods is attributed to the limitation of the microtomography method to characterize interfacial area associated with microscopic surface roughness due to resolution constraints.« less

Chemistry of the metal-polymer interfacial region.

PubMed

Leidheiser, H; Deck, P D

1988-09-02

In many polymer-metal systems, chemical bonds are formed that involve metal-oxygen-carbon complexes. Infrared and Mössbauer spectroscopic studies indicate that carboxylate groups play an important role in some systems. The oxygen sources may be the polymer, the oxygen present in the oxide on the metal surface, or atmospheric oxygen. Diffusion of metal ions from the substrate into the polymer interphase may occur in some systems that are cured at elevated temperatures. It is unclear whether a similar, less extensive diffusion occurs over long time periods in systems maintained at room temperature. The interfacial region is dynamic, and chemical changes occur with aging at room temperature. Positron annihilation spectroscopy may have application to characterizing the voids at the metal-polymer interface.

Formation of carbonaceous nano-layers under high interfacial pressures during lubrication with mineral and bio-based oils

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

Baltrus, John P.

In order to better protect steel surfaces against wear under high loads, understanding of chemical reactions between lubricants and metal at high interfacial pressures and elevated temperatures needs to be improved. Solutions at 5 to 20 wt. % of zinc di-2-ethylhexyl dithio phosphate (ZDDP) and chlorinated paraffins (CP) in inhibited paraffinic mineral oil (IPMO) and inhibited soy bean oil (ISBO) were compared on a Twist Compression Tribotester (TCT) at 200 MPa. Microscopy of wear tracks after 10 seconds tribotesting showed much smoother surface profiles than those of unworn areas. X-ray photoelectron spectroscopy (XPS) coupled with Ar-ion sputtering demonstrated that additivemore » solutions in ISBO formed 2–3 times thicker carbon-containing nano-layers compared to IPMO. The amounts of Cl, S or P were unexpectedly low and detectable only on the top surface with less than 5 nm penetration. CP blends in IPMO formed more inorganic chlorides than those in ISBO. It can be concluded that base oils are primarily responsible for the thickness of carbonaceous nano-layers during early stages of severe boundary lubrication, while CP or ZDDP additive contributions are important, but less significant.« less

Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

PubMed

Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

2016-01-14

In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested.

Li.sub.2 O-Al.sub.2 O.sub.3 -SiO.sub.2 glass ceramic-aluminum containing austenitic stainless steel composite body and a method of producing the same

DOEpatents

Cassidy, Roger T.

1990-05-01

The present invention relates to a hermetically sealed Li.sub.2 O-Al.sub.2 O.sub.3 -SiO.sub.2 glass ceramic-aluminum containing stainless steel composite body and a method of producing the body. The composite body includes an oxide interfacial region between the glass ceramic and metal, wherein the interfacial region consists essentially of an Al.sub.2 O.sub.3 layer. The interfacial Al.sub.2 O.sub.3 region includes constituents of both the metal and glass ceramic.

The electrode/ionic liquid interface: electric double layer and metal electrodeposition.

PubMed

Su, Yu-Zhuan; Fu, Yong-Chun; Wei, Yi-Min; Yan, Jia-Wei; Mao, Bing-Wei

2010-09-10

The last decade has witnessed remarkable advances in interfacial electrochemistry in room-temperature ionic liquids. Although the wide electrochemical window of ionic liquids is of primary concern in this new type of solvent for electrochemistry, the unusual bulk and interfacial properties brought about by the intrinsic strong interactions in the ionic liquid system also substantially influence the structure and processes at electrode/ionic liquid interfaces. Theoretical modeling and experimental characterizations have been indispensable in reaching a microscopic understanding of electrode/ionic liquid interfaces and in elucidating the physics behind new phenomena in ionic liquids. This Minireview describes the status of some aspects of interfacial electrochemistry in ionic liquids. Emphasis is placed on high-resolution and molecular-level characterization by scanning tunneling microscopy and vibrational spectroscopies of interfacial structures, and the initial stage of metal electrodeposition with application in surface nanostructuring.

Interfacial Reactivity Benchmarking of the Sodium Ion Conductors Na3PS4 and Sodium β-Alumina for Protected Sodium Metal Anodes and Sodium All-Solid-State Batteries.

PubMed

Wenzel, Sebastian; Leichtweiss, Thomas; Weber, Dominik A; Sann, Joachim; Zeier, Wolfgang G; Janek, Jürgen

2016-10-05

The interfacial stability of solid electrolytes at the electrodes is crucial for an application of all-solid-state batteries and protected electrodes. For instance, undesired reactions between sodium metal electrodes and the solid electrolyte form charge transfer hindering interphases. Due to the resulting large interfacial resistance, the charge transfer kinetics are altered and the overvoltage increases, making the interfacial stability of electrolytes the limiting factor in these systems. Driven by the promising ionic conductivities of Na 3 PS 4 , here we explore the stability and viability of Na 3 PS 4 as a solid electrolyte against metallic Na and compare it to that of Na-β″-Al 2 O 3 (sodium β-alumina). As expected, Na-β″-Al 2 O 3 is stable against sodium, whereas Na 3 PS 4 decomposes with an increasing overall resistance, making Na-β″-Al 2 O 3 the electrolyte of choice for protected sodium anodes and all-solid-state batteries.

Sum Frequency Generation Vibrational Spectroscopy Studies on ModelPeptide Adsorption at the Hydrophobic Solid-Water and HydrophilicSolid-Water Interfaces

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

York, Roger L.

2007-01-01

Sum frequency generation (SFG) vibrational spectroscopy has been used to study the interfacial structure of several polypeptides and amino acids adsorbed to hydrophobic and hydrophilic surfaces under a variety of experimental conditions. Peptide sequence, peptide chain length, peptide hydrophobicity, peptide side-chain type, surface hydrophobicity, and solution ionic strength all affect an adsorbed peptide's interfacial structure. Herein, it is demonstrated that with the choice of simple, model peptides and amino acids, surface specific SFG vibrational spectroscopy can be a powerful tool to elucidate the interfacial structure of these adsorbates. Herein, four experiments are described. In one, a series of isosequential amphiphilicmore » peptides are synthesized and studied when adsorbed to both hydrophobic and hydrophilic surfaces. On hydrophobic surfaces of deuterated polystyrene, it was determined that the hydrophobic part of the peptide is ordered at the solid-liquid interface, while the hydrophilic part of the peptide appears to have a random orientation at this interface. On a hydrophilic surface of silica, it was determined that an ordered peptide was only observed if a peptide had stable secondary structure in solution. In another experiment, the interfacial structure of a model amphiphilic peptide was studied as a function of the ionic strength of the solution, a parameter that could change the peptide's secondary structure in solution. It was determined that on a hydrophobic surface, the peptide's interfacial structure was independent of its structure in solution. This was in contrast to the adsorbed structure on a hydrophilic surface, where the peptide's interfacial structure showed a strong dependence on its solution secondary structure. In a third experiment, the SFG spectra of lysine and proline amino acids on both hydrophobic and hydrophilic surfaces were obtained by using a different experimental geometry that increases the SFG signal. Upon comparison of these spectra to the SFG spectra of interfacial polylysine and polyproline it was determined that the interfacial structure of a peptide is strongly dependent on its chain length. Lastly, SFG spectroscopy has been extended to the Amide I vibrational mode of a peptide (which is sensitive to peptide secondary structure) by building a new optical parametric amplifier based on lithium thioindate. Evidence is presented that suggests that the interfacial secondary structure of a peptide can be perturbed by a surface.« less

Giant and switchable surface activity of liquid metal via surface oxidation

PubMed Central

Khan, Mohammad Rashed; Eaker, Collin B.; Bowden, Edmond F.; Dickey, Michael D.

2014-01-01

We present a method to control the interfacial tension of a liquid alloy of gallium via electrochemical deposition (or removal) of the oxide layer on its surface. In sharp contrast with conventional surfactants, this method provides unprecedented lowering of surface tension (∼500 mJ/m2 to near zero) using very low voltage, and the change is completely reversible. This dramatic change in the interfacial tension enables a variety of electrohydrodynamic phenomena. The ability to manipulate the interfacial properties of the metal promises rich opportunities in shape-reconfigurable metallic components in electronic, electromagnetic, and microfluidic devices without the use of toxic mercury. This work suggests that the wetting properties of surface oxides—which are ubiquitous on most metals and semiconductors—are intrinsic “surfactants.” The inherent asymmetric nature of the surface coupled with the ability to actively manipulate its energetics is expected to have important applications in electrohydrodynamics, composites, and melt processing of oxide-forming materials. PMID:25228767

Keyhole and weld shapes for plasma arc welding under normal and zero gravity

NASA Technical Reports Server (NTRS)

Keanini, R. G.; Rubinsky, B.

1990-01-01

A first order study of the interfacial (keyhole) shape between a penetrating argon plasma arc jet and a stationary liquid metal weld pool is presented. The interface is determined using the Young-Laplace equation by assuming that the plasma jet behaves as a one-dimensional ideal gas flow and by neglecting flow within the weld pool. The solution for the keyhole shape allows an approximate determination of the liquid-solid metal phase boundary location based on the assumption that the liquid melt is a stagnant thermal boundary layer. Parametric studies examine the effect of plasma mass flow rate, initial plasma enthalpy, liquid metal surface tension, and jet shear on weldment shape under both normal and zero gravity. Among the more important findings of this study is that keyhole and weld geometries are minimally affected by gravity, suggesting that data gathered under gravity can be used in planning in-space welding.

The nature of interfacial instabilities in liquid metal batteries in a vertical magnetic field

NASA Astrophysics Data System (ADS)

Molokov, S.

2018-02-01

The nature of instabilities in liquid metal batteries in the presence of a vertical magnetic field has been studied. The battery consists of two liquid metal layers, connected to the collectors, and a layer with an electrolyte inbetween. The closed geometry in the horizontal plane has been replaced by a half-plane to get a better insight into the problem. As in aluminium reduction cells the instability is generated at the electrically insulating sidewall of the battery. A travelling-wave solution has been obtained, which shows that there are two modes of the instability, fast and slow. Either of these modes may be most unstable depending on the values of various parameters, the most important of which are the well-known parameter of the instability, β, and the density of the electrolyte. For the intermediate range of the electrolyte density the medium-size batteries may be expected to be stable.

Enhanced interfacial thermal transport in pnictogen tellurides metallized with a lead-free solder alloy

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

Devender,; Ramanath, Ganpati, E-mail: Ramanath@rpi.edu; Lofgreen, Kelly

2015-11-15

Controlling thermal transport across metal–thermoelectric interfaces is essential for realizing high efficiency solid-state refrigeration and waste-heat harvesting power generation devices. Here, the authors report that pnictogen chalcogenides metallized with bilayers of Sn{sub 96.5}Ag{sub 3}Cu{sub 0.5} solder and Ni barrier exhibit tenfold higher interfacial thermal conductance Γ{sub c} than that obtained with In/Ni bilayer metallization. X-ray diffraction and x-ray spectroscopy indicate that reduced interdiffusion and diminution of interfacial SnTe formation due to Ni layer correlates with the higher Γ{sub c}. Finite element modeling of thermoelectric coolers metallized with Sn{sub 96.5}Ag{sub 3}Cu{sub 0.5}/Ni bilayers presages a temperature drop ΔT ∼ 22 K that is 40%more » higher than that obtained with In/Ni metallization. Our results underscore the importance of controlling chemical intermixing at solder–metal–thermoelectric interfaces to increase the effective figure of merit, and hence, the thermoelectric cooling efficiency. These findings should facilitate the design and development of lead-free metallization for pnictogen chalcogenide-based thermoelectrics.« less

Interfacial and capillary phenomena in solidification processing of metal-matrix composites

NASA Technical Reports Server (NTRS)

Asthana, R.; Tewari, S. N.

1993-01-01

Chemical and hydrodynamic aspects of wetting and interfacial phenomena during the solidification processing of metal-matrix composites are reviewed. Significant experimental results on fiber-matrix interactions and wetting under equilibrium and non-equilibrium conditions in composites of engineering interest have been compiled, based on a survey of the recent literature. Finally, certain aspects of wetting relevant to stir-casting and infiltration processing of composites are discussed.

Nanoscale Insight and Control of Structural and Electronic Properties of Organic Semiconductor / Metal Interfaces

NASA Astrophysics Data System (ADS)

Maughan, Bret

Organic semiconductor interfaces are promising materials for use in next-generation electronic and optoelectronic devices. Current models for metal-organic interfacial electronic structure and dynamics are inadequate for strongly hybridized systems. This work aims to address this issue by identifying the factors most important for understanding chemisorbed interfaces with an eye towards tuning the interfacial properties. Here, I present the results of my research on chemisorbed interfaces formed between thin-films of phthalocyanine molecules grown on monocrystalline Cu(110). Using atomically-resolved nanoscale imaging in combination with surface-sensitive photoemission techniques, I show that single-molecule level interactions control the structural and electronic properties of the interface. I then demonstrate that surface modifications aimed at controlling interfacial interactions are an effective way to tailor the physical and electronic structure of the interface. This dissertation details a systematic investigation of the effect of molecular and surface functionalization on interfacial interactions. To understand the role of molecular structure, two types of phthalocyanine (Pc) molecules are studied: non-planar, dipolar molecules (TiOPc), and planar, non-polar molecules (H2Pc and CuPc). Multiple adsorption configurations for TiOPc lead to configuration-dependent self-assembly, Kondo screening, and electronic energy-level alignment. To understand the role of surface structure, the Cu(110) surface is textured and passivated by oxygen chemisorption prior to molecular deposition, which gives control over thin-film growth and interfacial electronic structure in H2Pc and CuPc films. Overall, the work presented here demonstrates a method for understanding interfacial electronic structure of strongly hybridized interfaces, an important first step towards developing more robust models for metal-organic interfaces, and reliable, predictive tuning of interfacial properties.

Comparison of Fluid-Fluid Interfacial Areas Measured with X-ray Microtomography and Interfacial Partitioning Tracer Tests for the same Samples.

PubMed

McDonald, Kieran; Carroll, Kenneth C; Brusseau, Mark L

2016-07-01

Two different methods are currently used for measuring interfacial areas between immiscible fluids within 3-D porous media, high-resolution microtomographic imaging and interfacial partitioning tracer tests (IPTT). Both methods were used in this study to measure non-wetting/wetting interfacial areas for a natural sand. The microtomographic imaging was conducted on the same packed columns that were used for the IPTTs. This is in contrast to prior studies comparing the two methods, for which in all cases different samples were used for the two methods. In addition, the columns were imaged before and after the IPTTs to evaluate the potential impacts of the tracer solution on fluid configuration and attendant interfacial area. The interfacial areas measured using IPTT are ~5 times larger than the microtomographic-measured values, which is consistent with previous work. Analysis of the image data revealed no significant impact of the tracer solution on NAPL configuration or interfacial area. Other potential sources of error were evaluated, and all were demonstrated to be insignificant. The disparity in measured interfacial areas between the two methods is attributed to the limitation of the microtomography method to characterize interfacial area associated with microscopic surface roughness due to resolution constraints.

Electrical Matching at Metal/Molecule Contacts for Efficient Heterogeneous Charge Transfer.

PubMed

Sato, Shino; Iwase, Shigeru; Namba, Kotaro; Ono, Tomoya; Hara, Kenji; Fukuoka, Atsushi; Uosaki, Kohei; Ikeda, Katsuyoshi

2018-02-27

In a metal/molecule hybrid system, unavoidable electrical mismatch exists between metal continuum states and frontier molecular orbitals. This causes energy loss in the electron conduction across the metal/molecule interface. For efficient use of energy in a metal/molecule hybrid system, it is necessary to control interfacial electronic structures. Here we demonstrate that electrical matching between a gold substrate and π-conjugated molecular wires can be obtained by using monatomic foreign metal interlayers, which can change the degree of d-π* back-donation at metal/anchor contacts. This interfacial control leads to energy level alignment between the Fermi level of the metal electrode and conduction molecular orbitals, resulting in resonant electron conduction in the metal/molecule hybrid system. When this method is applied to molecule-modified electrocatalysts, the heterogeneous electrochemical reaction rate is considerably improved with significant suppression of energy loss at the internal electron conduction.

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

Ivanov, Ilia N.; Simpson, John T.

A method of preparing a network comprises disposing a solution comprising particulate materials in a solvent onto a superhydrophobic surface comprising a plurality of superhydrophobic features and interfacial areas between the superhydrophobic features. The plurality of superhydrophobic features has a water contact angle of at least about 150.degree.. The method of preparing the network also comprises removing the solvent from the solution of the particulate materials, and forming a network of the particulate materials in the interfacial areas, the particulate materials receding to the interfacial areas as the solvent is removed.

Magneto-ionic control of interfacial magnetism

NASA Astrophysics Data System (ADS)

Bauer, Uwe; Yao, Lide; Tan, Aik Jun; Agrawal, Parnika; Emori, Satoru; Tuller, Harry L.; van Dijken, Sebastiaan; Beach, Geoffrey S. D.

2015-02-01

In metal/oxide heterostructures, rich chemical, electronic, magnetic and mechanical properties can emerge from interfacial chemistry and structure. The possibility to dynamically control interface characteristics with an electric field paves the way towards voltage control of these properties in solid-state devices. Here, we show that electrical switching of the interfacial oxidation state allows for voltage control of magnetic properties to an extent never before achieved through conventional magneto-electric coupling mechanisms. We directly observe in situ voltage-driven O2- migration in a Co/metal-oxide bilayer, which we use to toggle the interfacial magnetic anisotropy energy by >0.75 erg cm-2 at just 2 V. We exploit the thermally activated nature of ion migration to markedly increase the switching efficiency and to demonstrate reversible patterning of magnetic properties through local activation of ionic migration. These results suggest a path towards voltage-programmable materials based on solid-state switching of interface oxygen chemistry.

Topology-generating interfacial pattern formation during liquid metal dealloying

DOE PAGES

Geslin, Pierre -Antoine; McCue, Ian; Gaskey, Bernard; ...

2015-11-19

Liquid metal dealloying has emerged as a novel technique to produce topologically complex nanoporous and nanocomposite structures with ultra-high interfacial area and other unique properties relevant for diverse material applications. This process is empirically known to require the selective dissolution of one element of a multicomponent solid alloy into a liquid metal to obtain desirable structures. However, how structures form is not known. Here we demonstrate, using mesoscale phase-field modelling and experiments, that nano/microstructural pattern formation during dealloying results from the interplay of (i) interfacial spinodal decomposition, forming compositional domain structures enriched in the immiscible element, and (ii) diffusion-coupled growthmore » of the enriched solid phase and the liquid phase into the alloy. We highlight how those two basic mechanisms interact to yield a rich variety of topologically disconnected and connected structures. Furthermore, we deduce scaling laws governing microstructural length scales and dealloying kinetics.« less

Topology-generating interfacial pattern formation during liquid metal dealloying.

PubMed

Geslin, Pierre-Antoine; McCue, Ian; Gaskey, Bernard; Erlebacher, Jonah; Karma, Alain

2015-11-19

Liquid metal dealloying has emerged as a novel technique to produce topologically complex nanoporous and nanocomposite structures with ultra-high interfacial area and other unique properties relevant for diverse material applications. This process is empirically known to require the selective dissolution of one element of a multicomponent solid alloy into a liquid metal to obtain desirable structures. However, how structures form is not known. Here we demonstrate, using mesoscale phase-field modelling and experiments, that nano/microstructural pattern formation during dealloying results from the interplay of (i) interfacial spinodal decomposition, forming compositional domain structures enriched in the immiscible element, and (ii) diffusion-coupled growth of the enriched solid phase and the liquid phase into the alloy. We highlight how those two basic mechanisms interact to yield a rich variety of topologically disconnected and connected structures. Moreover, we deduce scaling laws governing microstructural length scales and dealloying kinetics.

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

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

Gao, Yue; Zhao, Yuming; Li, Yuguang C.

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

DOE PAGES

Gao, Yue; Zhao, Yuming; Li, Yuguang C.; ...

2017-10-06

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Optimization of residual stresses in MMC's through the variation of interfacial layer architectures and processing parameters

NASA Technical Reports Server (NTRS)

Pindera, Marek-Jerzy; Salzar, Robert S.

1996-01-01

The objective of this work was the development of efficient, user-friendly computer codes for optimizing fabrication-induced residual stresses in metal matrix composites through the use of homogeneous and heterogeneous interfacial layer architectures and processing parameter variation. To satisfy this objective, three major computer codes have been developed and delivered to the NASA-Lewis Research Center, namely MCCM, OPTCOMP, and OPTCOMP2. MCCM is a general research-oriented code for investigating the effects of microstructural details, such as layered morphology of SCS-6 SiC fibers and multiple homogeneous interfacial layers, on the inelastic response of unidirectional metal matrix composites under axisymmetric thermomechanical loading. OPTCOMP and OPTCOMP2 combine the major analysis module resident in MCCM with a commercially-available optimization algorithm and are driven by user-friendly interfaces which facilitate input data construction and program execution. OPTCOMP enables the user to identify those dimensions, geometric arrangements and thermoelastoplastic properties of homogeneous interfacial layers that minimize thermal residual stresses for the specified set of constraints. OPTCOMP2 provides additional flexibility in the residual stress optimization through variation of the processing parameters (time, temperature, external pressure and axial load) as well as the microstructure of the interfacial region which is treated as a heterogeneous two-phase composite. Overviews of the capabilities of these codes are provided together with a summary of results that addresses the effects of various microstructural details of the fiber, interfacial layers and matrix region on the optimization of fabrication-induced residual stresses in metal matrix composites.

Interfacial Ferromagnetism in LaNiO3/CaMnO3 Superlattices

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

Grutter, Alexander J.; Yang, Hao; Kirby, B. J.

2013-08-01

We observe interfacial ferromagnetism in superlattices of the paramagnetic metal LaNiO3 and the antiferromagnetic insulator CaMnO3. LaNiO3 exhibits a thickness dependent metal-insulator transition and we find the emergence of ferromagnetism to be coincident with the conducting state of LaNiO3. That is, only superlattices in which the LaNiO3 layers are metallic exhibit ferromagnetism. Using several magnetic probes, we have determined that the ferromagnetism arises in a single unit cell of CaMnO3 at the interface. Together these results suggest that ferromagnetism can be attributed to a double exchange interaction among Mn ions mediated by the adjacent itinerant metal.

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

Zhou, Weidong; Li, Yutao; Xin, Sen

A reversible plating/stripping of a dendrite-free metallic-sodium anode with a reduced anode/ceramic interfacial resistance is created by a thin interfacial interlayer formed in situ or by the introduction of a dry polymer film. Wetting of the sodium on the interfacial interlayer suppresses dendrite formation and growth at different discharge/charge C-rates. Furthermore, all-solid-state batteries were obtained with a high cycling stability and Coulombic efficiency at 65 °C.

Effects of surface treatments and bonding types on the interfacial behavior of fiber metal laminate based on magnesium alloy

NASA Astrophysics Data System (ADS)

Zhang, Xi; Ma, Quanyang; Dai, Yu; Hu, Faping; Liu, Gang; Xu, Zouyuan; Wei, Guobing; Xu, Tiancai; Zeng, Qingwen; Xie, Weidong

2018-01-01

Fiber metal laminates based on magnesium alloys (MgFML) with different surface treatments and different bonding types were tested and analyzed. By using dynamic contact angle measurement and scanning electron microscopy (SEM), it was found that phosphating treatment can significantly improve the surface energy and wettability of magnesium alloy, and the surface energy of phosphated magnesium alloy was approximately 50% higher than that of abraded-only magnesium alloy. The single cantilever beam (SCB) test showed that the interfacial fracture energies of directly bonded MgFMLs based on abraded-only magnesium and abraded + phosphated magnesium were 650 J/m2 and 1030 J/m2, respectively, whereas the interfacial fracture energies of indirectly bonded MgFMLs were 1650 J/m2 and 2260 J/m2, respectively. Phosphating treatment and modified polypropylene interleaf were observed to improve the tensile strength and interfacial fracture toughness of MgFML. In addition, the rougher surface was more conducive to enhance the bonding strength and interfacial fracture toughness of MgFML.

Role of polar compensation in interfacial ferromagnetism of LaNiO3/CaMnO3 superlattices

NASA Astrophysics Data System (ADS)

Flint, C. L.; Jang, H.; Lee, J.-S.; N'Diaye, A. T.; Shafer, P.; Arenholz, E.; Suzuki, Y.

2017-07-01

Polar compensation can play an important role in the determination of interfacial electronic and magnetic properties in oxide heterostructures. Using x-ray absorption spectroscopy, x-ray magnetic circular dichroism, bulk magnetometry, and transport measurements, we find that interfacial charge redistribution via polar compensation is essential for explaining the evolution of interfacial ferromagnetism in LaNiO3/CaMnO3 superlattices as a function of LaNiO3 layer thickness. In insulating superlattices (four unit cells or less of LaNiO3), magnetism is dominated by Ni-Mn superexchange, while itinerant electron-based Mn-Mn double exchange plays a role in thicker metallic superlattices. X-ray magnetic circular dichroism and resonant x-ray scattering show that Ni-Mn superexchange contributes to the magnetization even in metallic superlattices. This Ni-Mn superexchange interaction can be explained in terms of polar compensation at the LaNiO3-CaMnO3 interface. These results highlight the different mechanisms responsible for interfacial ferromagnetism and the importance of understanding compensation due to polar mismatch at oxide-based interfaces when engineering magnetic properties.

Investigation of energy band alignments and interfacial properties of rutile NMO2/TiO2 (NM = Ru, Rh, Os, and Ir) by first-principles calculations.

PubMed

Yang, Chen; Zhao, Zong-Yan

2017-11-08

In the field of photocatalysis, constructing hetero-structures is an efficient strategy to improve quantum efficiency. However, a lattice mismatch often induces unfavorable interfacial states that can act as recombination centers for photo-generated electron-hole pairs. If the hetero-structure's components have the same crystal structure, this disadvantage can be easily avoided. Conversely, in the process of loading a noble metal co-catalyst onto the TiO 2 surface, a transition layer of noble metal oxides is often formed between the TiO 2 layer and the noble metal layer. In this article, interfacial properties of hetero-structures composed of a noble metal dioxide and TiO 2 with a rutile crystal structure have been systematically investigated using first-principles calculations. In particular, the Schottky barrier height, band bending, and energy band alignments are studied to provide evidence for practical applications. In all cases, no interfacial states exist in the forbidden band of TiO 2 , and the interfacial formation energy is very small. A strong internal electric field generated by interfacial electron transfer leads to an efficient separation of photo-generated carriers and band bending. Because of the differences in the atomic properties of the components, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures demonstrate band dividing, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures have a pseudo-gap near the Fermi energy level. Furthermore, NMO 2 /TiO 2 hetero-structures show upward band bending. Conversely, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures present a relatively strong infrared light absorption, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures show an obvious absorption edge in the visible light region. Overall, considering all aspects of their properties, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures are more suitable than others for improving the photocatalytic performance of TiO 2 . These findings will provide useful information for understanding the role and effects of a noble metal dioxide as a transition layer between a noble metal co-catalyst and a TiO 2 photocatalyst.

Oxidation state and interfacial effects on oxygen vacancies in tantalum pentoxide

DOE PAGES

Bondi, Robert J.; Marinella, Matthew J.

2015-02-28

First-principles density-functional theory (DFT) calculations are used to study the atomistic structure, structural energetics, and electron density near the O monovacancy (V O n; n=0,1+,2+) in both bulk, amorphous tantalum pentoxide (a-Ta 2O 5) and also at vacuum and metallic Ta interfaces. We calculate multivariate vacancy formation energies to evaluate stability as a function of oxidation state, distance from interface plane, and Fermi energy. V O n of all oxidation states preferentially segregate at both Ta and vacuum interfaces, where the metallic interface exhibits global formation energy minima. In a-Ta 2O 5, V O 0 are characterized by structural contractionmore » and electron density localization, while V O 2+ promote structural expansion and are depleted of electron density. In contrast, interfacial V O 0 and V O 2+ show nearly indistinguishable ionic and electronic signatures indicative of a reduced V O center. Interfacial V O 2+ extract electron density from metallic Ta indicating V O 2+ is spontaneously reduced at the expense of the metal. This oxidation/reduction behavior suggests careful selection and processing of both oxide layer and metal electrodes for engineering memristor device operation.« less

Activating "Invisible" Glue: Using Electron Beam for Enhancement of Interfacial Properties of Graphene-Metal Contact.

PubMed

Kim, Songkil; Russell, Michael; Kulkarni, Dhaval D; Henry, Mathias; Kim, Steve; Naik, Rajesh R; Voevodin, Andrey A; Jang, Seung Soon; Tsukruk, Vladimir V; Fedorov, Andrei G

2016-01-26

Interfacial contact of two-dimensional graphene with three-dimensional metal electrodes is crucial to engineering high-performance graphene-based nanodevices with superior performance. Here, we report on the development of a rapid "nanowelding" method for enhancing properties of interface to graphene buried under metal electrodes using a focused electron beam induced deposition (FEBID). High energy electron irradiation activates two-dimensional graphene structure by generation of structural defects at the interface to metal contacts with subsequent strong bonding via FEBID of an atomically thin graphitic interlayer formed by low energy secondary electron-assisted dissociation of entrapped hydrocarbon contaminants. Comprehensive investigation is conducted to demonstrate formation of the FEBID graphitic interlayer and its impact on contact properties of graphene devices achieved via strong electromechanical coupling at graphene-metal interfaces. Reduction of the device electrical resistance by ∼50% at a Dirac point and by ∼30% at the gate voltage far from the Dirac point is obtained with concurrent improvement in thermomechanical reliability of the contact interface. Importantly, the process is rapid and has an excellent insertion potential into a conventional fabrication workflow of graphene-based nanodevices through single-step postprocessing modification of interfacial properties at the buried heterogeneous contact.

High Tc superconducting films from metallo-organic precursors

NASA Astrophysics Data System (ADS)

Davison, W. W.; Shyu, S. G.; Buchanan, R. C.

High Tc superconducting films of heavy metal soaps (derived from carboxylic acid precursors) have been prepared on Si and other substrates. The precursors were synthesized and mixed in appropriate molar ratios to form the high Tc compound YBa2Cu3O(7-x), using a high boiling point common solvent base. The precursor solution was deposited by a spin casting technique on the substrates. Film thicknesses of 0.1-1.0 micron were achieved after heat treatment at 550-850 C at not longer than 4 hours. Films were analyzed as to orientation, appropriate phase, interfacial reaction, and superconducting properties.

Structural modifications due to interface chemistry at metal-nitride interfaces

DOE PAGES

Yadav, S. K.; Shao, S.; Wang, J.; ...

2015-11-27

Based on accurate first principles density functional theory (DFT) calculations, an unusual phenomenon of interfacial structural modifications, due to the interface chemistry influence is identified at two metal-nitride interfaces with strong metal-nitrogen affinity, Al/TiN {111} and Al/VN {111} interfaces. It is shown that at such interfaces, a faulted stacking structure is energetically preferred on the Al side of the interface. And both intrinsic and extrinsic stacking fault energies in the vicinity Al layers are negligibly small. However, such phenomenon does not occur in Pt/TiN and Pt/VN interfaces because of the weak Pt-N affinity. As a result, corresponding to structural energiesmore » of metal-nitride interfaces, the linear elasticity analysis predicts characteristics of interfacial misfit dislocations at metal-nitride interfaces.« less

Structural modifications due to interface chemistry at metal-nitride interfaces

PubMed Central

Yadav, S. K.; Shao, S.; Wang, J.; Liu, X.-Y.

2015-01-01

Based on accurate first principles density functional theory (DFT) calculations, an unusual phenomenon of interfacial structural modifications, due to the interface chemistry influence is identified at two metal-nitride interfaces with strong metal-nitrogen affinity, Al/TiN {111} and Al/VN {111} interfaces. It is shown that at such interfaces, a faulted stacking structure is energetically preferred on the Al side of the interface. And both intrinsic and extrinsic stacking fault energies in the vicinity Al layers are negligibly small. However, such phenomenon does not occur in Pt/TiN and Pt/VN interfaces because of the weak Pt-N affinity. Corresponding to structural energies of metal-nitride interfaces, the linear elasticity analysis predicts characteristics of interfacial misfit dislocations at metal-nitride interfaces. PMID:26611639

Fabrication of metal nanoelectrodes by interfacial reactions.

PubMed

Zhu, Xinyu; Qiao, Yonghui; Zhang, Xin; Zhang, Sensen; Yin, Xiaohong; Gu, Jing; Chen, Ye; Zhu, Zhiwei; Li, Meixian; Shao, Yuanhua

2014-07-15

Despite great improvements in the past decades, the controllable fabrication of metal nanoelectrodes still remains very challenging. In this work, a simple and general way to fabricate metal nanoelectrodes (Ag, Au, and Pt) is developed. On the basis of interfacial reactions at nano-liquid/liquid interfaces supported at nanopipettes, the nanoparticles can be formed in situ and have been used to block the orifices of pipettes to make nanoelectrodes. The effect of the driving force for interfacial reaction at the liquid/liquid interface, the ratio of redox species in organic and aqueous phases, and the surface charge of the inner wall of a pipette have been studied. The fabricated nanoelectrodes have been characterized by scanning electron microscopy (SEM) and electrochemical techniques. A silver electrode with about 10 nm in radius has been employed as the scanning electrochemical microscopy (SECM) probe to explore the thickness of a water/nitrobenzene (W/NB) interface, and this value is equal to 0.8 ± 0.1 nm (n = 5). This method of fabrication of nanoelectrodes can be extended to other metal or semiconductor electrodes.

Nitride passivation reduces interfacial traps in atomic-layer-deposited Al{sub 2}O{sub 3}/GaAs (001) metal-oxide-semiconductor capacitors using atmospheric metal-organic chemical vapor deposition

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

Aoki, T., E-mail: aokit@sc.sumitomo-chem.co.jp; Fukuhara, N.; Osada, T.

2014-07-21

Using an atmospheric metal-organic chemical vapor deposition system, we passivated GaAs with AlN prior to atomic layer deposition of Al{sub 2}O{sub 3}. This AlN passivation incorporated nitrogen at the Al{sub 2}O{sub 3}/GaAs interface, improving the capacitance-voltage (C–V) characteristics of the resultant metal-oxide-semiconductor capacitors (MOSCAPs). The C–V curves of these devices showed a remarkable reduction in the frequency dispersion of the accumulation capacitance. Using the conductance method at various temperatures, we extracted the interfacial density of states (D{sub it}). The D{sub it} was reduced over the entire GaAs band gap. In particular, these devices exhibited D{sub it} around the midgap ofmore » less than 4 × 10{sup 12} cm{sup −2}eV{sup −1}, showing that AlN passivation effectively reduced interfacial traps in the MOS structure.« less

Interface Schottky barrier engineering via strain in metal-semiconductor composites

NASA Astrophysics Data System (ADS)

Ma, Xiangchao; Dai, Ying; Yu, Lin; Huang, Baibiao

2016-01-01

The interfacial carrier transfer property, which is dominated by the interface Schottky barrier height (SBH), plays a crucial role in determining the performance of metal-semiconductor heterostructures in a variety of applications. Therefore, artificially controlling the interface SBH is of great importance for their industrial applications. As a model system, the Au/TiO2 (001) heterostructure is studied using first-principles calculations and the tight-binding method in the present study. Our investigation demonstrates that strain can be an effective way to decrease the interface SBH and that the n-type SBH can be more effectively decreased than the p-type SBH. Astonishingly, strain affects the interface SBH mainly by changing the intrinsic properties of Au and TiO2, whereas the interfacial potential alignment is almost independent of strain due to two opposite effects, which are induced by strain at the interfacial region. These observed trends can be understood on the basis of the general free-electron gas model of typical metals, the tight-binding theory and the crystal-field theory, which suggest that similar trends may be generalized for many other metal-semiconductor heterostructures. Given the commonness and tunability of strain in typical heterostructures, we anticipate that the tunability of the interface SBH with strain described here can provide an alternative effective way for realizing more efficient applications of relevant heterostructures.The interfacial carrier transfer property, which is dominated by the interface Schottky barrier height (SBH), plays a crucial role in determining the performance of metal-semiconductor heterostructures in a variety of applications. Therefore, artificially controlling the interface SBH is of great importance for their industrial applications. As a model system, the Au/TiO2 (001) heterostructure is studied using first-principles calculations and the tight-binding method in the present study. Our investigation demonstrates that strain can be an effective way to decrease the interface SBH and that the n-type SBH can be more effectively decreased than the p-type SBH. Astonishingly, strain affects the interface SBH mainly by changing the intrinsic properties of Au and TiO2, whereas the interfacial potential alignment is almost independent of strain due to two opposite effects, which are induced by strain at the interfacial region. These observed trends can be understood on the basis of the general free-electron gas model of typical metals, the tight-binding theory and the crystal-field theory, which suggest that similar trends may be generalized for many other metal-semiconductor heterostructures. Given the commonness and tunability of strain in typical heterostructures, we anticipate that the tunability of the interface SBH with strain described here can provide an alternative effective way for realizing more efficient applications of relevant heterostructures. Electronic supplementary information (ESI) available: The changes of Au 5d DOS, valence bands of TiO2, the interfacial bond length and interfacial energy with strain, and the local DOS results for the change of SBH with strain. See DOI: 10.1039/c5nr05583k

Detection of amide I signals of interfacial proteins in situ using SFG.

PubMed

Wang, Jie; Even, Mark A; Chen, Xiaoyun; Schmaier, Alvin H; Waite, J Herbert; Chen, Zhan

2003-08-20

In this Communication, we demonstrate the novel observation that it is feasible to collect amide signals from polymer/protein solution interfaces in situ using sum frequency generation (SFG) vibrational spectroscopy. Such SFG amide signals allow for acquisition of more detailed molecular level information of entire interfacial protein structures. Proteins investigated include bovine serum albumin, mussel protein mefp-2, factor XIIa, and ubiquitin. Our studies indicate that different proteins generate different SFG amide signals at the polystyrene/protein solution interface, showing that they have different interfacial coverage, secondary structure, or orientation.

Multiligand Metal-Phenolic Assembly from Green Tea Infusions.

PubMed

Rahim, Md Arifur; Björnmalm, Mattias; Bertleff-Zieschang, Nadja; Ju, Yi; Mettu, Srinivas; Leeming, Michael G; Caruso, Frank

2018-03-07

The synthesis of hybrid functional materials using the coordination-driven assembly of metal-phenolic networks (MPNs) is of interest in diverse areas of materials science. To date, MPN assembly has been explored as monoligand systems (i.e., containing a single type of phenolic ligand) where the phenolic components are primarily obtained from natural sources via extraction, isolation, and purification processes. Herein, we demonstrate the fabrication of MPNs from a readily available, crude phenolic source-green tea (GT) infusions. We employ our recently introduced rust-mediated continuous assembly strategy to prepare these GT MPN systems. The resulting hollow MPN capsules contain multiple phenolic ligands and have a shell thickness that can be controlled through the reaction time. These multiligand MPN systems have different properties compared to the analogous MPN systems reported previously. For example, the Young's modulus (as determined using colloidal-probe atomic force microscopy) of the GT MPN system presented herein is less than half that of MPN systems prepared using tannic acid and iron salt solutions, and the disassembly kinetics are faster (∼50%) than other, comparable MPN systems under identical disassembly conditions. Additionally, the use of rust-mediated assembly enables the formation of stable capsules under conditions where the conventional approach (i.e., using iron salt solutions) results in colloidally unstable dispersions. These differences highlight how the choice of phenolic ligand and its source, as well as the assembly protocol (e.g., using solution-based or solid-state iron sources), can be used to tune the properties of MPNs. The strategy presented herein expands the toolbox of MPN assembly while also providing new insights into the nature and robustness of metal-phenolic interfacial assembly when using solution-based or solid-state metal sources.

Single-Molecule Interfacial Electron Transfer

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

Lu, H. Peter

This project is focused on the use of single-molecule high spatial and temporal resolved techniques to study molecular dynamics in condensed phase and at interfaces, especially, the complex reaction dynamics associated with electron and energy transfer rate processes. The complexity and inhomogeneity of the interfacial ET dynamics often present a major challenge for a molecular level comprehension of the intrinsically complex systems, which calls for both higher spatial and temporal resolutions at ultimate single-molecule and single-particle sensitivities. Combined single-molecule spectroscopy and electrochemical atomic force microscopy approaches are unique for heterogeneous and complex interfacial electron transfer systems because the static andmore » dynamic inhomogeneities can be identified and characterized by studying one molecule at a specific nanoscale surface site at a time. The goal of our project is to integrate and apply these spectroscopic imaging and topographic scanning techniques to measure the energy flow and electron flow between molecules and substrate surfaces as a function of surface site geometry and molecular structure. We have been primarily focusing on studying interfacial electron transfer under ambient condition and electrolyte solution involving both single crystal and colloidal TiO 2 and related substrates. The resulting molecular level understanding of the fundamental interfacial electron transfer processes will be important for developing efficient light harvesting systems and broadly applicable to problems in fundamental chemistry and physics. We have made significant advancement on deciphering the underlying mechanism of the complex and inhomogeneous interfacial electron transfer dynamics in dyesensitized TiO 2 nanoparticle systems that strongly involves with and regulated by molecule-surface interactions. We have studied interfacial electron transfer on TiO 2 nanoparticle surfaces by using ultrafast single-molecule spectroscopy and electrochemical AFM metal tip scanning microscopy, focusing on understanding the interfacial electron transfer dynamics at specific nanoscale electron transfer sites with high-spatially and temporally resolved topographic-and-spectroscopic characterization at individual molecule basis, characterizing single-molecule rate processes, reaction driving force, and molecule-substrate electronic coupling. One of the most significant characteristics of our new approach is that we are able to interrogate the complex interfacial electron transfer dynamics by actively pin-point energetic manipulation of the surface interaction and electronic couplings, beyond the conventional excitation and observation.« less

Electron-selective contacts via ultra-thin organic interface dipoles for silicon organic heterojunction solar cells

NASA Astrophysics Data System (ADS)

Reichel, Christian; Würfel, Uli; Winkler, Kristina; Schleiermacher, Hans-Frieder; Kohlstädt, Markus; Unmüssig, Moritz; Messmer, Christoph A.; Hermle, Martin; Glunz, Stefan W.

2018-01-01

In the last years, novel materials for the formation of electron-selective contacts on n-type crystalline silicon (c-Si) heterojunction solar cells were explored as an interfacial layer between the metal electrode and the c-Si wafer. Besides inorganic materials like transition metal oxides or alkali metal fluorides, also interfacial layers based on organic molecules with a permanent dipole moment are promising candidates to improve the contact properties. Here, the dipole effect plays an essential role in the modification of the interface and effective work function of the contact. The amino acids L-histidine, L-tryptophan, L-phenylalanine, glycine, and sarcosine, the nucleobase adenine, and the heterocycle 4-hydroxypyridine were investigated as dipole materials for an electron-selective contact on the back of p- and n-type c-Si with a metal electrode based on aluminum (Al). Furthermore, the effect of an added fluorosurfactant on the resulting contact properties was examined. The performance of n-type c-Si solar cells with a boron diffusion on the front was significantly increased when L-histidine and/or the fluorosurfactant was applied as a full-area back surface field. This improvement was attributed to the modification of the interface and the effective work function of the contact by the dipole material which was corroborated by numerical device simulations. For these solar cells, conversion efficiencies of 17.5% were obtained with open-circuit voltages (Voc) of 625 mV and fill factors of 76.3%, showing the potential of organic interface dipoles for silicon organic heterojunction solar cells due to their simple formation by solution processing and their low thermal budget requirements.

Synthesis, integration, and characterization of metal oxide films as alternative gate dielectric materials

NASA Astrophysics Data System (ADS)

Lin, You-Sheng

ZrO2 and HfO2 were investigated in this study to replace SiO2 as the potential gate dielectric materials in metal-oxide-semiconductor field effect transistors. ZrO2 and HfO2 films were deposited on p-type Si (100) wafers by an atomic layer chemical vapor deposition (ALCVD) process using zirconium (IV) t-butoxide and hafnium (IV) t-butoxide as the metal precursors, respectively. Oxygen was used alternatively with these metal alkoxide precursors into the reactor with purging and evacuation in between. The as-deposited ZrO2 and HfO2 films were stoichiometric and uniform based on X-ray photoemission spectroscopy and ellipsometry measurements. X-ray diffraction analysis indicated that the deposited films were amorphous, however, the high-resolution transmission electron microscopy showed an interfacial layer formation on the silicon substrate. Time-of-flight secondary ion mass spectrometry and medium energy ion scattering analysis showed significant intermixing between metal oxides and Si, indicating the formation of metal silicates, which were confirmed by their chemical etching resistance in HF solutions. The thermal stability of ZrO2 and HfO2 thin films on silicon was examined by monitoring their decomposition temperatures in ultra-high vacuum, using in-situ synchrotron radiation ultra-violet photoemission spectroscopy. The as-deposited ZrO2 and HfO2 thin films were thermally stable up to 880°C and 950°C in vacuum, respectively. The highest achieveable dielectric constants of as-deposited ZrO 2 and HfO2 were 21 and 24, respectively, which were slightly lower than the reported dielectric constants of bulk ZrO2 and HfO 2. These slight reductions in dielectric constants were attributed to the formation of the interfacial metal silicate layers. Very small hysteresis and interface state density were observed for both metal oxide films. Their leakage currents were a few orders of magnitude lower than that of SiO 2 at the same equivalent oxide thickness. NMOSFETs were also fabricated with the as-deposited metal oxide films, and reasonable ID-V D and IG-VG results were obtained. The electron mobilities were high from devices built using a plasma etching process to pattern the metal oxide films. However, they can be degraded if an HF wet etching process was used due to the large contact resistences. Upon oxygen annealing, the formation of SiOx at the interface improved the thermal stability of the as-deposited metal oxide films, however, lower overall dielectric constant and higher leakage current were observed. Upon ammonia annealing, the formation of SiOxNy improved not only the thermal stability but also reduced the leakage current. However, the overall dielectric constant of the film was still reduced due to the formation of the additional interfacial layer.

Metal-Organic Framework-Stabilized CO2/Water Interfacial Route for Photocatalytic CO2 Conversion.

PubMed

Luo, Tian; Zhang, Jianling; Li, Wei; He, Zhenhong; Sun, Xiaofu; Shi, Jinbiao; Shao, Dan; Zhang, Bingxing; Tan, Xiuniang; Han, Buxing

2017-11-29

Here, we propose a CO 2 /water interfacial route for photocatalytic CO 2 conversion by utilizing a metal-organic framework (MOF) as both an emulsifier and a catalyst. The CO 2 reduction occurring at the CO 2 /water interface produces formate with remarkably enhanced efficiency as compared with that in conventional solvent. The route is efficient, facile, adjustable, and environmentally benign, which is applicable for the CO 2 transformation photocatalyzed by different kinds of MOFs.

Engineered metal based nanomaterials in aqueous environments: Interactions, transformations and implications

NASA Astrophysics Data System (ADS)

Mudunkotuwa, Imali Ama

Nanoscience and nanotechnology offer potential routes towards addressing critical issues such as clean and sustainable energy, environmental protection and human health. Specifically, metal and metal oxide nanomaterials are found in a wide range of applications and therefore hold a greater potential of possible release into the environment or for the human to be exposed. Understanding the aqueous phase behavior of metal and metal oxide nanomaterials is a key factor in the safe design of these materials because their interactions with living systems are always mediated through the aqueous phase. Broadly the transformations in the aqueous phase can be classified as dissolution, aggregation and adsorption which are dependent and linked processes to one another. The complexity of these processes at the liquid-solid interface has therefore been one of the grand challenges that has persisted since the beginning of nanotechnology. Although classical models provide guidance for understanding dissolution and aggregation of nanoparticles in water, there are many uncertainties associated with the recent findings. This is often due to a lack of fundamental knowledge of the surface structure and surface energetics for very small particles. Therefore currently the environmental health and safety studies related to nanomaterials are more focused on understanding the surface chemistry that governs the overall processes in the liquid-solid interfacial region at the molecular level. The metal based nanomaterials focused on in this dissertation include TiO2, ZnO, Cu and CuO. These are among the most heavily used in a number of applications ranging from uses in the construction industry to cosmetic formulation. Therefore they are produced in large scale and have been detected in the environment. There is debate within the scientific community related to their safety as a result of the lack of understanding on the surface interactions that arise from the detailed nature of the surfaces. Specifically, the interactions of these metal and metal oxide nanoparticles with environmental and biological ligands in the solutions have demonstrated dramatic alterations in their aqueous phase behavior in terms of dissolution and aggregation. Dissolution and aggregation are among the determining factors of nanoparticle uptake and toxicity. Furthermore, solution conditions such as ionic strength and pH can act as controlling parameters for surface ligand adsorption while adsorbed ligands themselves undergo surface induced structural and conformational changes. Because, nanomaterials in both the environment and in biological systems are subjected to a wide range of matrix conditions they are in fact dynamic and not static entities. Thus monitoring and tracking these nanomaterials in real systems can be extremely challenging which requires a thorough understanding of the surface chemistry governing their transformations. The work presented in this dissertation attempts to bridge the gap between the dynamic processing of these nanomaterials, the details of the molecular level processes that occur at the liquid-solid interfacial region and potential environmental and biological interactions. Extensive nanomaterial characterization is an integral part of these investigations and all the materials presented here are thoroughly analyzed for particle size, shape, surface area, bulk and surface compositions. Detailed spectroscopic analysis was used to acquire molecular information of the processes in the liquid-solid interfacial region and the outcomes are linked with the macroscopic analysis with the aid of dynamic and static light scattering techniques. Furthermore, emphasis is given to the size dependent behavior and theoretical modeling is adapted giving careful consideration to the details of the physicochemical characterization and molecular information unique to the nanomaterials.

Improved interfacial and electrical properties of GaAs metal-oxide-semiconductor capacitors with HfTiON as gate dielectric and TaON as passivation interlayer

NASA Astrophysics Data System (ADS)

Wang, L. S.; Xu, J. P.; Zhu, S. Y.; Huang, Y.; Lai, P. T.

2013-08-01

The interfacial and electrical properties of sputtered HfTiON on sulfur-passivated GaAs with or without TaON as interfacial passivation layer (IPL) are investigated. Experimental results show that the GaAs metal-oxide-semiconductor capacitor with HfTiON/TaON stacked gate dielectric annealed at 600 °C exhibits low interface-state density (1.0 × 1012 cm-2 eV-1), small gate leakage current (7.3 × 10-5 A cm-2 at Vg = Vfb + 1 V), small capacitance equivalent thickness (1.65 nm), and large equivalent dielectric constant (26.2). The involved mechanisms lie in the fact that the TaON IPL can effectively block the diffusions of Hf, Ti, and O towards GaAs surface and suppress the formation of interfacial As-As bonds, Ga-/As-oxides, thus unpinning the Femi level at the TaON/GaAs interface and improving the interface quality and electrical properties of the device.

The hydration structure at yttria-stabilized cubic zirconia (110)-water interface with sub-Ångström resolution

DOE PAGES

Hou, Binyang; Kim, Seunghyun; Kim, Taeho; ...

2016-06-15

The interfacial hydration structure of yttria-stabilized cubic zirconia (110) surface in contact with water was determined with ~0.5 Å resolution by high-resolution X-ray reflectivity measurement. The terminal layer shows a reduced electron density compared to the following substrate lattice layers, which indicates there are additional defects generated by metal depletion as well as intrinsic oxygen vacancies, both of which are apparently filled by water species. Above this top surface layer, two additional adsorbed layers are observed forming a characteristic interfacial hydration structure. The first adsorbed layer shows abnormally high density as pure water and likely includes metal species, whereas themore » second layer consists of pure water. The observed interfacial hydration structure seems responsible for local equilibration of the defective surface in water and eventually regulating the long-term degradation processes. As a result, the multitude of water interactions with the zirconia surface results in the complex but highly ordered interfacial structure constituting the reaction front.« less

Rechargeable sodium all-solid-state battery

DOE PAGES

Zhou, Weidong; Li, Yutao; Xin, Sen; ...

2017-01-03

A reversible plating/stripping of a dendrite-free metallic-sodium anode with a reduced anode/ceramic interfacial resistance is created by a thin interfacial interlayer formed in situ or by the introduction of a dry polymer film. Wetting of the sodium on the interfacial interlayer suppresses dendrite formation and growth at different discharge/charge C-rates. Furthermore, all-solid-state batteries were obtained with a high cycling stability and Coulombic efficiency at 65 °C.

Rechargeable Sodium All-Solid-State Battery

PubMed Central

2017-01-01

A reversible plating/stripping of a dendrite-free metallic-sodium anode with a reduced anode/ceramic interfacial resistance is created by a thin interfacial interlayer formed in situ or by the introduction of a dry polymer film. Wetting of the sodium on the interfacial interlayer suppresses dendrite formation and growth at different discharge/charge C-rates. All-solid-state batteries were obtained with a high cycling stability and Coulombic efficiency at 65 °C. PMID:28149953

Substrate-induced interfacial plasmonics for photovoltaic conversion

PubMed Central

Li, Xinxi; Jia, Chuancheng; Ma, Bangjun; Wang, Wei; Fang, Zheyu; Zhang, Guoqing; Guo, Xuefeng

2015-01-01

Surface plasmon resonance (SPR) is widely used as light trapping schemes in solar cells, because it can concentrate light fields surrounding metal nanostructures and realize light management at the nanoscale. SPR in photovoltaics generally occurs at the metal/dielectric interfaces. A well-defined interface is therefore required to elucidate interfacial SPR processes. Here, we designed a photovoltaic device (PVD) with an atomically flat TiO2 dielectric/dye/graphene/metal nanoparticle (NP) interface for quantitatively studying the SPR enhancement of the photovoltaic conversion. Theoretical and experimental results indicated that the graphene monolayer was transparent to the electromagnetic field. This transparency led to significant substrate-induced plasmonic hybridization at the heterostructure interface. Combined with interparticle plasmonic coupling, the substrate-induced plasmonics concentrated light at the interface and enhanced the photo-excitation of dyes, thus improving the photoelectric conversion. Such a mechanistic understanding of interfacial plasmonic enhancement will further promote the development of efficient plasmon-enhanced solar cells and composite photocatalysts. PMID:26412576

Smart Capsules for Lead Removal from Industrial Wastewater.

PubMed

Tylkowski, Bartosz; Jastrząb, Renata

2017-04-10

Ground and especially drinking water could be contaminated by heavy metal ions such as lead and chromium, or the metalloid arsenic, discarded from industrial wastewater. These heavy metal ions are regarded as highly toxic pollutants which could cause a wide range of health problems in case of a long-term accumulation in the body. Thus, there have been many efforts to reduce the concentration of lead ions in effluent wastewater. They have included the establishment of stringent permissible discharge levels and management policies, the application of various pollution-control technologies, and the development of adsorbent materials for lead reduction. According to Science [1] encapsulation, developed approximately 65 years ago, has been defined as a major interdisciplinary research technology. Encapsulation has been used to deliver almost everything from advanced drugs to unique consumer sensory experiences. In this chapter we review the art of encapsulation technology as a potential breakthrough solution for a recyclable removal system for lead ions. Moreover, in order to provide the readers with a comprehensive and in-depth understanding of recent developments and innovative applications in this field, we highlight some remarkable advantages of encapsulation for heavy metal remove, such as simplicity of preparation, applicability for a wide range of selective extractants, large special interfacial area, ability for concentration of metal ions from dilute solutions, and less leakage of harmful components to the environment.

Interfacial Reaction During High Energy Ball Milling Dispersion of Carbon Nanotubes into Ti6Al4V

NASA Astrophysics Data System (ADS)

Adegbenjo, A. O.; Olubambi, P. A.; Potgieter, J. H.; Nsiah-Baafi, E.; Shongwe, M. B.

2017-12-01

The unique thermal and mechanical properties of carbon nanotubes (CNTs) have made them choice reinforcements for metal matrix composites (MMCs). However, there still remains a critical challenge in achieving homogeneous dispersion of CNTs in metallic matrices. Although high energy ball milling (HEBM) has been reported as an effective method of dispersing CNTs into metal matrices, a careful selection of the milling parameters is important not to compromise the structural integrity of CNTs which may cause interfacial reactions with the matrix. In this study, multi-walled carbon nanotubes (MWCNTs) were purified by annealing in argon and vacuum atmospheres at 1000 and 1800 °C, respectively, for 5 h to remove possible metallic catalyst impurities. Subsequently, 1, 2 and 3 wt.% MWCNTs were dispersed by adapted HEBM into Ti6Al4V alloy metal matrix. Raman spectroscopy (RS), x-ray diffraction, scanning electron microscopy, energy-dispersive x-ray spectrometry and transmission electron microscopy techniques were used to characterize the as-received and annealed MWCNTs, as well as the admixed MWCNT/Ti6Al4V nanocomposite powders. The experimental results showed that vacuum annealing successfully eliminated retained nickel (Ni) catalysts from MWCNTs, while the adapted HEBM method achieved a relative homogeneous dispersion of MWCNTs into the Ti6Al4V matrix and helped to control interfacial reactions between defective MWCNTs and the metal matrix.

Interfacial metal and antibody recognition.

PubMed

Zhou, Tongqing; Hamer, Dean H; Hendrickson, Wayne A; Sattentau, Quentin J; Kwong, Peter D

2005-10-11

The unique ligation properties of metal ions are widely exploited by proteins, with approximately one-third of all proteins estimated to be metalloproteins. Although antibodies use various mechanisms for recognition, to our knowledge, none has ever been characterized that uses an interfacial metal. We previously described a family of CD4-reactive antibodies, the archetype being Q425. CD4:Q425 engagement does not interfere with CD4:HIV-1 gp120 envelope glycoprotein binding, but it blocks subsequent steps required for viral entry. Here, we use surface-plasmon resonance to show that Q425 requires calcium for recognition of CD4. Specifically, Q425 binding of calcium resulted in a 55,000-fold enhancement in affinity for CD4. X-ray crystallographic analyses of Q425 in the presence of Ca(2+), Ba(2+), or EDTA revealed an exposed metal-binding site, partially coordinated by five atoms contributed from four antibody complementarity-determining regions. The results suggest that Q425 recognition of CD4 involves direct ligation of antigen by the Q425-held calcium, with calcium binding each ligating atom of CD4 with approximately 1.5 kcal/mol of binding energy. This energetic contribution, which is greater than that from a typical protein atom, demonstrates how interfacial metal ligation can play a unique role in antigen recognition.

Interfacial metal and antibody recognition

PubMed Central

Zhou, Tongqing; Hamer, Dean H.; Hendrickson, Wayne A.; Sattentau, Quentin J.; Kwong, Peter D.

2005-01-01

The unique ligation properties of metal ions are widely exploited by proteins, with approximately one-third of all proteins estimated to be metalloproteins. Although antibodies use various mechanisms for recognition, to our knowledge, none has ever been characterized that uses an interfacial metal. We previously described a family of CD4-reactive antibodies, the archetype being Q425. CD4:Q425 engagement does not interfere with CD4:HIV-1 gp120 envelope glycoprotein binding, but it blocks subsequent steps required for viral entry. Here, we use surface-plasmon resonance to show that Q425 requires calcium for recognition of CD4. Specifically, Q425 binding of calcium resulted in a 55,000-fold enhancement in affinity for CD4. X-ray crystallographic analyses of Q425 in the presence of Ca2+, Ba2+, or EDTA revealed an exposed metal-binding site, partially coordinated by five atoms contributed from four antibody complementarity-determining regions. The results suggest that Q425 recognition of CD4 involves direct ligation of antigen by the Q425-held calcium, with calcium binding each ligating atom of CD4 with ≈1.5 kcal/mol of binding energy. This energetic contribution, which is greater than that from a typical protein atom, demonstrates how interfacial metal ligation can play a unique role in antigen recognition. PMID:16195378

Interfacial Materials for Organic Solar Cells: Recent Advances and Perspectives

PubMed Central

Yin, Zhigang; Wei, Jiajun

2016-01-01

Organic solar cells (OSCs) have shown great promise as low‐cost photovoltaic devices for solar energy conversion over the past decade. Interfacial engineering provides a powerful strategy to enhance efficiency and stability of OSCs. With the rapid advances of interface layer materials and active layer materials, power conversion efficiencies (PCEs) of both single‐junction and tandem OSCs have exceeded a landmark value of 10%. This review summarizes the latest advances in interfacial layers for single‐junction and tandem OSCs. Electron or hole transporting materials, including metal oxides, polymers/small‐molecules, metals and metal salts/complexes, carbon‐based materials, organic‐inorganic hybrids/composites, and other emerging materials, are systemically presented as cathode and anode interface layers for high performance OSCs. Meanwhile, incorporating these electron‐transporting and hole‐transporting layer materials as building blocks, a variety of interconnecting layers for conventional or inverted tandem OSCs are comprehensively discussed, along with their functions to bridge the difference between adjacent subcells. By analyzing the structure–property relationships of various interfacial materials, the important design rules for such materials towards high efficiency and stable OSCs are highlighted. Finally, we present a brief summary as well as some perspectives to help researchers understand the current challenges and opportunities in this emerging area of research. PMID:27812480

Size-dependent single electron transfer and semi-metal-to-insulator transitions in molecular metal oxide electronics

NASA Astrophysics Data System (ADS)

Balliou, Angelika; Bouroushian, Mirtat; Douvas, Antonios M.; Skoulatakis, George; Kennou, Stella; Glezos, Nikos

2018-07-01

All-inorganic self-arranged molecular transition metal oxide hyperstructures based on polyoxometalate molecules (POMs) are fabricated and tested as electronically tunable components in emerging electronic devices. POM hyperstructures reveal great potential as charging nodes of tunable charging level for molecular memories and as enhancers of interfacial electron/hole injection for photovoltaic stacks. STM, UPS, UV–vis spectroscopy and AFM measurements show that this functionality stems from the films’ ability to structurally tune their HOMO–LUMO levels and electron localization length at room temperature. By adapting POM nanocluster size in solution, self-doping and current modulation of four orders of magnitude is monitored on a single nanocluster on SiO2 at voltages as low as 3 Volt. Structurally driven insulator-to-semi-metal transitions and size-dependent current regulation through single electron tunneling are demonstrated and examined with respect to the stereochemical and electronic structure of the molecular entities. This extends the value of self-assembly as a tool for correlation length and electronic properties tuning and demonstrate POM hyperstructures’ plausibility for on-chip molecular electronics operative at room temperature.

Size-dependent single electron transfer and semi-metal-to-insulator transitions in molecular metal oxide electronics.

PubMed

Balliou, Angelika; Bouroushian, Mirtat; Douvas, Antonios M; Skoulatakis, George; Kennou, Stella; Glezos, Nikos

2018-07-06

All-inorganic self-arranged molecular transition metal oxide hyperstructures based on polyoxometalate molecules (POMs) are fabricated and tested as electronically tunable components in emerging electronic devices. POM hyperstructures reveal great potential as charging nodes of tunable charging level for molecular memories and as enhancers of interfacial electron/hole injection for photovoltaic stacks. STM, UPS, UV-vis spectroscopy and AFM measurements show that this functionality stems from the films' ability to structurally tune their HOMO-LUMO levels and electron localization length at room temperature. By adapting POM nanocluster size in solution, self-doping and current modulation of four orders of magnitude is monitored on a single nanocluster on SiO 2 at voltages as low as 3 Volt. Structurally driven insulator-to-semi-metal transitions and size-dependent current regulation through single electron tunneling are demonstrated and examined with respect to the stereochemical and electronic structure of the molecular entities. This extends the value of self-assembly as a tool for correlation length and electronic properties tuning and demonstrate POM hyperstructures' plausibility for on-chip molecular electronics operative at room temperature.

Mechanistic insights from DGT and soil solution measurements on the uptake of Ni and Cd by radish.

PubMed

Luo, Jun; Cheng, Hao; Ren, Jinghua; Davison, William; Zhang, Hao

2014-07-01

This work tests the previously proposed hypothesis that plant uptake of metals is determined dominantly by diffusional controlled or plant limiting uptake mechanisms at, respectively, low and high metal concentrations. Radish (Raphanus sativus) was grown in 13 soils spiked with Ni (10 and 100 mg kg(-1)) and Cd (0.5 and 4 mg kg(-1)) for 4 weeks to investigate the mechanisms affecting plant uptake. Soil solution concentrations, Css, of Ni and Cd were measured, along with the DGT interfacial concentration, CDGT, and the derived effective concentration in soil solution, CE. Free ion activities, aNi(2+) and aCd(2+), were obtained using WHAM 6. Although there was a poor relationship between Ni in radish roots and either Css or aNi(2+) in unamended soils, the distribution of data could be rationalized in terms of the extent of release of Ni from the soil solid phase, as identified by DGT and soil solution measurements. By contrast Ni in radish was linearly related to CE, demonstrating diffusion limited uptake. For soils amended with high concentrations of Ni, linear relationships were obtained for Ni in radish plotted against, Css, aNi(2+), and CE, consistent with the plant controlling uptake. For Ni the hypothesis concerning dominant diffusional and plant limiting uptake mechanisms was demonstrated. Poor relationships between Cd in radish and Css, aCd(2+), and CE, irrespective of amendment by Cd, showed the importance of factors other than diffusional supply, such as rhizosphere and inhibitory processes, and that fulfilment of this hypothesis is plant and metal specific.

Enhanced Corrosion Resistance and Interfacial Conductivity of TiC x/a-C Nanolayered Coatings via Synergy of Substrate Bias Voltage for Bipolar Plates Applications in PEMFCs.

PubMed

Yi, Peiyun; Zhang, Weixin; Bi, Feifei; Peng, Linfa; Lai, Xinmin

2018-06-06

Proton-exchange membrane fuel cells are one kind of renewable and clean energy conversion device, whose metallic bipolar plates are one of the key components. However, high interfacial contact resistance and poor corrosion resistance are still great challenges for the commercialization of metallic bipolar plates. In this study, we demonstrated a novel strategy for depositing TiC x /amorphous carbon (a-C) nanolayered coatings by synergy of 60 and 300 V bias voltage to enhance corrosion resistance and interfacial conductivity. The synergistic effects of bias voltage on the composition, microstructure, surface roughness, electrochemical corrosion behaviors, and interfacial conductivity of TiC x /a-C coatings were explored. The results revealed that the columnar structures in the inner layer were suppressed and the surface became rougher with the 300 V a-C layer outside. The composition analysis indicated that the sp 2 content increased with an increase of 300 V sputtering time. Due to the synergy strategy of bias voltage, lower corrosion current densities were achieved both in potentiostatic polarization (1.6 V vs standard hydrogen electrode) and potentiodynamic polarization. With the increase of 300 V sputtering time, the interfacial conductivity was improved. The enhanced corrosion resistance and interfacial conductivity of the TiC x /a-C coatings would provide new opportunities for commercial bipolar plates.

Decreased Charge Transport Barrier and Recombination of Organic Solar Cells by Constructing Interfacial Nanojunction with Annealing-Free ZnO and Al Layers.

PubMed

Liu, Chunyu; Zhang, Dezhong; Li, Zhiqi; Zhang, Xinyuan; Guo, Wenbin; Zhang, Liu; Ruan, Shengping; Long, Yongbing

2017-07-05

To overcome drawbacks of the electron transport layer, such as complex surface defects and unmatched energy levels, we successfully employed a smart semiconductor-metal interfacial nanojunciton in organic solar cells by evaporating an ultrathin Al interlayer onto annealing-free ZnO electron transport layer, resulting in a high fill factor of 73.68% and power conversion efficiency of 9.81%. The construction of ZnO-Al nanojunction could effectively fill the surface defects of ZnO and reduce its work function because of the electron transfer from Al to ZnO by Fermi level equilibrium. The filling of surface defects decreased the interfacial carrier recombination in midgap trap states. The reduced surface work function of ZnO-Al remodulated the interfacial characteristics between ZnO and [6,6]-phenyl C71-butyric acid methyl ester (PC 71 BM), decreasing or even eliminating the interfacial barrier against the electron transport, which is beneficial to improve the electron extraction capacity. The filled surface defects and reduced interfacial barrier were realistically observed by photoluminescence measurements of ZnO film and the performance of electron injection devices, respectively. This work provides a simple and effective method to simultaneously solve the problems of surface defects and unmatched energy level for the annealing-free ZnO or other metal oxide semiconductors, paving a way for the future popularization in photovoltaic devices.

Isonitrile-functionalized ruthenium nanoparticles: intraparticle charge delocalization through Ru=C=N interfacial bonds

NASA Astrophysics Data System (ADS)

Zhang, Fengqi; Huang, Lin; Zou, Jiasui; Yang, Jun; Kang, Xiongwu; Chen, Shaowei

2017-09-01

Ruthenium nanoparticles (2.06 ± 0.46 nm in diameter) stabilized by 1-hexyl-4-isocyanobenzene (CNBH), denoted as RuCNBH, were prepared by the self-assembly of isonitrile molecules onto the surface of "bare" Ru colloids by virtue of the formation of Ru=C=N- interfacial bonds. FTIR measurements showed that the stretching vibration of the terminal -N≡C bonds at 2119 cm-1 for the monomeric ligands disappeared and concurrently three new bands at 2115, 2043, and 1944 cm-1 emerged with RuCNBH nanoparticles, which was ascribed to the transformation of -N≡C to Ru=C=N- by back donation of Ru-d electrons to the π* orbital of the organic ligands. Metathesis reaction of RuCNBH with vinyl derivatives further corroborated the nature of the Ru=C interfacial bonds. When 1-isocyanopyrene (CNPy) was bounded onto the Ru nanoparticles surface through Ru=C=N interfacial bond (denoted as RuCNPy), the emission maximum was found to red-shift by 27 nm, as compared to that of the CNPy monomers, along with a reduced fluorescence lifetime, due to intraparticle charge delocalization that arose from the conjugated Ru=C=N- interfacial bonds. The results of this study further underline the significance of metal-organic interfacial bonds in the control of intraparticle charge-transfer dynamics and the optical and electronic properties of metal nanoparticles. [Figure not available: see fulltext.

Effect of sucrose ester concentration on the interfacial characteristics and physical properties of sodium caseinate-stabilized oil-in-water emulsions.

PubMed

Zhao, Qiangzhong; Liu, Daolin; Long, Zhao; Yang, Bao; Fang, Min; Kuang, Wanmei; Zhao, Mouming

2014-05-15

The effect of sucrose ester (SE) concentration on interfacial tension and surface dilatational modulus of SE and sodium caseinate (NaCas)-SE solutions were investigated. The critical micelle concentration (CMC) of SE was presumed to be 0.05% by measuring interfacial tension of SE solution. The interfacial tension of NaCas-SE solution decreased with increased SE concentration. A sharp increase in surface dilatational modulus of NaCas solution was observed when 0.01% SE was added and a decline was occurred at higher SE level. The influence of SE concentration on droplet size and confocal micrograph, surface protein concentration, ζ-potential and rheological properties of oil-in-water (O/W) emulsions prepared with 1% NaCas was also examined. The results showed that addition of SE reduced droplet size and surface protein concentration of the O/W emulsions. The ζ-potential of the O/W emulsions increased initially and decreased afterward with increased SE concentration. All the O/W emulsions exhibited a shear-thinning behaviour and the data were well-fitted into the Herschel-Bulkley model. Copyright © 2013 Elsevier Ltd. All rights reserved.

Investigation of the wett-ability of various pure metals and alloys and beryllium

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

Gilliland, Ralph Gerald

1963-06-13

Thesis submitted to University of Tennessee, Knoxville. Activities in a program to determine the wetting behavior of pure metals such as Au, Ag, Ge, Al, and Cu on solid Be are reported. Results of similar investigations of binary alloys such as Be--Ti, Be-Zr, and Be--Pd are also included. The contact angles of the molten metals on Be as a function of temperature, exposure time, and atmosphere were measured. The solid-liquid interfacial reactions occurring as a function of test temperature and atmosphere were investigated, and the liquid- vapor and internal surface tensions for those systems in which interfacial reactions did notmore » appear to occur were calculated.« less

Mathematical modeling of liquid/liquid hollow fiber membrane contactor accounting for interfacial transport phenomena: Extraction of lanthanides as a surrogate for actinides

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

Rogers, J.D.

1994-08-04

This report is divided into two parts. The second part is divided into the following sections: experimental protocol; modeling the hollow fiber extractor using film theory; Graetz model of the hollow fiber membrane process; fundamental diffusive-kinetic model; and diffusive liquid membrane device-a rigorous model. The first part is divided into: membrane and membrane process-a concept; metal extraction; kinetics of metal extraction; modeling the membrane contactor; and interfacial phenomenon-boundary conditions-applied to membrane transport.

Interfacial oxide re-growth in thin film metal oxide III-V semiconductor systems

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

McDonnell, S.; Dong, H.; Hawkins, J. M.

2012-04-02

The Al{sub 2}O{sub 3}/GaAs and HfO{sub 2}/GaAs interfaces after atomic layer deposition are studied using in situ monochromatic x-ray photoelectron spectroscopy. Samples are deliberately exposed to atmospheric conditions and interfacial oxide re-growth is observed. The extent of this re-growth is found to depend on the dielectric material and the exposure temperature. Comparisons with previous studies show that ex situ characterization can result in misleading conclusions about the interface reactions occurring during the metal oxide deposition process.

Auger compositional depth profiling of the metal contact-TlBr interface

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Swanberg, E. L.; Voss, L. F.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Kim, H.; Cirignano, L.; Shah, K.

2015-08-01

Degradation of room temperature operation of TlBr radiation detectors with time is thought to be due to electromigration of Tl and Br vacancies within the crystal as well as the metal contacts migrating into the TlBr crystal itself due to electrochemical reactions at the metal/TlBr interface. Scanning Auger electron spectroscopy (AES) in combination with sputter depth profiling was used to investigate the metal contact surface/interfacial structure on TlBr devices. Device-grade TlBr was polished and subjected to a 32% HCl etch to remove surface damage and create a TlBr1-xClx surface layer prior to metal contact deposition. Auger compositional depth profiling results reveal non-equilibrium interfacial diffusion after device operation in both air and N2 at ambient temperature. These results improve our understanding of contact/device degradation versus operating environment for further enhancing radiation detector performance.

Biocompatibility evaluation of sputtered zirconium-based thin film metallic glass-coated steels.

PubMed

Subramanian, Balasubramanian; Maruthamuthu, Sundaram; Rajan, Senthilperumal Thanka

2015-01-01

Thin film metallic glasses comprised of Zr48Cu36Al8Ag8 (at.%) of approximately 1.5 μm and 3 μm in thickness were prepared using magnetron sputtering onto medical grade 316L stainless steel. Their structural and mechanical properties, in vitro corrosion, and antimicrobial activity were analyzed. The amorphous thin film metallic glasses consisted of a single glassy phase, with an absence of any detectable peaks corresponding to crystalline phases. Elemental composition close to the target alloy was noted from EDAX analysis of the thin film. The surface morphology of the film showed a smooth surface on scanning electron microscopy and atomic force microscopy. In vitro electrochemical corrosion studies indicated that the zirconium-based metallic glass could withstand body fluid, showing superior resistance to corrosion and electrochemical stability. Interactions between the coated surface and bacteria were investigated by agar diffusion, solution suspension, and wet interfacial contact methods. The results indicated a clear zone of inhibition against the growth of microorganisms such as Escherichia coli and Staphylococcus aureus, confirming the antimicrobial activity of the thin film metallic glasses. Cytotoxicity studies using L929 fibroblast cells showed these coatings to be noncytotoxic in nature.

Biocompatibility evaluation of sputtered zirconium-based thin film metallic glass-coated steels

PubMed Central

Subramanian, Balasubramanian; Maruthamuthu, Sundaram; Rajan, Senthilperumal Thanka

2015-01-01

Thin film metallic glasses comprised of Zr48Cu36Al8Ag8 (at.%) of approximately 1.5 μm and 3 μm in thickness were prepared using magnetron sputtering onto medical grade 316L stainless steel. Their structural and mechanical properties, in vitro corrosion, and antimicrobial activity were analyzed. The amorphous thin film metallic glasses consisted of a single glassy phase, with an absence of any detectable peaks corresponding to crystalline phases. Elemental composition close to the target alloy was noted from EDAX analysis of the thin film. The surface morphology of the film showed a smooth surface on scanning electron microscopy and atomic force microscopy. In vitro electrochemical corrosion studies indicated that the zirconium-based metallic glass could withstand body fluid, showing superior resistance to corrosion and electrochemical stability. Interactions between the coated surface and bacteria were investigated by agar diffusion, solution suspension, and wet interfacial contact methods. The results indicated a clear zone of inhibition against the growth of microorganisms such as Escherichia coli and Staphylococcus aureus, confirming the antimicrobial activity of the thin film metallic glasses. Cytotoxicity studies using L929 fibroblast cells showed these coatings to be noncytotoxic in nature. PMID:26491304

Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid.

PubMed

Yang, Chunpeng; Fu, Kun; Zhang, Ying; Hitz, Emily; Hu, Liangbing

2017-09-01

High-energy lithium-metal batteries are among the most promising candidates for next-generation energy storage systems. With a high specific capacity and a low reduction potential, the Li-metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li-metal anodes. Recent studies have shown that the performance and safety of Li-metal anodes can be significantly improved via organic electrolyte modification, Li-metal interface protection, Li-electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid-state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li-metal batteries. Inspired by the bright prospects of solid Li-metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li-metal batteries, such as low ionic conductivity of the electrolyte and Li-electrolyte interfacial problems. Here, the approaches to protect Li-metal anodes from liquid batteries to solid-state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li-metal anodes are discussed to facilitate the practical application of Li-metal batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interfacial activity in alkaline flooding enhanced oil recovery

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

Chan, M.K.

1981-01-01

The ionization of long-chained organic acids in the crude oil to form soaps was shown to be primarily responsible for the lowering of oil-water interfacial tension at alkaline pH. These active acids can be concentrated by silica gel chromatography into a minor polar fraction. An equilibrium chemical model was proposed based on 2 competing reactions: the ionization of acids to form active anions, and the formation of undissociated soap between acid anions and sodium ions. It correlates the interfacial activity with the interfacial concentration of active acid anions which is expressed in terms of the concentrations of the chemical speciesmore » in the system. The model successfully predicts the observed oil-alkaline solution interfacial phenomenon, including its dependence on pH, alkali and salt concentrations, type of acid present and type of soap formed. Flooding at different alkali concentrations to activate different acid species present in the crude was shown to give better recovery than flooding at a single high alkali concentration. Treating the crude oil with a dilute solution of mineral acids liberates additional free active acids and yields better interfacial activity during subsequent alkali contact.« less

Metallic nanoshells on porphyrin-stabilized emulsions

DOEpatents

Wang, Haorong; Song, Yujiang; Shelnutt, John A; Medforth, Craig J

2013-10-29

Metal nanostructures formed by photocatalytic interfacial synthesis using a porphyrin-stabilized emulsion template and the method for making the nanostructures. Catalyst-seeded emulsion droplets are employed as templates for hollow-nanoshell growth. The hollow metal nanospheres may be formed with or without inclusions of other materials.

The Au(111)/IL interfacial nanostructure in the presence of precursors and its influence on the electrodeposition process.

PubMed

Borisenko, Natalia; Lahiri, Abhishek; Pulletikurthi, Giridhar; Cui, Tong; Carstens, Timo; Zahlbach, Janine; Atkin, Rob; Endres, Frank

2018-01-01

Ionic liquids have attracted significant interest as electrolytes for the electrodeposition of metals and semiconductors, but the details of the deposition processes are not yet well understood. In this paper, we give an overview of how the addition of various precursors (TaF 5 , SiCl 4 , and GaCl 3 ) affects the solid/IL interfacial structure. In situ Atomic Force Microscopy (AFM) and vibrational spectroscopy have been employed to study the changes of the Au(111)/IL interface and in the electrolytes, respectively. Ionic liquids with the 1-butyl-1-methylpyrrolidinium ([Py 1,4 ] + ) cation and bis(trifluoromethylsulfonyl)amide ([TFSA] - ), trifluoromethylsulfonate ([TfO] - ) and tris(pentafluoroethyl)trifluorophosphate ([FAP] - ) as anions were chosen for this purpose. In situ AFM force-distance measurements reveal that both the anion of the IL and the solutes (TaF 5 or GaCl 3 ) influence the Electrical Double Layer (EDL) structure of the Au(111)/IL interface, which can affect the deposition process of Ta and the morphology of the Ga electrodeposits, respectively. Furthermore, the concentration of the precursor can significantly alter the Au(111)/[Py 1,4 ][FAP]-SiCl 4 interfacial structure wherein the presence of 0.25 M SiCl 4 a double layer structure forms that facilitates Si deposition. This study may provide some critical insights into the structure of the electrode/IL interface for specific applications.

Effects of Gibbs free energy of interfacial metal oxide on resistive switching characteristics of solution-processed HfOx films

NASA Astrophysics Data System (ADS)

Hsu, Chih-Chieh; Sun, Jhen-Kai; Tsao, Che-Chang; Chuang, Po-Yang

2017-08-01

Effects of bottom electrodes (BEs) of Al, Mo, and Pt on resistive switching characteristics of sol-gel HfOx films were investigated in this work. To avoid influences of plasma or thermal energy on HfOx RS characteristic, the top electrodes were formed by pressing indium balls onto the HfOx surface rather than by using a sputter or an evaporator. When using Mo as the BE, the as-deposited HfOx film can give a forming-free resistive switching behavior with low set/reset voltages of 0.28 V / - 0.54 V. In contrast, non-switching characteristics of the HfOx films were observed when using Al and Pt as the BEs. The HfOx conduction current was found to be highly dependent on the BE. However, when an annealing process at 350 °C in an oxygen ambient was performed to the HfOx films on different BEs, the resistive switching behavior of the HfOx/Mo was absent while it can be found in the HfOx/Al sample. Differences in I-V characteristics of the HfOx films on different BEs were explained by considering Gibbs free energies of interfacial oxide layers. X-ray photoelectron spectroscopy (XPS) depth profile was used to examine the interfacial oxide layer. The resistive switching mechanism was also studied.

Measurement of dielectric constant of organic solvents by indigenously developed dielectric probe

NASA Astrophysics Data System (ADS)

Keshari, Ajay Kumar; Rao, J. Prabhakar; Rao, C. V. S. Brahmmananda; Ramakrishnan, R.; Ramanarayanan, R. R.

2018-04-01

The extraction, separation and purification of actinides (uranium and plutonium) from various matrices are an important step in nuclear fuel cycle. One of the separation process adopted in an industrial scale is the liquid-liquid extraction or solvent extraction. Liquid-liquid extraction uses a specific ligand/extractant in conjunction with suitable diluent. Solvent extraction or liquid-liquid extraction, involves the partitioning of the solute between two immiscible phases. In most cases, one of the phases is aqueous, and the other one is an organic solvent. The solvent used in solvent extraction should be selective for the metal of interest, it should have optimum distribution ratio, and the loaded metal from the organic phase should be easily stripped under suitable experimental conditions. Some of the important physical properties which are important for the solvent are density, viscosity, phase separation time, interfacial surface tension and the polarity of the extractant.

Rational composition control of mixed-lanthanide metal-organic frameworks by an interfacial reaction with metal ion-doped polymer substrates

NASA Astrophysics Data System (ADS)

Tsuruoka, Takaaki; Miyanaga, Ayumi; Ohhashi, Takashi; Hata, Manami; Takashima, Yohei; Akamatsu, Kensuke

2017-09-01

A simple composition control route to mixed-lanthanide metal-organic frameworks (MOFs) was developed based on an interfacial reaction with mixed-lanthanide metal ion-doped polymer substrates. By controlling the composition of lanthanide ion (Eu3+ and Tb3+) dopants in polymer substrates to be used as metal ion precursors and scaffolding for the formation of MOFs, [EuxTb2-x(bdc)3(H2O)4]n crystals with a tunable metal composition could be routinely prepared on polymer substrates. Inductively coupled plasma (ICP) measurements revealed that the composition of the obtained frameworks was almost the same as that of the initial polymer substrates. In addition, the resulting [EuxTb2-x(bdc)3(H2O)4]n crystals showed strong phosphorescence because of Eu3+ transitions, indicating that the energy transfer from Tb3+ to Eu3+ ions in the frameworks could be achieved with high efficiency.

Interfacial dilatational deformation accelerates particle formation in monoclonal antibody solutions.

PubMed

Lin, Gigi L; Pathak, Jai A; Kim, Dong Hyun; Carlson, Marcia; Riguero, Valeria; Kim, Yoen Joo; Buff, Jean S; Fuller, Gerald G

2016-04-14

Protein molecules are amphiphilic moieties that spontaneously adsorb at the air/solution (A/S) interface to lower the surface energy. Previous studies have shown that hydrodynamic disruptions to these A/S interfaces can result in the formation of protein aggregates that are of concern to the pharmaceutical industry. Interfacial hydrodynamic stresses encountered by protein therapeutic solutions under typical manufacturing, filling, and shipping conditions will impact protein stability, prompting a need to characterize the contribution of basic fluid kinematics to monoclonal antibody (mAb) destabilization. We demonstrate that dilatational surface deformations are more important to antibody stability when compared to constant-area shear of the A/S interface. We have constructed a dilatational interfacial rheometer that utilizes simultaneous pressure and bubble shape measurements to study the mechanical stability of mAbs under interfacial aging. It has a distinct advantage over methods utilizing the Young-Laplace equation, which incorrectly describes viscoelastic interfaces. We provide visual evidence of particle ejection from dilatated A/S interfaces and spectroscopic data of ejected mAb particles. These rheological studies frame a molecular understanding of the protein-protein interactions at the complex-fluid interface.

Passivation of GaSb using molecular beam epitaxy Y{sub 2}O{sub 3} to achieve low interfacial trap density and high-performance self-aligned inversion-channel p-metal-oxide-semiconductor field-effect-transistors

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

Chu, R. L.; Chiang, T. H.; Hsueh, W. J.

2014-11-03

Molecular beam epitaxy deposited rare-earth oxide of Y{sub 2}O{sub 3} has effectively passivated GaSb, leading to low interfacial trap densities of (1–4) × 10{sup 12 }cm{sup −2} eV{sup −1} across the energy bandgap of GaSb. A high saturation drain current density of 130 μA/μm, a peak transconductance of 90 μS/μm, a low subthreshold slope of 147 mV/decade, and a peak field-effect hole mobility of 200 cm{sup 2}/V-s were obtained in 1 μm-gate-length self-aligned inversion-channel GaSb p-Metal-Oxide-Semiconductor Field-Effect-Transistors (MOSFETs). In this work, high-κ/GaSb interfacial properties were better in samples with a high substrate temperature of 200 °C than in those with high κ's deposited at room temperature, in terms of themore » interfacial electrical properties, particularly, the reduction of interfacial trap densities near the conduction band and the MOSFET device performance.« less

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Comprehensive studies of interfacial strain and oxygen vacancy on metal-insulator transition of VO2 film

NASA Astrophysics Data System (ADS)

Fan, L. L.; Chen, S.; Liao, G. M.; Chen, Y. L.; Ren, H.; Zou, C. W.

2016-06-01

As a typical strong correlation material, vanadium dioxide (VO2) has attracted wide interest due to its particular metal-insulator transition (MIT) property. However, the relatively high critical temperature (T c) of ~68 °C seriously hinders its practical applications. Thus modulating the phase transition process and decreasing the T c close to room temperature have been hot topics for VO2 study. In the current work, we conducted a multi-approach strategy to control the phase transition of VO2 films, including the interfacial tensile/compressive strain and oxygen vacancies. A synchrotron radiation reciprocal space mapping technique was used to directly record the interfacial strain evolution and variations of lattice parameters. The effects of interfacial strain and oxygen vacancies in the MIT process were systematically investigated based on band structure and d-orbital electron occupation. It was suggested that the MIT behavior can be modulated through the combined effects of the interfacial strain and oxygen vacancies, achieving the distinct phase transition close to room temperature. The current findings not only provide better understanding for strain engineering and oxygen vacancies controlling phase transition behavior, but also supply a combined way to control the phase transition of VO2 film, which is essential for VO2 film based device applications in the future.

Comprehensive studies of interfacial strain and oxygen vacancy on metal-insulator transition of VO2 film.

PubMed

Fan, L L; Chen, S; Liao, G M; Chen, Y L; Ren, H; Zou, C W

2016-06-29

As a typical strong correlation material, vanadium dioxide (VO2) has attracted wide interest due to its particular metal-insulator transition (MIT) property. However, the relatively high critical temperature (T c) of ~68 °C seriously hinders its practical applications. Thus modulating the phase transition process and decreasing the T c close to room temperature have been hot topics for VO2 study. In the current work, we conducted a multi-approach strategy to control the phase transition of VO2 films, including the interfacial tensile/compressive strain and oxygen vacancies. A synchrotron radiation reciprocal space mapping technique was used to directly record the interfacial strain evolution and variations of lattice parameters. The effects of interfacial strain and oxygen vacancies in the MIT process were systematically investigated based on band structure and d-orbital electron occupation. It was suggested that the MIT behavior can be modulated through the combined effects of the interfacial strain and oxygen vacancies, achieving the distinct phase transition close to room temperature. The current findings not only provide better understanding for strain engineering and oxygen vacancies controlling phase transition behavior, but also supply a combined way to control the phase transition of VO2 film, which is essential for VO2 film based device applications in the future.

Amorphous Mixed-Metal Oxide Thin Films from Aqueous Solution Precursors with Near-Atomic Smoothness.

PubMed

Kast, Matthew G; Cochran, Elizabeth A; Enman, Lisa J; Mitchson, Gavin; Ditto, Jeffrey; Siefe, Chris; Plassmeyer, Paul N; Greenaway, Ann L; Johnson, David C; Page, Catherine J; Boettcher, Shannon W

2016-12-28

Thin films with tunable and homogeneous composition are required for many applications. We report the synthesis and characterization of a new class of compositionally homogeneous thin films that are amorphous solid solutions of Al 2 O 3 and transition metal oxides (TMO x ) including VO x , CrO x , MnO x , Fe 2 O 3 , CoO x , NiO, CuO x , and ZnO. The synthesis is enabled by the rapid decomposition of molecular transition-metal nitrates TM(NO 3 ) x at low temperature along with precondensed oligomeric Al(OH) x (NO 3 ) 3-x cluster species, both of which can be processed from aq solution. The films are dense, ultrasmooth (R rms < 1 nm, near 0.1 nm in many cases), and atomically mixed amorphous metal-oxide alloys over a large composition range. We assess the chemical principles that favor the formation of amorphous homogeneous films over rougher phase-segregated nanocrystalline films. The synthesis is easily extended to other compositions of transition and main-group metal oxides. To demonstrate versatility, we synthesized amorphous V 0.1 Cr 0.1 Mn 0.1 Fe 0.1 Zn 0.1 Al 0.5 O x and V 0.2 Cr 0.2 Fe 0.2 Al 0.4 O x with R rms ≈ 0.1 nm and uniform composition. The combination of ideal physical properties (dense, smooth, uniform) and broad composition tunability provides a platform for film synthesis that can be used to study fundamental phenomena when the effects of transition metal cation identity, solid-state concentration of d-electrons or d-states, and/or crystallinity need to be controlled. The new platform has broad potential use in controlling interfacial phenomena such as electron transfer in solar-cell contacts or surface reactivity in heterogeneous catalysis.

Structure that encapsulates lithium metal for high energy density battery anode

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

Cui, Yi; Yan, Kai; Chu, Steven

A battery includes 1) an anode, 2) a cathode, and 3) an electrolyte disposed between the anode and the cathode. The anode includes a current collector and an interfacial layer disposed over the current collector, and the interfacial layer includes an array of interconnected, protruding regions that define spaces.

Plasmonic engineering of metal-oxide nanowire heterojunctions in integrated nanowire rectification units

NASA Astrophysics Data System (ADS)

Lin, Luchan; Zou, Guisheng; Liu, Lei; Duley, Walt W.; Zhou, Y. Norman

2016-05-01

We show that irradiation with femtosecond laser pulses can produce robust nanowire heterojunctions in coupled non-wetting metal-oxide Ag-TiO2 structures. Simulations indicate that joining arises from the effect of strong plasmonic localization in the region of the junction. Strong electric field effects occur in both Ag and TiO2 resulting in the modification of both surfaces and an increase in wettability of TiO2, facilitating the interconnection of Ag and TiO2 nanowires. Irradiation leads to the creation of a thin layer of highly defected TiO2 in the contact region between the Ag and TiO2 nanowires. The presence of this layer allows the formation of a heterojunction and offers the possibility of engineering the electronic characteristics of interfacial structures. Rectifying junctions with single and bipolar properties have been generated in Ag-TiO2 nanowire circuits incorporating asymmetrical and symmetrical interfacial structures, respectively. This fabrication technique should be applicable for the interconnection of other heterogeneous metal-oxide nanowire components and demonstrates that femtosecond laser irradiation enables interfacial engineering for electronic applications of integrated nanowire structures.

Asymmetrical interfacial reactions of Ni/SAC101(NiIn)/Ni solder joint induced by current stressing

NASA Astrophysics Data System (ADS)

Lin, Chen-Yi; Chiu, Tsung-Chieh; Lin, Kwang-Lung

2018-03-01

An electric current can asymmetrically trigger either atomic migration or interfacial reactions between a cathode and an anode. The present study investigated the dissolution of metallization and formation of an interfacial intermetallic compound (IMC) in the Cu/Ni/Sn1.0Ag0.1Cu0.02Ni0.05In/Ni/Cu solder joint at various current densities in the order of 103 A/cm2 at temperatures ranging from 100 °C to 150 °C. The polarization behavior of Ni dissolution and IMC formation under current stressing were systematically investigated. The asymmetrical interfacial reactions of the solder joint were found to be greatly influenced by ambient temperature. The dissolution of Ni and its effect on interfacial IMC formation were also discussed.

Evaluation of physics-based numerical modelling for diverse design architecture of perovskite solar cells

NASA Astrophysics Data System (ADS)

Mishra, A. K.; Catalan, Jorge; Camacho, Diana; Martinez, Miguel; Hodges, D.

2017-08-01

Solution processed organic-inorganic metal halide perovskite based solar cells are emerging as a new cost effective photovoltaic technology. In the context of increasing the power conversion efficiency (PCE) and sustainability of perovskite solar cells (PSC) devices, we comprehensively analyzed a physics-based numerical modelling for doped and un-doped PSC devices. Our analytics emphasized the role of different charge carrier layers from the view point of interfacial adhesion and its influence on charge extraction rate and charge recombination mechanism. Morphological and charge transport properties of perovskite thin film as a function of device architecture are also considered to investigate the photovoltaic properties of PSC. We observed that photocurrent is dominantly influenced by interfacial recombination process and photovoltage has functional relationship with defect density of perovskite absorption layer. A novel contour mapping method to understand the characteristics of current density-voltage (J-V) curves for each device as a function of perovskite layer thickness provide an important insight about the distribution spectrum of photovoltaic properties. Functional relationship of device efficiency and fill factor with absorption layer thickness are also discussed.

Anomalous positive flatband voltage shifts in metal gate stacks containing rare-earth oxide capping layers

NASA Astrophysics Data System (ADS)

Caraveo-Frescas, J. A.; Hedhili, M. N.; Wang, H.; Schwingenschlögl, U.; Alshareef, H. N.

2012-03-01

It is shown that the well-known negative flatband voltage (VFB) shift, induced by rare-earth oxide capping in metal gate stacks, can be completely reversed in the absence of the silicon overlayer. Using TaN metal gates and Gd2O3-doped dielectric, we measure a ˜350 mV negative shift with the Si overlayer present and a ˜110 mV positive shift with the Si overlayer removed. This effect is correlated to a positive change in the average electrostatic potential at the TaN/dielectric interface which originates from an interfacial dipole. The dipole is created by the replacement of interfacial oxygen atoms in the HfO2 lattice with nitrogen atoms from TaN.

Schottky barrier at graphene/metal oxide interfaces: insight from first-principles calculations

NASA Astrophysics Data System (ADS)

Cheng, Kai; Han, Nannan; Su, Yan; Zhang, Junfeng; Zhao, Jijun

2017-02-01

Anode materials play an important role in determining the performance of lithium ion batteries. In experiment, graphene (GR)/metal oxide (MO) composites possess excellent electrochemical properties and are promising anode materials. Here we perform density functional theory calculations to explore the interfacial interaction between GR and MO. Our result reveals generally weak physical interactions between GR and several MOs (including Cu2O, NiO). The Schottky barrier height (SBH) in these metal/semiconductor heterostructures are computed using the macroscopically averaged electrostatic potential method, and the role of interfacial dipole is discussed. The calculated SBHs below 1 eV suggest low contact resistance; thus these GR/MO composites are favorable anode materials for better lithium ion batteries.

Schottky barrier at graphene/metal oxide interfaces: insight from first-principles calculations.

PubMed

Cheng, Kai; Han, Nannan; Su, Yan; Zhang, Junfeng; Zhao, Jijun

2017-02-06

Anode materials play an important role in determining the performance of lithium ion batteries. In experiment, graphene (GR)/metal oxide (MO) composites possess excellent electrochemical properties and are promising anode materials. Here we perform density functional theory calculations to explore the interfacial interaction between GR and MO. Our result reveals generally weak physical interactions between GR and several MOs (including Cu2O, NiO). The Schottky barrier height (SBH) in these metal/semiconductor heterostructures are computed using the macroscopically averaged electrostatic potential method, and the role of interfacial dipole is discussed. The calculated SBHs below 1 eV suggest low contact resistance; thus these GR/MO composites are favorable anode materials for better lithium ion batteries.

Reduced Capillary Length Scale in the Application of Ostwald Ripening Theory to the Coarsening of Charged Colloidal Crystals in Electrolyte Solutions

NASA Astrophysics Data System (ADS)

Rowe, Jeffrey D.; Baird, James K.

2007-06-01

A colloidal crystal suspended in an electrolyte solution will ordinarily exchange ions with the surrounding solution and develop a net surface charge density and a corresponding double layer. The interfacial tension of the charged surface has contributions arising from: (a) background interfacial tension of the uncharged surface, (b) the entropy associated with the adsorption of ions on the surface, and (c) the polarizing effect of the electrostatic field within the double layer. The adsorption and polarization effects make negative contributions to the surface free energy and serve to reduce the interfacial tension below the value to be expected for the uncharged surface. The diminished interfacial tension leads to a reduced capillary length scale. According to the Ostwald ripening theory of particle coarsening, the reduced capillary length will cause the solute supersaturation to decay more rapidly and the colloidal particles to be smaller in size and greater in number than in the absence of the double layer. Although the length scale for coarsening should be little affected in the case of inorganic colloids, such as AgI, it should be greatly reduced in the case of suspensions of protein crystals, such as apoferritin, catalase, and thaumatin.

Synthesis of metallic nanoshells on porphyrin-stabilized emulsions

DOEpatents

Wang, Haorong [Albuquerque, NM; Song, Yujiang [Albuquerque, NM; Shelnutt, John A [Tijeras, NM; Medforth, Craig J [Winters, CA

2011-12-13

Metal nanostructures formed by photocatalytic interfacial synthesis using a porphyrin-stabilized emulsion template and the method for making the nanostructures. Catalyst-seeded emulsion droplets are employed as templates for hollow-nanoshell growth. The hollow metal nanospheres may be formed with or without inclusions of other materials.

Effects of metallic nanoparticle doped flux on the interfacial intermetallic compounds between lead-free solder ball and copper substrate

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

Sujan, G.K., E-mail: sgkumer@gmail.com; Haseeb, A.S.M.A., E-mail: haseeb@um.edu.my; Afifi, A.B.M., E-mail: amalina@um.edu.my

2014-11-15

Lead free solders currently in use are prone to develop thick interfacial intermetallic compound layers with rough morphology which are detrimental to the long term solder joint reliability. A novel method has been developed to control the morphology and growth of intermetallic compound layers between lead-free Sn–3.0Ag–0.5Cu solder ball and copper substrate by doping a water soluble flux with metallic nanoparticles. Four types of metallic nanoparticles (nickel, cobalt, molybdenum and titanium) were used to investigate their effects on the wetting behavior and interfacial microstructural evaluations after reflow. Nanoparticles were dispersed manually with a water soluble flux and the resulting nanoparticlemore » doped flux was placed on copper substrate. Lead-free Sn–3.0Ag–0.5Cu solder balls of diameter 0.45 mm were placed on top of the flux and were reflowed at a peak temperature of 240 °C for 45 s. Angle of contact, wetting area and interfacial microstructure were studied by optical microscopy, field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. It was observed that the angle of contact increased and wetting area decreased with the addition of cobalt, molybdenum and titanium nanoparticles to flux. On the other hand, wettability improved with the addition of nickel nanoparticles. Cross-sectional micrographs revealed that both nickel and cobalt nanoparticle doping transformed the morphology of Cu{sub 6}Sn{sub 5} from a typical scallop type to a planer one and reduced the intermetallic compound thickness under optimum condition. These effects were suggested to be related to in-situ interfacial alloying at the interface during reflow. The minimum amount of nanoparticles required to produce the planer morphology was found to be 0.1 wt.% for both nickel and cobalt. Molybdenum and titanium nanoparticles neither appear to undergo alloying during reflow nor have any influence at the solder/substrate interfacial reaction. Thus, doping of flux with appropriate metallic nanoparticles can be successfully used to control the morphology and growth of intermetallic compound layers at the solder/substrate interface which is expected to lead to better reliability of electronic devices. - Highlights: • A novel nanodoped flux method has been developed to control the growth of IMCs. • Ni doped flux improves the wettability, but Co, Mo and Ti deteriorate it. • Ni and Co doped flux gives planer IMC morphology through in-situ alloying effect. • 0.1 wt.% Ni and Co addition into flux gives the lowest interfacial IMC thickness. • Mo and Ti doped flux does not have any influence at the interfacial reaction.« less

Dynamic Stabilization of Metal Oxide–Water Interfaces

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

McBriarty, Martin E.; von Rudorff, Guido Falk; Stubbs, Joanne E.

2017-02-08

The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe2O3) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the structure of the (1102) termination is dynamically stabilized by picosecond water exchange. Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locationsmore » and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies. Frequent water exchange occurs even for an ultrathin adsorbed water film persisting on the surface under a dry atmosphere. The resulting time-averaged interfacial structure consists of a ridged lateral arrangement of adsorbed water molecules hydrogen bonded to terminal aquo groups. Surface pKa prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface. Our findings provide important new insights for understanding complex interfacial chemical processes at metal oxide–water interfaces.« less

Effect of Concentration on the Interfacial and Bulk Structure of Ionic Liquids in Aqueous Solution.

PubMed

Cheng, H-W; Weiss, H; Stock, P; Chen, Y-J; Reinecke, C R; Dienemann, J-N; Mezger, M; Valtiner, M

2018-02-27

Bio and aqueous applications of ionic liquids (IL) such as catalysis in micelles formed in aqueous IL solutions or extraction of chemicals from biologic materials rely on surface-active and self-assembly properties of ILs. Here, we discuss qualitative relations of the interfacial and bulk structuring of a water-soluble surface-active IL ([C 8 MIm][Cl]) on chemically controlled surfaces over a wide range of water concentrations using both force probe and X-ray scattering experiments. Our data indicate that IL structuring evolves from surfactant-like surface adsorption at low IL concentrations, to micellar bulk structure adsorption above the critical micelle concentration, to planar bilayer formation in ILs with <1 wt % of water and at high charging of the surface. Interfacial structuring is controlled by mesoscopic bulk structuring at high water concentrations. Surface chemistry and surface charges decisively steer interfacial ordering of ions if the water concentration is low and/or the surface charge is high. We also demonstrate that controlling the interfacial forces by using self-assembled monolayer chemistry allows tuning of interfacial structures. Both the ratio of the head group size to the hydrophobic tail volume as well as the surface charging trigger the bulk structure and offer a tool for predicting interfacial structures. Based on the applied techniques and analyses, a qualitative prediction of molecular layering of ILs in aqueous systems is possible.

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

PubMed Central

Liu, Yayuan; Lin, Dingchang; Jin, Yang; Liu, Kai; Tao, Xinyong; Zhang, Qiuhong; Zhang, Xiaokun; Cui, Yi

2017-01-01

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellent adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g−1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm−2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature. PMID:29062894

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

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

Liu, Yayuan; Lin, Dingchang; Jin, Yang

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellentmore » adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g -1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm -2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature.« less

An insight into intrinsic interfacial properties between Li metals and Li10GeP2S12 solid electrolytes.

PubMed

Chen, Bingbing; Ju, Jiangwei; Ma, Jun; Zhang, Jianjun; Xiao, Ruijuan; Cui, Guanglei; Chen, Liquan

2017-11-29

Density functional theory simulations and experimental studies were performed to investigate the interfacial properties, including lithium ion migration kinetics, between lithium metal anode and solid electrolyte Li 10 GeP 2 S 12 (LGPS). The LGPS[001] plane was chosen as the studied surface because the easiest Li + migration pathway is along this direction. The electronic structure of the surface states indicated that the electrochemical stability was reduced at both the PS 4 - and GeS 4 -teminated surfaces. For the interface cases, the equilibrium interfacial structures of lithium metal against the PS 4 -terminated LGPS[001] surface (Li/PS 4 -LGPS) and the GeS 4 -terminated LGPS[001] surface (Li/GeS 4 -LGPS) were revealed based on the structural relaxation and adhesion energy analysis. Solid electrolyte interphases were expected to be formed at both Li/PS 4 -LGPS and Li/GeS 4 -LGPS interfaces, resulting in an unstable state of interface and large interfacial resistance, which was verified by the EIS results of the Li/LGPS/Li cell. In addition, the simulations of the migration kinetics show that the energy barriers for Li + crossing the Li/GeS 4 -LGPS interface were relatively low compared with the Li/PS 4 -LGPS interface. This may contribute to the formation of Ge-rich phases at the Li/LGPS interface, which can tune the interfacial structures to improve the ionic conductivity for future all-solid-state batteries. This work will offer a thorough understanding of the Li/LGPS interface, including local structures, electronic states and Li + diffusion behaviors in all-solid-state batteries.

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

DOE PAGES

Liu, Yayuan; Lin, Dingchang; Jin, Yang; ...

2017-10-01

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellentmore » adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g -1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm -2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature.« less

Tunneling Anomalous and Spin Hall Effects.

PubMed

Matos-Abiague, A; Fabian, J

2015-07-31

We predict, theoretically, the existence of the anomalous Hall effect when a tunneling current flows through a tunnel junction in which only one of the electrodes is magnetic. The interfacial spin-orbit coupling present in the barrier region induces a spin-dependent momentum filtering in the directions perpendicular to the tunneling current, resulting in a skew tunneling even in the absence of impurities. This produces an anomalous Hall conductance and spin Hall currents in the nonmagnetic electrode when a bias voltage is applied across the tunneling heterojunction. If the barrier is composed of a noncentrosymmetric material, the anomalous Hall conductance and spin Hall currents become anisotropic with respect to both the magnetization and crystallographic directions, allowing us to separate this interfacial phenomenon from the bulk anomalous and spin Hall contributions. The proposed effect should be useful for proving and quantifying the interfacial spin-orbit fields in metallic and metal-semiconductor systems.

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.

Interfacial Control of Dzyaloshinskii-Moriya Interaction in Heavy Metal/Ferromagnetic Metal Thin Film Heterostructures

NASA Astrophysics Data System (ADS)

Ma, Xin; Yu, Guoqiang; Li, Xiang; Wang, Tao; Wu, Di; Olsson, Kevin; Chu, Zhaodong; An, Kyongmo; Xiao, John; Wang, Kang; Li, Xiaoqin

The interfacial Dzyaloshinskii-Moriya Interaction (DMI) in ultrathin magnetic thin film heterostructures provides a new approach for controlling spin textures on mesoscopic length scales. Here we investigate the dependence of the interfacial DMI constant D on a Pt wedge insertion layer in Ta/CoFeB/Pt(wedge)/MgO thin films by observing the asymmetric spin wave dispersion using Brillouin light scattering. Continuous tuning of D by more than a factor of three is realized by inserting less than one monolayer of Pt. The observations provide new insights for designing magnetic thin film heterostructures with tailored D for controlling skyrmions and magnetic domain wall chirality and dynamics. The work at UT-Austin and UCLA are supported by SHINES, an Energy Frontier Research Center funded by the U.S. DoE, Office of Science, Basic Energy Science (BES) under award # DE-SC0012670.

Detrimental effect of interfacial Dzyaloshinskii-Moriya interaction on perpendicular spin-transfer-torque magnetic random access memory

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

Jang, Peong-Hwa; Lee, Seo-Won, E-mail: swlee-sci@korea.ac.kr, E-mail: kj-lee@korea.ac.kr; Song, Kyungmi

2015-11-16

Interfacial Dzyaloshinskii-Moriya interaction in ferromagnet/heavy metal bilayers is recently of considerable interest as it offers an efficient control of domain walls and the stabilization of magnetic skyrmions. However, its effect on the performance of perpendicular spin transfer torque memory has not been explored yet. We show based on numerical studies that the interfacial Dzyaloshinskii-Moriya interaction decreases the thermal energy barrier while increases the switching current. As high thermal energy barrier as well as low switching current is required for the commercialization of spin torque memory, our results suggest that the interfacial Dzyaloshinskii-Moriya interaction should be minimized for spin torque memorymore » applications.« less

Atomic structure and bonding of the interfacial bilayer between Au nanoparticles and epitaxially regrown MgAl{sub 2}O{sub 4} substrates

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

Zhu, Guo-zhen; Canadian Centre of Electron Microscopy and Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario L8S 4M1; Majdi, Tahereh

2014-12-08

A unique metal/oxide interfacial bilayer formed between Au nanoparticles and MgAl{sub 2}O{sub 4} substrates following thermal treatment is reported. Associated with the formation of the bilayer was the onset of an abnormal epitaxial growth of the substrate under the nanoparticle. According to the redistribution of atoms and the changes of their electronic structure probed across the interface by a transmission electron microscopy, we suggest two possible atomic models of the interfacial bilayer.

Submicroporous/microporous and compatible/incompatible multi-functional dual-layer polymer electrolytes and their interfacial characteristics with lithium metal anode

NASA Astrophysics Data System (ADS)

Lee, Young-Gi; Kyhm, Kwangseuk; Choi, Nam-Soon; Ryu, Kwang Sun

A novel multi-functional dual-layer polymer electrolyte was prepared by impregnating the interconnected pores with an ethylene carbonate (EC)/dimethyl carbonate (DMC)/lithium hexafluorophosphate (LiPF 6) solution. An incompatible layer is based on a microporous polyethylene (PE) and a compatible layer, based on a poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) is sub-microporous and compatible with an electrolyte solution. The Li electrode/the dual-layer polymer electrolyte/Li[Ni 0.15Li 0.23M n0.62]O 2 cell showed stable cycle performance under prolonged cycle number. This behavior is due to the enhanced compatibility between the matrix polymer and the liquid electrolytes within the submicroporous compatible layer, which could lead to a controlled Li + deposition on the Li anode surface by forming homegeneous electrolyte zone near the anode.

Evaluating the Role of the Air-Solution Interface on the Mechanism of Subvisible Particle Formation Caused by Mechanical Agitation for an IgG1 mAb.

PubMed

Ghazvini, Saba; Kalonia, Cavan; Volkin, David B; Dhar, Prajnaparamita

2016-05-01

Mechanical agitation of monoclonal antibody (mAb) solutions often leads to protein particle formation. In this study, various formulations of an immunoglobulin G (IgG) 1 mAb were subjected to different controlled interfacial stresses using a Langmuir trough, and protein particles formed at the interface and measured in bulk solution were characterized using atomic force microscopy and flow digital imaging. Results were compared to mAb solutions agitated in glass vials and unstressed controls. At lower pH, mAb solutions exhibited larger hysteresis in their surface pressure versus area isotherms and increased number of particles in bulk solution, when subjected to interfacial stresses. mAb samples subjected to 750-1000 interfacial compression-expansion cycles in 6 h contained high particle numbers in bulk solution, and displayed similar particulation trends when agitated in vials. At compression rates of 50 cycles in 6 h, however, particle levels in mAb solutions were comparable to unstressed controls, despite protein aggregates being present at the air-solution interface. These results suggest that while the air-solution interface serves as a nucleation site for initiating protein aggregation, the number of protein particles measured in bulk mAb solutions depends on the total number of compression cycles that proteins at the air-solution interface are subjected to within a fixed time. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Influence of interfacial viscosity on the dielectrophoresis of drops

NASA Astrophysics Data System (ADS)

Mandal, Shubhadeep; Chakraborty, Suman

2017-05-01

The dielectrophoresis of a Newtonian uncharged drop in the presence of an axisymmetric nonuniform DC electric field is studied analytically. The present study is focused on the effects of interfacial viscosities on the dielectrophoretic motion and shape deformation of an isolated suspended drop. The interfacial viscosities generate surface-excess viscous stress which is modeled as a two-dimensional Newtonian fluid which obeys the Boussinesq-Scriven constitutive law with constant values of interfacial tension, interfacial shear, and dilatational viscosities. In the regime of small drop deformation, we have obtained analytical solution for the drop velocity and deformed shape by neglecting surface charge convection and fluid inertia. Our study demonstrates that the drop velocity is independent of the interfacial shear viscosity, while the interfacial dilatational viscosity strongly affects the drop velocity. The interfacial viscous effects always retard the dielectrophoretic motion of a perfectly conducting/dielectric drop. Notably, the interfacial viscous effects can retard or augment the dielectrophoretic motion of a leaky dielectric drop depending on the electrohydrodynamic properties. The shape deformation of a leaky dielectric drop is found to decrease (or increase) due to interfacial shear (or dilatational) viscosity.

Heteromorphic NiCo2S4/Ni3S2/Ni Foam as a Self-Standing Electrode for Hydrogen Evolution Reaction in Alkaline Solution.

PubMed

Liu, Hui; Ma, Xiao; Rao, Yuan; Liu, Yang; Liu, Jialiang; Wang, Luyang; Wu, Mingbo

2018-04-04

Considerable works have been devoted on developing high-efficiency nonplatinum electrocatalysts for hydrogen evolution reaction (HER). Herein, 3D heteromorphic NiCo 2 S 4 /Ni 3 S 2 nanosheets network has been constructed on Ni foam (denoted as NiCo 2 S 4 /Ni 3 S 2 /NF) serving as a self-standing electrocatalyst through directly thermal sulfurization of a single-source NiCo-layered double hydroxide precursor. The resultant NiCo 2 S 4 /Ni 3 S 2 /NF electrode exhibits outstanding electrocatalytic HER performance with an extremely low onset overpotential of 15 mV and long-term durability in alkaline solution. Such enhanced HER performance can be credited to (1) the massive exposed active sites provided by mixed transition metal chalcogenides (NiCo 2 S 4 and Ni 3 S 2 ), (2) the strong interfacial interaction at NiCo 2 S 4 /Ni 3 S 2 heterojunction interfaces with the strengthened H binding, and (3) the porous highly conductive Ni foam substrate with accelerated electron transfer. This work opens up a new direction to fabricate effective and non-noble-metal electrodes for water splitting and hydrogen generation.

Bipolar electrochemical mechanism for the propulsion of catalytic nanomotors in hydrogen peroxide solutions.

PubMed

Wang, Yang; Hernandez, Rose M; Bartlett, David J; Bingham, Julia M; Kline, Timothy R; Sen, Ayusman; Mallouk, Thomas E

2006-12-05

Bimetallic nanorods are propelled in aqueous solutions by the catalytic decomposition of hydrogen peroxide to oxygen and water. Several mechanisms (interfacial tension gradients, bubble recoil, viscous Brownian ratchet, self-electrophoresis) have been proposed for the transduction of chemical to mechanical energy in this system. From Tafel plots of anodic and cathodic hydrogen peroxide reactions at various metal (Au, Pt, Rh, Ni, Ru, and Pd) ultramicroelectrodes, we determine the potential at which the anodic and cathodic reaction rates are equal for each metal. These measurements allow one to predict the direction of motion of all possible bimetallic combinations according to the bipolar electrochemical (or self-electrophoretic) mechanism. These predictions are consistent with the observed direction of motion in all cases studied, providing strong support for the mechanism. We also find that segmented nanorods with one Au end and one poly(pyrrole) end containing catalase, an enzyme that decomposes hydrogen peroxide nonelectrochemically, perform the overall catalytic reaction at a rate similar to that of nanorods containing Au and Pt segments. However, in this case there is no observed axial movement, again supporting the bipolar electrochemical propulsion mechanism for bimetallic nanorods.

Real-Time X-Ray Transmission Microscopy of Solidifying Al-In Alloys

NASA Technical Reports Server (NTRS)

Curreri, Peter A.; Kaukler, William F.

1997-01-01

Real-time observations of transparent analog materials have provided insight, yet the results of these observations are not necessarily representative of opaque metallic systems. In order to study the detailed dynamics of the solidification process, we develop the technologies needed for real-time X ray microscopy of solidifying metallic systems, which has not previously been feasible with the necessary resolution, speed, and contrast. In initial studies of Al-In monotectic alloys unidirectionally solidified in an X-ray transparent furnace, in situ records of the evolution of interface morphologies, interfacial solute accumulation, and formation of the monotectic droplets were obtained for the first time: A radiomicrograph of Al-30In grown during aircraft parabolic maneuvers is presented, showing the volumetric phase distribution in this specimen. The benefits of using X-ray microscopy for postsolidification metallography include ease of specimen preparation, increased sensitivity, and three-dimensional analysis of phase distribution. Imaging of the solute boundary layer revealed that the isoconcentration lines are not parallel (as is often assumed) to the growth interface. Striations in the solidified crystal did not accurately decorate the interface position and shape. The monotectic composition alloy under some conditions grew in an uncoupled manner.

Role of adsorption in liquid lubrication

NASA Technical Reports Server (NTRS)

Groszek, A. J.

1973-01-01

Changes at solid-liquid interfaces caused by adsorption from solution are discussed paying attention to the following aspects: (1) stability of adsorbed films and the structure of metal-additive-film-liquid interface and effect of adsorbate orientation. (2) chemical versus physical adsorption, (3) heat of adsorption, (4) adsorption of additives, (5) activated adsorption, effect of activating adsorbates, (6) displacement phenomena at solid-liquid interfaces, (7) competition of antiwear additives, their solvents, and water, (8) effect of adsorption on the orientation of liquid in the interfacial region, and (9) relation between the chemical nature of solid surfaces and their interaction with liquid lubricants. The relevance of the above adsorption phenomena to lubrication is discussed, referring where possible to specific examples.

Threshold voltage control in TmSiO/HfO2 high-k/metal gate MOSFETs

NASA Astrophysics Data System (ADS)

Dentoni Litta, E.; Hellström, P.-E.; Östling, M.

2015-06-01

High-k interfacial layers have been proposed as a way to extend the scalability of Hf-based high-k/metal gate CMOS technology, which is currently limited by strong degradations in threshold voltage control, channel mobility and device reliability when the chemical oxide (SiOx) interfacial layer is scaled below 0.4 nm. We have previously demonstrated that thulium silicate (TmSiO) is a promising candidate as a high-k interfacial layer, providing competitive advantages in terms of EOT scalability and channel mobility. In this work, the effect of the TmSiO interfacial layer on threshold voltage control is evaluated, showing that the TmSiO/HfO2 dielectric stack is compatible with threshold voltage control techniques commonly used with SiOx/HfO2 stacks. Specifically, we show that the flatband voltage can be set in the range -1 V to +0.5 V by the choice of gate metal and that the effective workfunction of the stack is properly controlled by the metal workfunction in a gate-last process flow. Compatibility with a gate-first approach is also demonstrated, showing that integration of La2O3 and Al2O3 capping layers can induce a flatband voltage shift of at least 150 mV. Finally, the effect of the annealing conditions on flatband voltage is investigated, finding that the duration of the final forming gas anneal can be used as a further process knob to tune the threshold voltage. The evaluation performed on MOS capacitors is confirmed by the fabrication of TmSiO/HfO2/TiN MOSFETs achieving near-symmetric threshold voltages at sub-nm EOT.

Large capacitance enhancement induced by metal-doping in graphene-based supercapacitors: a first-principles-based assessment.

PubMed

Paek, Eunsu; Pak, Alexander J; Hwang, Gyeong S

2014-08-13

Chemically doped graphene-based materials have recently been explored as a means to improve the performance of supercapacitors. In this work, we investigate the effects of 3d transition metals bound to vacancy sites in graphene with [BMIM][PF6] ionic liquid on the interfacial capacitance; these results are compared to the pristine graphene case with particular attention to the relative contributions of the quantum and electric double layer capacitances. Our study highlights that the presence of metal-vacancy complexes significantly increases the availability of electronic states near the charge neutrality point, thereby enhancing the quantum capacitance drastically. In addition, the use of metal-doped graphene electrodes is found to only marginally influence the microstructure and capacitance of the electric double layer. Our findings indicate that metal-doping of graphene-like electrodes can be a promising route toward increasing the interfacial capacitance of electrochemical double layer capacitors, primarily by enhancing the quantum capacitance.

Stochastic level-set variational implicit-solvent approach to solute-solvent interfacial fluctuations

PubMed Central

Zhou, Shenggao; Sun, Hui; Cheng, Li-Tien; Dzubiella, Joachim; McCammon, J. Andrew

2016-01-01

Recent years have seen the initial success of a variational implicit-solvent model (VISM), implemented with a robust level-set method, in capturing efficiently different hydration states and providing quantitatively good estimation of solvation free energies of biomolecules. The level-set minimization of the VISM solvation free-energy functional of all possible solute-solvent interfaces or dielectric boundaries predicts an equilibrium biomolecular conformation that is often close to an initial guess. In this work, we develop a theory in the form of Langevin geometrical flow to incorporate solute-solvent interfacial fluctuations into the VISM. Such fluctuations are crucial to biomolecular conformational changes and binding process. We also develop a stochastic level-set method to numerically implement such a theory. We describe the interfacial fluctuation through the “normal velocity” that is the solute-solvent interfacial force, derive the corresponding stochastic level-set equation in the sense of Stratonovich so that the surface representation is independent of the choice of implicit function, and develop numerical techniques for solving such an equation and processing the numerical data. We apply our computational method to study the dewetting transition in the system of two hydrophobic plates and a hydrophobic cavity of a synthetic host molecule cucurbit[7]uril. Numerical simulations demonstrate that our approach can describe an underlying system jumping out of a local minimum of the free-energy functional and can capture dewetting transitions of hydrophobic systems. In the case of two hydrophobic plates, we find that the wavelength of interfacial fluctuations has a strong influence to the dewetting transition. In addition, we find that the estimated energy barrier of the dewetting transition scales quadratically with the inter-plate distance, agreeing well with existing studies of molecular dynamics simulations. Our work is a first step toward the inclusion of fluctuations into the VISM and understanding the impact of interfacial fluctuations on biomolecular solvation with an implicit-solvent approach. PMID:27497546

Interfacial properties of stanene-metal contacts

NASA Astrophysics Data System (ADS)

Guo, Ying; Pan, Feng; Ye, Meng; Wang, Yangyang; Pan, Yuanyuan; Zhang, Xiuying; Li, Jingzhen; Zhang, Han; Lu, Jing

2016-09-01

Recently, two-dimensional buckled honeycomb stanene has been manufactured by molecular beam epitaxy growth. Free-standing stanene is predicted to have a sizable opened band gap of 100 meV at the Dirac point due to spin-orbit coupling (SOC), resulting in many fascinating properties such as quantum spin Hall effect, quantum anomalous Hall effect, and quantum valley Hall effect. In the first time, we systematically study the interfacial properties of stanene-metal interfaces (metals = Ag, Au, Cu, Al, Pd, Pt, Ir, and Ni) by using ab initio electronic structure calculations considering the SOC effects. The honeycomb structure of stanene is preserved on the metal supports, but the buckling height is changed. The buckling of stanene on the Au, Al, Ag, and Cu metal supports is higher than that of free-standing stanene. By contrast, a planar graphene-like structure is stabilized for stanene on the Ir, Pd, Pt, and Ni metal supports. The band structure of stanene is destroyed on all the metal supports, accompanied by a metallization of stanene because the covalent bonds between stanene and the metal supports are formed and the structure of stanene is distorted. Besides, no tunneling barrier exists between stanene and the metal supports. Therefore, stanene and the eight metals form a good vertical Ohmic contact.

Residual stress within nanoscale metallic multilayer systems during thermal cycling

DOE PAGES

Economy, David Ross; Cordill, Megan Jo; Payzant, E. Andrew; ...

2015-09-21

Projected applications for nanoscale metallic multilayers will include wide temperature ranges. Since film residual stress has been known to alter system reliability, stress development within new film structures with high interfacial densities should be characterized to identify potential long-term performance barriers. To understand factors contributing to thermal stress evolution within nanoscale metallic multilayers, stress in Cu/Nb systems adhered to Si substrates was calculated from curvature measurements collected during cycling between 25 °C and 400 °C. Additionally, stress within each type of component layers was calculated from shifts in the primary peak position from in-situ heated X-ray diffraction. The effects ofmore » both film architecture (layer thickness) and layer order in metallic multilayers were tracked and compared with monolithic Cu and Nb films. Analysis indicated that the thermoelastic slope of nanoscale metallic multilayer films depends on thermal expansion mismatch, elastic modulus of the components, and also interfacial density. The layer thickness (i.e. interfacial density) affected thermoelastic slope magnitude while layer order had minimal impact on stress responses after the initial thermal cycle. When comparing stress responses of monolithic Cu and Nb films to those of the Cu/Nb systems, the nanoscale metallic multilayers show a similar increase in stress above 200 °C to the Nb monolithic films, indicating that Nb components play a larger role in stress development than Cu. Local stress calculations from X-ray diffraction peak shifts collected during heating reveal that the component layers within a multilayer film respond similarly to their monolithic counterparts.« less

Inelastic deformation of metal matrix composites

NASA Technical Reports Server (NTRS)

Lissenden, C. J.; Herakovich, C. T.; Pindera, M-J.

1993-01-01

A theoretical model capable of predicting the thermomechanical response of continuously reinforced metal matrix composite laminates subjected to multiaxial loading was developed. A micromechanical model is used in conjunction with nonlinear lamination theory to determine inelastic laminae response. Matrix viscoplasticity, residual stresses, and damage to the fiber/matrix interfacial zone are explicitly included in the model. The representative cell of the micromechanical model is considered to be in a state of generalized plane strain, enabling a quasi two-dimensional analysis to be performed. Constant strain finite elements are formulated with elastic-viscoplastic constitutive equations. Interfacial debonding is incorporated into the model through interface elements based on the interfacial debonding theory originally presented by Needleman, and modified by Tvergaard. Nonlinear interfacial constitutive equations relate interfacial tractions to displacement discontinuities at the interface. Theoretical predictions are compared with the results of an experimental program conducted on silicon carbide/titanium (SiC/Ti) unidirectional, (O4), and angle-ply, (+34)(sub s), tubular specimens. Multiaxial loading included increments of axial tension, compression, torque, and internal pressure. Loadings were chosen in an effort to distinguish inelastic deformation due to damage from matrix plasticity and separate time-dependent effects from time-independent effects. Results show that fiber/matrix debonding is nonuniform throughout the composite and is a major factor in the effective response. Also, significant creep behavior occurs at relatively low applied stress levels at room temperature.

Long life hydrocarbon conversion catalyst and method of making

DOEpatents

Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Gao, Yufei [Kennewick, WA

2002-11-12

The present invention includes a catalyst that has at least four layers, (1) porous support, (2) buffer layer, (3) interfacial layer, and optionally (4) catalyst layer. The buffer layer provides a transition of thermal expansion coefficient from the porous support to the interfacial layer thereby reducing thermal expansion stress as the catalyst is heated to high operating temperatures. The method of the present invention for making the at least three layer catalyst has the steps of (1) selecting a porous support, (2) solution depositing an interfacial layer thereon, and optionally (3) depositing a catalyst material onto the interfacial layer; wherein the improvement comprises (4) depositing a buffer layer between the porous support and the interfacial layer.

Electrochemical Impedance Spectroscopy for Real-Time Detection of Lipid Membrane Damage Based on a Porous Self-Assembly Monolayer Support.

PubMed

Zhang, Meng; Zhai, Qingyu; Wan, Liping; Chen, Li; Peng, Yu; Deng, Chunyan; Xiang, Juan; Yan, Jiawei

2018-06-19

Layer-by-layer dissolution and permeable pore formation are two typical membrane damage pathways, which induce membrane function disorder and result in serious disease, such as Alzheimer's disease, Keshan disease, Sickle-cell disease, and so on. To effectively distinguish and sensitively monitor these two typical membrane damage pathways, a facile electrochemical impedance strategy was developed on a porous self-assembly monolayer (pSAM) supported bilayer lipid membrane (BLM). The pSAM was prepared by selectively electrochemical reductive desorption of the mercaptopropionic acid in a mixed mercaptopropionic acid/11-mercaptoundecanoic acid self-assembled monolayer, which created plenty of nanopores with tens of nanometers in diameter and several nanometers in height (defined as inner-pores). The ultralow aspect ratio of the inner-pores was advantageous to the mass transfer of electrochemical probe [Fe(CN) 6 ] 3-/4- , simplifying the equivalent electric circuit for electrochemical impedance spectroscopy analysis at the electrode/membrane interface. [Fe(CN) 6 ] 3-/4- transferring from the bulk solution into the inner-pore induce significant changes of the interfacial impedance properties, improving the detection sensitivity. Based on these, the different membrane damage pathways were effectively distinguished and sensitively monitored with the normalized resistance-capacitance changes of inner-pore-related parameters including the electrolyte resistance within the pore length ( R pore ) and the metal/inner-pore interfacial capacitance ( C pore ) and the charge-transfer resistance ( R ct-in ) at the metal/inner-pore interface.

Electronic and chemical structure of metal-silicon interfaces

NASA Technical Reports Server (NTRS)

Grunthaner, P. J.; Grunthaner, F. J.

1984-01-01

This paper reviews our current understanding of the near-noble metal silicides and the interfaces formed with Si(100). Using X-ray photoemission spectroscopy, we compare the chemical composition and electronic structure of the room temperature metal-silicon and reacted silicide-silicon interfaces. The relationship between the interfacial chemistry and the Schottky barrier heights for this class of metals on silicon is explored.

Mechanical properties of Al/Al[sub 2]O[sub 3] and Cu/Al[sub 2]O[sub 3] composites with interpenetrating networks

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

Knechtel, M.; Prielipp, H.; Claussen, N.

The rising fracture resistance with crack length in metal-toughened ceramics due to ductile bridging has been discussed from some selected microstructures and metal-ceramic combinations. An intriguing feature of these composites is the influence of interfacial fracture strength. Strong interfacial bonding leads to high geometrical constraint for the metal and high degree of triaxial tension in the metal ligament, thereby increasing the uniaxial yield strength by a factor of 5--7. This in turn increases the closure stress of the metal ligament, but ultimately limits the total plastic dissipation in the ductile reinforcement. The intent of this paper is to provide somemore » insight on the influence of metal ligament size on both fracture toughness and fracture strength. The materials chosen are Al/Al[sub 2]O[sub 3] and Cu/Al[sub 2]O[sub 3] composites, both prepared by gas-pressure metal-infiltration of porous alumina preforms. SEM observations of fracture surfaces in conjunction with preliminary TEM and PEELS investigations of the metal-ceramic interfaces are used to explain the trends in mechanical property data.« less

Multifunctional interphase

NASA Astrophysics Data System (ADS)

Rosy, Noked, Malachi

2018-04-01

Realization of rechargeable batteries with alkali metal anodes is challenged by their high reactivity and dendritic growth. Now, an alloy-based, artificial solid electrolyte interphase is shown to allow smooth metal deposition, enhance interfacial charge transfer, protect against parasitic reactions and offer extra energy storage.

Migration of interfacial oxygen ions modulated resistive switching in oxide-based memory devices

NASA Astrophysics Data System (ADS)

Chen, C.; Gao, S.; Zeng, F.; Tang, G. S.; Li, S. Z.; Song, C.; Fu, H. D.; Pan, F.

2013-07-01

Oxides-based resistive switching memory induced by oxygen ions migration is attractive for future nonvolatile memories. Numerous works had focused their attentions on the sandwiched oxide materials for depressing the characteristic variations, but the comprehensive studies of the dependence of electrodes on the migration behavior of oxygen ions are overshadowed. Here, we investigated the interaction of various metals (Ni, Co, Al, Ti, Zr, and Hf) with oxygen atoms at the metal/Ta2O5 interface under electric stress and explored the effect of top electrode on the characteristic variations of Ta2O5-based memory device. It is demonstrated that chemically inert electrodes (Ni and Co) lead to the scattering switching characteristics and destructive gas bubbles, while the highly chemically active metals (Hf and Zr) formed a thick and dense interfacial intermediate oxide layer at the metal/Ta2O5 interface, which also degraded the resistive switching behavior. The relatively chemically active metals (Al and Ti) can absorb oxygen ions from the Ta2O5 film and avoid forming the problematic interfacial layer, which is benefit to the formation of oxygen vacancies composed conduction filaments in Ta2O5 film thus exhibit the minimum variations of switching characteristics. The clarification of oxygen ions migration behavior at the interface can lead further optimization of resistive switching performance in Ta2O5-based memory device and guide the rule of electrode selection for other oxide-based resistive switching memories.

Interfacial Stability of Li Metal-Solid Electrolyte Elucidated via in Situ Electron Microscopy.

PubMed

Ma, Cheng; Cheng, Yongqiang; Yin, Kuibo; Luo, Jian; Sharafi, Asma; Sakamoto, Jeff; Li, Juchuan; More, Karren L; Dudney, Nancy J; Chi, Miaofang

2016-11-09

Despite their different chemistries, novel energy-storage systems, e.g., Li-air, Li-S, all-solid-state Li batteries, etc., face one critical challenge of forming a conductive and stable interface between Li metal and a solid electrolyte. An accurate understanding of the formation mechanism and the exact structure and chemistry of the rarely existing benign interfaces, such as the Li-cubic-Li 7-3x Al x La 3 Zr 2 O 12 (c-LLZO) interface, is crucial for enabling the use of Li metal anodes. Due to spatial confinement and structural and chemical complications, current investigations are largely limited to theoretical calculations. Here, through an in situ formation of Li-c-LLZO interfaces inside an aberration-corrected scanning transmission electron microscope, we successfully reveal the interfacial chemical and structural progression. Upon contact with Li metal, the LLZO surface is reduced, which is accompanied by the simultaneous implantation of Li + , resulting in a tetragonal-like LLZO interphase that stabilizes at an extremely small thickness of around five unit cells. This interphase effectively prevented further interfacial reactions without compromising the ionic conductivity. Although the cubic-to-tetragonal transition is typically undesired during LLZO synthesis, the similar structural change was found to be the likely key to the observed benign interface. These insights provide a new perspective for designing Li-solid electrolyte interfaces that can enable the use of Li metal anodes in next-generation batteries.

Gate-Induced Interfacial Superconductivity in 1T-SnSe2.

PubMed

Zeng, Junwen; Liu, Erfu; Fu, Yajun; Chen, Zhuoyu; Pan, Chen; Wang, Chenyu; Wang, Miao; Wang, Yaojia; Xu, Kang; Cai, Songhua; Yan, Xingxu; Wang, Yu; Liu, Xiaowei; Wang, Peng; Liang, Shi-Jun; Cui, Yi; Hwang, Harold Y; Yuan, Hongtao; Miao, Feng

2018-02-14

Layered metal chalcogenide materials provide a versatile platform to investigate emergent phenomena and two-dimensional (2D) superconductivity at/near the atomically thin limit. In particular, gate-induced interfacial superconductivity realized by the use of an electric-double-layer transistor (EDLT) has greatly extended the capability to electrically induce superconductivity in oxides, nitrides, and transition metal chalcogenides and enable one to explore new physics, such as the Ising pairing mechanism. Exploiting gate-induced superconductivity in various materials can provide us with additional platforms to understand emergent interfacial superconductivity. Here, we report the discovery of gate-induced 2D superconductivity in layered 1T-SnSe 2 , a typical member of the main-group metal dichalcogenide (MDC) family, using an EDLT gating geometry. A superconducting transition temperature T c ≈ 3.9 K was demonstrated at the EDL interface. The 2D nature of the superconductivity therein was further confirmed based on (1) a 2D Tinkham description of the angle-dependent upper critical field B c2 , (2) the existence of a quantum creep state as well as a large ratio of the coherence length to the thickness of superconductivity. Interestingly, the in-plane B c2 approaching zero temperature was found to be 2-3 times higher than the Pauli limit, which might be related to an electric field-modulated spin-orbit interaction. Such results provide a new perspective to expand the material matrix available for gate-induced 2D superconductivity and the fundamental understanding of interfacial superconductivity.

Direct observation of interfacial Au atoms on TiO₂ in three dimensions.

PubMed

Gao, Wenpei; Sivaramakrishnan, Shankar; Wen, Jianguo; Zuo, Jian-Min

2015-04-08

Interfacial atoms, which result from interactions between the metal nanoparticles and support, have a large impact on the physical and chemical properties of nanoparticles. However, they are difficult to observe; the lack of knowledge has been a major obstacle toward unraveling their role in chemical transformations. Here we report conclusive evidence of interfacial Au atoms formed on the rutile (TiO2) (110) surfaces by activation using high-temperature (∼500 °C) annealing in air. Three-dimensional imaging was performed using depth-sectioning enabled by aberration-corrected scanning transmission electron microscopy. Results show that the interface between Au nanocrystals and TiO2 (110) surfaces consists of a single atomic layer with Au atoms embedded inside Ti-O. The number of interfacial Au atoms is estimated from ∼1-8 in an interfacial atomic column. Direct impact of interfacial Au atoms is observed on an enhanced Au-TiO2 interaction and the reduction of surface TiO2; both are critical to Au catalysis.

Research on the interfacial behaviors of plate-type dispersion nuclear fuel elements

NASA Astrophysics Data System (ADS)

Wang, Qiming; Yan, Xiaoqing; Ding, Shurong; Huo, Yongzhong

2010-04-01

The three-dimensional constitutive relations are constructed, respectively, for the fuel particles, the metal matrix and the cladding of dispersion nuclear fuel elements, allowing for the effects of large deformation and thermal-elastoplasticity. According to the constitutive relations, the method of modeling their irradiation behaviors in ABAQUS is developed and validated. Numerical simulations of the interfacial performances between the fuel meat and the cladding are implemented with the developed finite element models for different micro-structures of the fuel meat. The research results indicate that: (1) the interfacial tensile stresses and shear stresses for some cases will increase with burnup, but the relative stresses will decrease with burnup for some micro-structures; (2) at the lower burnups, the interfacial stresses increase with the particle sizes and the particle volume fractions; however, it is not the case at the higher burnups; (3) the particle distribution characteristics distinctly affect the interfacial stresses, and the face-centered cubic case has the best interfacial performance of the three considered cases.

Understanding Thermal Transport in Graded, Layered and Hybrid Materials

DTIC Science & Technology

2014-04-01

interfacial chemistries, including metallic and carbide layers, and; (iv) mimic the observed interface structure on a TDTR specimen by manipulating the...surface carbides , which were extracted from several different composites via acid dissolution of Cu, continued throughout the last 12 months of the...effort. The previously-reported electron probe microanalysis (EPMA) based techniques were employed to estimate the interfacial carbide layer thickness

Development of FRP composite structural biomaterials: ultimate strength of the fiber/matrix interfacial bond in in vivo simulated environments.

PubMed

Latour, R A; Black, J

1992-05-01

Fiber reinforced polymer (FRP) composites are being developed as alternatives to metals for structural orthopedic implant applications. FRP composite fracture behavior and environmental interactions are distinctly different from those which occur in metals. These differences must be accounted for in the design and evaluation of implant performance. Fiber/matrix interfacial bond strength in a FRP composite is known to strongly influence fracture behavior. The interfacial bond strength of four candidate fiber/matrix combinations (carbon fiber/polycarbonate, carbon fiber/polysulfone, polyaramid fiber/polycarbonate, polyaramid fiber/polysulfone) were investigated at 37 degrees C in dry and in vivo simulated (saline, exudate) environments. Ultimate bond strength was measured by a single fiber-microdroplet pull-out test. Dry bond strengths were significantly decreased following exposure to either saline or exudate with bond strength loss being approximately equal in both the saline and exudate. Bond strength loss is attributed to the diffusion of water and/or salt ions into the sample and their interaction with interfacial bonding. Because bond degradation is dependent upon diffusion, diffusional equilibrium must be obtained in composite test samples before the full effect of the test environment upon composite mechanical behavior can be determined.

Life prediction of coated and uncoated metallic interconnect for solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Liu, W. N.; Sun, X.; Stephens, E.; Khaleel, M. A.

In this paper, we present an integrated experimental and modeling methodology in predicting the life of coated and uncoated metallic interconnect (IC) for solid oxide fuel cell (SOFC) applications. The ultimate goal is to provide cell designer and manufacture with a predictive methodology such that the life of the IC system can be managed and optimized through different coating thickness to meet the overall cell designed life. Crofer 22 APU is used as the example IC material system. The life of coated and uncoated Crofer 22 APU under isothermal cooling was predicted by comparing the predicted interfacial strength and the interfacial stresses induced by the cooling process from the operating temperature to room temperature, together with the measured oxide scale growth kinetics. It was found that the interfacial strength between the oxide scale and the Crofer 22 APU substrate decreases with the growth of the oxide scale, and that the interfacial strength for the oxide scale/spinel coating interface is much higher than that of the oxide scale/Crofer 22 APU substrate interface. As expected, the predicted life of the coated Crofer 22 APU is significantly longer than that of the uncoated Crofer 22 APU.

A Novel Charged Medium Consisting of Gas-Liquid Interfacial Plasmas

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

Kaneko, Toshiro; Hatakeyama, Rikizo

Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we succeed in creating the reactive gas (plasmas)--liquid (ionic liquids) interfacial field under a low gas pressure condition, where the plasma ion behavior can be controlled. The effects of the plasma ion irradiation on the liquid medium are quantitatively revealed for the first time. In connection with the plasma ion irradiation, the potential structure and optical emission properties of the gas-liquid interfacial plasma are investigated by changing a polarity of the electrode in the liquid to evaluate the plasma-liquid interactions. Thesemore » results would contribute to synthesizing the metal nanoparticles with carbon nanotubes as a template in the ionic liquid. It is found that the high density, mono-dispersed, and isolated metal nanoparticles are synthesized between or inside the carbon nanotubes by controlling the gas-liquid interfacial plasmas. Furthermore, we can form novel nano-bio composite materials, such as DNA encapsulated carbon nanotubes using the plasma ion irradiation method in an electrolyte plasma with DNA, and demonstrate modifications of the electrical properties of the carbon nanotubes depending on the kinds of encapsulated DNA for the first time.« less

Atomic layer deposition of ZrO2 on W for metal-insulator-metal capacitor application

NASA Astrophysics Data System (ADS)

Lee, Sang-Yun; Kim, Hyoungsub; McIntyre, Paul C.; Saraswat, Krishna C.; Byun, Jeong-Soo

2003-04-01

A metal-insulator-metal (MIM) capacitor using ZrO2 on tungsten (W) metal bottom electrode was demonstrated and characterized in this letter. Both ZrO2 and W metal were synthesized by an atomic layer deposition (ALD) method. High-quality 110˜115 Å ZrO2 films were grown uniformly on ALD W using ZrCl4 and H2O precursors at 300 °C, and polycrystalline ZrO2 in the ALD regime could be obtained. A 13˜14-Å-thick interfacial layer between ZrO2 and W was observed after fabrication, and it was identified as WOx through angle-resolved x-ray photoelectron spectroscopy analysis with wet chemical etching. The apparent equivalent oxide thickness was 20˜21 Å. An effective dielectric constant of 22˜25 including an interfacial WOx layer was obtained by measuring capacitance and thickness of MIM capacitors with Pt top electrodes. High capacitance per area (16˜17 fF/μm2) and low leakage current (10-7 A/cm2 at ±1 V) were achieved.

Conjugated Polymer Zwitterions: Efficient Interlayer Materials in Organic Electronics.

PubMed

Liu, Yao; Duzhko, Volodimyr V; Page, Zachariah A; Emrick, Todd; Russell, Thomas P

2016-11-15

Conjugated polymer zwitterions (CPZs) are neutral, hydrophilic, polymer semiconductors. The pendent zwitterions, viewed as side chain dipoles, impart solubility in polar solvents for solution processing, and open opportunities as interfacial components of optoelectronic devices, for example, between metal electrodes and organic semiconductor active layers. Such interlayers are crucial for defining the performance of organic electronic devices, e.g., field-effect transistors (OFETs), light-emitting diodes (OLEDs), and photovoltaics (OPVs), all of which consist of multilayer structures. The interlayers reduce the Schottky barrier height and thus improve charge injection in OFETs and OLEDs. In OPVs, the interlayers serve to increase the built-in electric potential difference (V bi ) across the active layer, ensuring efficient extraction of photogenerated charge carriers. In general, polar and even charged electronically active polymers have gained recognition for their ability to modify metal/semiconductor interfaces to the benefit of organic electronics. While conjugated polyelectrolytes (CPEs) as interlayer materials are well-documented, open questions remain about the role of mobile counterions in CPE-containing devices. CPZs possess the processing advantages of CPEs, but as neutral molecules lack any potential complications associated with counterions. The electronic implications of CPZs on metal electrodes stem from the orientation of the zwitterion dipole moment in close proximity to the metal surface, and the resultant surface-induced polarization. This generates an interfacial dipole (Δ) at the CPZ/metal interface, altering the work function of the electrode, as confirmed by ultraviolet photoelectron spectroscopy (UPS), and improving device performance. An ideal cathode interlayer would reduce electrode work function, have orthogonal processability to the active layer, exhibit good film forming properties (i.e., wettability/uniformity), prevent exciton quenching, possess optimal electron affinity that neither limits the work function reduction nor impedes the charge extraction, transport electrons selectively, and exhibit long-term stability. Our recent discoveries show that CPZs achieve many of these attributes, and are poised for further expansion and development in the interfacial science of organic electronics. This Account reviews a recent collaboration that began with the synthesis of CPZs and a study of their structural and electronic properties on metals, then extended to their application as interlayer materials for OPVs. We discuss CPZ structure-property relationships based on several material platforms, ranging from homopolymers to copolymers, and from materials with intrinsic p-type conjugated backbones to those with intrinsic n-type conjugated backbones. We discuss key components of such interlayers, including (i) the origin of work function reduction of CPZ interlayers on metals; (ii) the role of the frontier molecular orbital energy levels and their trade-offs in optimizing electronic and device properties; and (iii) the role of polymer conductivity type and the magnitude of charge carrier mobility. Our motivation is to present our prior use and current understanding of CPZs as interlayer materials in organic electronics, and describe outstanding issues and future potential directions.

The principle of minimal episteric distortion of the water matrix and its steering role in protein folding

NASA Astrophysics Data System (ADS)

Fernández, Ariel

2013-08-01

A significant episteric ("around a solid") distortion of the hydrogen-bond structure of water is promoted by solutes with nanoscale surface detail and physico-chemical complexity, such as soluble natural proteins. These structural distortions defy analysis because the discrete nature of the solvent at the interface is not upheld by the continuous laws of electrostatics. This work derives and validates an electrostatic equation that governs the episteric distortions of the hydrogen-bond matrix. The equation correlates distortions from bulk-like structural patterns with anomalous polarization components that do not align with the electrostatic field of the solute. The result implies that the interfacial energy stored in the orthogonal polarization correlates with the distortion of the water hydrogen-bond network. The result is validated vis-à-vis experimental data on protein interfacial thermodynamics and is interpreted in terms of the interaction energy between the electrostatic field of the solute and the dipole moment induced by the anomalous polarization of interfacial water. Finally, we consider solutes capable of changing their interface through conformational transitions and introduce a principle of minimal episteric distortion (MED) of the water matrix. We assess the importance of the MED principle in the context of protein folding, concluding that the native fold may be identified topologically with the conformation that minimizes the interfacial tension or disruption of the water matrix.

Creep and stress relaxation induced by interface diffusion in metal matrix composites

NASA Astrophysics Data System (ADS)

Li, Yinfeng; Li, Zhonghua

2013-03-01

An analytical solution is developed to predict the creep rate induced by interface diffusion in unidirectional fiber-reinforced and particle reinforced composites. The driving force for the interface diffusion is the normal stress acting on the interface, which is obtained from rigorous Eshelby inclusion theory. The closed-form solution is an explicit function of the applied stress, volume fraction and radius of the fiber, as well as the modulus ratio between the fiber and the matrix. It is interesting that the solution is formally similar to that of Coble creep in polycrystalline materials. For the application of the present solution in the realistic composites, the scale effect is taken into account by finite element analysis based on a unit cell. Based on the solution, a closed-form solution is also given as a description of stress relaxation induced by interfacial diffusion under constant strain. In addition, the analytical solution for the interface stress presented in this study gives some insight into the relationship between the interface diffusion and interface slip. This work was supported by the financial support from the Nature Science Foundation of China (No. 10932007), the National Basic Research Program of China (No. 2010CB631003/5), and the Doctoral Program of Higher Education of China (No. 20100073110006).

New flange correction formula applied to interfacial resistance measurements of ohmic contacts to GaAs

NASA Technical Reports Server (NTRS)

Lieneweg, Udo; Hannaman, David J.

1987-01-01

A quasi-two-dimensional analytical model is developed to account for vertical and horizontal current flow in and adjacent to a square ohmic contact between a metal and a thin semiconducting strip which is wider than the contact. The model includes side taps to the contact area for voltage probing and relates the 'apparent' interfacial resistivity to the (true) interfacial resistivity, the sheet resistance of the semiconducting layer, the contact size, and the width of the 'flange' around the contact. This relation is checked against numerical simulations. With the help of the model, interfacial resistivities of ohmic contacts to GaAs were extracted and found independent of contact size in the range of 1.5-10 microns.

Environment-dependent interfacial strength using first principles thermodynamics: The example of the Pt-HfO2 interface

NASA Astrophysics Data System (ADS)

Cardona Quintero, Y.; Ramanath, Ganpati; Ramprasad, R.

2013-10-01

A parameter-free, quantitative, first-principles methodology to determine the environment-dependent interfacial strength of metal-metal oxide interfaces is presented. This approach uses the notion of the weakest link to identify the most likely cleavage plane, and first principles thermodynamics to calculate the average work of separation as a function of the environment (in this case, temperature and oxygen pressure). The method is applied to the case of the Pt-HfO2 interface, and it is shown that the computed environment-dependent work of separation is in quantitative agreement with available experimental data.

Gradiently Polymerized Solid Electrolyte Meets with Micro/Nano-Structured Cathode Array.

PubMed

Dong, Wei; Zeng, Xian-Xiang; Zhang, Xu-Dong; Li, Jin-Yi; Shi, Ji-Lei; Xiao, Yao; Shi, Yang; Wen, Rui; Yin, Ya-Xia; Wang, Tai-Shan; Wang, Chun-Ru; Guo, Yu-Guo

2018-05-02

The poor contact between the solid-state electrolyte and cathode materials leads to high interfacial resistance, severely limiting the rate capability of solid Li metal batteries. Herein, an integrative battery design is introduced with a gradiently polymerized solid electrolyte (GPSE), a micro-channel current collector array and nano-sized cathode particles. In-situ formed GPSE encapsulates cathode nanoparticles in the micro-channel with ductile inclusions to lower interfacial impedance, and the stiff surface layer of GPSE toward anode suppresses Li dendrites growth. Li metal batteries based on GPSE and Li-free hydrogenated V2O5 (V2O5-H) cathode exhibit an outstanding high-rate response of up to 5 C (the capacity ratio of 5 C / 1 C is 90.3%) and an ultralow capacity fade rate of 0.07% per cycle over 300 cycles. Other Li-containing cathodes as LiFePO4 and LiNi0.5Mn0.3Co0.2O2 can also operate effectively at 5 C and 2 C rate, respectively. Such an ingenious design may provide new insights into other solid metal batteries through interfacial engineering manipulation at micro and nano level.

Influence of charged defects on the interfacial bonding strength of tantalum- and silver-doped nanograined TiO2.

PubMed

Azadmanjiri, Jalal; Wang, James; Berndt, Christopher C; Kapoor, Ajay; Zhu, De Ming; Ang, Andrew S M; Srivastava, Vijay K

2017-05-17

A nano-grained layer including line defects was formed on the surface of a Ti alloy (Ti alloy , Ti-6Al-4V ELI). Then, the micro- and nano-grained Ti alloy with the formation of TiO 2 on its top surface was coated with a bioactive Ta layer with or without incorporating an antibacterial agent of Ag that was manufactured by magnetron sputtering. Subsequently, the influence of the charged defects (the defects that can be electrically charged on the surface) on the interfacial bonding strength and hardness of the surface system was studied via an electronic model. Thereby, material systems of (i) Ta coated micro-grained titanium alloy (Ta/MGTi alloy ), (ii) Ta coated nano-grained titanium alloy (Ta/NGTi alloy ), (iii) TaAg coated micro-grained titanium alloy (TaAg/MGTi alloy ) and (iv) TaAg coated nano-grained titanium alloy (TaAg/NGTi alloy ) were formed. X-ray photoelectron spectroscopy was used to probe the electronic structure of the micro- and nano-grained Ti alloy , and so-formed heterostructures. The thin film/substrate interfaces exhibited different satellite peak intensities. The satellite peak intensity may be related to the interfacial bonding strength and hardness of the surface system. The interfacial layer of TaAg/NGTi alloy exhibited the highest satellite intensity and maximum hardness value. The increased bonding strength and hardness in the TaAg/NGTi alloy arises due to the negative core charge of the dislocations and neighbor space charge accumulation, as well as electron accumulation in the created semiconductor phases of larger band gap at the interfacial layer. These two factors generate interfacial polarization and enhance the satellite intensity. Consequently, the interfacial bonding strength and hardness of the surface system are improved by the formation of mixed covalent-ionic bonding structures around the dislocation core area and the interfacial layer. The bonding strength relationship by in situ XPS on the metal/TiO 2 interfacial layer may be examined with other noble metals and applied in diverse fields.

Thermocapillary migration of a drop: an exact solution with Newtonian interfacial rheology and stretching/shrinkage of interfacial area elements for small Marangoni numbers

NASA Technical Reports Server (NTRS)

Balasubramaniam, R.; Subramanian, R. Shankar

2004-01-01

In this paper we analyze the effects of the following phenomena associated with the thermocapillary migration of a drop. The first is the influence of Newtonian surface rheology of the interface and the second is that of the energy changes associated with stretching and shrinkage of the interfacial area elements, when the drop is in motion. The former occurs because of dissipative processes in the interfacial region, such as when surfactant molecules are adsorbed at the interface in sufficient concentration. The interface is typically modeled in this instance by ascribing to it a surface viscosity. This is a different effect from that of interfacial tension gradients arising from surfactant concentration gradients. The stretching and shrinkage of interfacial area elements leads to changes in the internal energy of these elements that affects the transport of energy in the fluids adjoining the interface. When an element on the interface is stretched, its internal energy increases because of the increase in its area. This energy is supplied by the neighboring fluids that are cooled as a consequence. Conversely, when an element on the interface shrinks, the adjoining fluids are warmed. In the case of a moving drop, elements of interfacial area are stretched in the forward half of the drop, and are shrunk in the rear half. Consequently, the temperature variation on the surface of the drop and its migration speed are modified. The analysis of the motion of a drop including these effects was first performed by LeVan in 1981, in the limit when convective transport of momentum and energy are negligible. We extend the analysis of LeVan to include the convective transport of momentum by demonstrating that an exact solution of the momentum equation is obtained for an arbitrary value of the Reynolds number. This solution is then used to calculate the slightly deformed shape of the drop from a sphere.

High reduction of interfacial charge recombination in colloidal quantum dot solar cells by metal oxide surface passivation.

PubMed

Chang, Jin; Kuga, Yuki; Mora-Seró, Iván; Toyoda, Taro; Ogomi, Yuhei; Hayase, Shuzi; Bisquert, Juan; Shen, Qing

2015-03-12

Bulk heterojunction (BHJ) solar cells based on colloidal QDs and metal oxide nanowires (NWs) possess unique and outstanding advantages in enhancing light harvesting and charge collection in comparison to planar architectures. However, the high surface area of the NW structure often brings about a large amount of recombination (especially interfacial recombination) and limits the open-circuit voltage in BHJ solar cells. This problem is solved here by passivating the surface of the metal oxide component in PbS colloidal quantum dot solar cells (CQDSCs). By coating thin TiO2 layers onto ZnO-NW surfaces, the open-circuit voltage and power conversion efficiency have been improved by over 40% in PbS CQDSCs. Characterization by transient photovoltage decay and impedance spectroscopy indicated that the interfacial recombination was significantly reduced by the surface passivation strategy. An efficiency as high as 6.13% was achieved through the passivation approach and optimization for the length of the ZnO-NW arrays (device active area: 16 mm2). All solar cells were tested in air, and exhibited excellent air storage stability (without any performance decline over more than 130 days). This work highlights the significance of metal oxide passivation in achieving high performance BHJ solar cells. The charge recombination mechanism uncovered in this work could shed light on the further improvement of PbS CQDSCs and/or other types of solar cells.

On 'large-scale' stable fiber displacement during interfacial failure in metal matrix composites

NASA Technical Reports Server (NTRS)

Petrich, R. R.; Koss, D. A.; Hellmann, J. R.; Kallas, M. N.

1993-01-01

Experimental results are presented to show that interfacial failure in sapphire-reinforced niobium is characterized by 'large-scale' (5-15 microns) plasticity-controlled fiber displacements occurring under increasing loads. The results are based on the responses during thin-slice fiber pushout tests wherein the fiber is supported over a hole twice the fiber diameter. The results describe an interfacial failure process that should also occur near fiber ends during pullout when a fiber is well-bonded to a soft, ductile matrix, such that eventual failure occurs by shear within the matrix near the interface.

A phenomenological model of coating/substrate adhesion and interfacial bimetallic peeling stress in composite mirrors

NASA Technical Reports Server (NTRS)

Mcelroy, Paul M.; Lawson, Daniel D.

1990-01-01

Adhesion and interfacial stress between metal films and structural composite material substrates is discussed. A theoretical and conceptual basis for selecting coating materials for composite mirror substrates is described. A phenomenological model that interrelates cohesive tensile strength of thin film coatings and interfacial peeling stresses is presented. The model serves as a basis in determining gradiated materials response and compatibility of composite substrate and coating combinations. Parametric evaluation of material properties and geometrical factors such as coating thickness are used to determine the threshold stress levels for maintaining adhesion at the different interfaces.

Multidimensional equilibria and their stability in copolymer-solvent mixtures

NASA Astrophysics Data System (ADS)

Glasner, Karl; Orizaga, Saulo

2018-06-01

This paper discusses localized equilibria which arise in copolymer-solvent mixtures. A free boundary problem associated with the sharp-interface limit of a density functional model is used to identify both lamellar and concentric domain patterns composed of a finite number of layers. Stability of these morphologies is studied through explicit linearization of the free boundary evolution. For the multilayered lamellar configuration, transverse instability is observed for sufficiently small dimensionless interfacial energies. Additionally, a crossover between small and large wavelength instabilities is observed depending on whether solvent-polymer or monomer-monomer interfacial energy is dominant. Concentric domain patterns resembling multilayered micelles and vesicles exhibit bifurcations wherein they only exist for sufficiently small dimensionless interfacial energies. The bifurcation of large radii vesicle solutions is studied analytically, and a crossover from a supercritical case with only one solution branch to a subcritical case with two is observed. Linearized stability of these configurations shows that azimuthal perturbation may lead to instabilities as interfacial energy is decreased.

Optimization of the Energy Level Alignment between the Photoactive Layer and the Cathode Contact Utilizing Solution-Processed Hafnium Acetylacetonate as Buffer Layer for Efficient Polymer Solar Cells.

PubMed

Yu, Lu; Li, Qiuxiang; Shi, Zhenzhen; Liu, Hao; Wang, Yaping; Wang, Fuzhi; Zhang, Bing; Dai, Songyuan; Lin, Jun; Tan, Zhan'ao

2016-01-13

The insertion of an appropriate interfacial buffer layer between the photoactive layer and the contact electrodes makes a great impact on the performance of polymer solar cells (PSCs). Ideal interfacial buffer layers could minimize the interfacial traps and the interfacial barriers caused by the incompatibility between the photoactive layer and the electrodes. In this work, we utilized solution-processed hafnium(IV) acetylacetonate (Hf(acac)4) as an effective cathode buffer layer (CBL) in PSCs to optimize the energy level alignment between the photoactive layer and the cathode contact, with the short-circuit current density (Jsc), open-circuit voltage (Voc), and fill factor (FF) all simultaneously improved with Hf(acac)4 CBL, leading to enhanced power conversion efficiencies (PCEs). Ultraviolet photoemission spectroscopy (UPS) and scanning Kelvin probe microscopy (SKPM) were performed to confirm that the interfacial dipoles were formed with the same orientation direction as the built-in potential between the photoactive layer and Hf(acac)4 CBL, benefiting the exciton separation and electron transport/extraction. In addition, the optical characteristics and surface morphology of the Hf(acac)4 CBL were also investigated.

Effect of adhesive applied to the tooth-wood interface on metal-plate connections loaded in tension

Treesearch

Leslie H. Groom

1991-01-01

The structural behavior of metal-plate connections (MPCs) is affected not only by the isolated properties of the adjoining wood members and metal plate but also by the interfacial region between individual teeth and the surrounding wood. This study looked at maintaining a good interface by applying an epoxy adhesive to metal-plate teeth immediately preceding joint...

Liquid metal embrittlement. [crack propagation in metals with liquid metal in crack space

NASA Technical Reports Server (NTRS)

Tiller, W. A.

1973-01-01

Crack propagation is discussed for metals with liquid metal in the crack space. The change in electrochemical potential of an electron in a metal due to changes in stress level along the crack surface was investigated along with the change in local chemistry, and interfacial energy due to atomic redistribution in the liquid. Coupled elastic-elastrostatic equations, stress effects on electron energy states, and crack propagation via surface roughening are discussed.

Ion adsorption at the rutile-water interface: linking molecular and macroscopic properties.

PubMed

Zhang, Z; Fenter, P; Cheng, L; Sturchio, N C; Bedzyk, M J; Predota, M; Bandura, A; Kubicki, J D; Lvov, S N; Cummings, P T; Chialvo, A A; Ridley, M K; Bénézeth, P; Anovitz, L; Palmer, D A; Machesky, M L; Wesolowski, D J

2004-06-08

A comprehensive picture of the interface between aqueous solutions and the (110) surface of rutile (alpha-TiO2) is being developed by combining molecular-scale and macroscopic approaches, including experimental measurements, quantum calculations, molecular simulations, and Gouy-Chapman-Stern models. In situ X-ray reflectivity and X-ray standing-wave measurements are used to define the atomic arrangement of adsorbed ions, the coordination of interfacial water molecules, and substrate surface termination and structure. Ab initio calculations and molecular dynamics simulations, validated through direct comparison with the X-ray results, are used to predict ion distributions not measured experimentally. Potentiometric titration and ion adsorption results for rutile powders having predominant (110) surface expression provide macroscopic constraints of electrical double layer (EDL) properties (e.g., proton release) which are evaluated by comparison with a three-layer EDL model including surface oxygen proton affinities calculated using ab initio bond lengths and partial charges. These results allow a direct correlation of the three-dimensional, crystallographically controlled arrangements of various species (H2O, Na+, Rb+, Ca2+, Sr2+, Zn2+, Y3+, Nd3+) with macroscopic observables (H+ release, metal uptake, zeta potential) and thermodynamic/electrostatic constraints. All cations are found to be adsorbed as "inner sphere" species bonded directly to surface oxygen atoms, while the specific binding geometries and reaction stoichiometries are dependent on ionic radius. Ternary surface complexes of sorbed cations with electrolyte anions are not observed. Finally, surface oxygen proton affinities computed using the MUSIC model are improved by incorporation of ab initio bond lengths and hydrogen bonding information derived from MD simulations. This multitechnique and multiscale approach demonstrates the compatibility of bond-valence models of surface oxygen proton affinities and Stern-based models of the EDL structure, with the actual molecular interfacial distributions observed experimentally, revealing new insight into EDL properties including specific binding sites and hydration states of sorbed ions, interfacial solvent properties (structure, diffusivity, dielectric constant), surface protonation and hydrolysis, and the effect of solution ionic strength.

Salting out the polar polymorph: analysis by alchemical solvent transformation.

PubMed

Duff, Nathan; Dahal, Yuba Raj; Schmit, Jeremy D; Peters, Baron

2014-01-07

We computationally examine how adding NaCl to an aqueous solution with α- and γ-glycine nuclei alters the structure and interfacial energy of the nuclei. The polar γ-glycine nucleus in pure aqueous solution develops a melted layer of amorphous glycine around the nucleus. When NaCl is added, a double layer is formed that stabilizes the polar glycine polymorph and eliminates the surface melted layer. In contrast, the non-polar α-glycine nucleus is largely unaffected by the addition of NaCl. To quantify the stabilizing effect of NaCl on γ-glycine nuclei, we alchemically transform the aqueous glycine solution into a brine solution of glycine. The alchemical transformation is performed both with and without a nucleus in solution and for nuclei of α-glycine and γ-glycine polymorphs. The calculations show that adding 80 mg/ml NaCl reduces the interfacial free energy of a γ-glycine nucleus by 7.7 mJ/m(2) and increases the interfacial free energy of an α-glycine nucleus by 3.1 mJ/m(2). Both results are consistent with experimental reports on nucleation rates which suggest: J(α, brine) < J(γ, brine) < J(α, water). For γ-glycine nuclei, Debye-Hückel theory qualitatively, but not quantitatively, captures the effect of salt addition. Only the alchemical solvent transformation approach can predict the results for both polar and non-polar polymorphs. The results suggest a general "salting out" strategy for obtaining polar polymorphs and also a general approach to computationally estimate the effects of solvent additives on interfacial free energies for nucleation.

Surface-bubble-modulated liquid chromatography: a new approach for manipulation of chromatographic retention and investigation of solute distribution at water/hydrophobic interfaces.

PubMed

Nakamura, Keisuke; Nakamura, Hiroki; Saito, Shingo; Shibukawa, Masami

2015-01-20

In this paper, we present a new chromatographic method termed surface-bubble-modulated liquid chromatography (SBMLC), that has a hybrid separation medium incorporated with surface nanobubbles. Nanobubbles or nanoscale gas phases can be fixed at the interface between water and a hydrophobic material by delivering water into a dry column packed with a nanoporous material. The incorporation of a gas phase at the hydrophobic surface leads to the formation of the hybrid separation system consisting of the gas phase, hydrophobic moieties, and the water/hydrophobic interface or the interfacial water. One can change the volume of the gas phase by pressure applied to the column, which in turn alters the area of water/hydrophobic interface or the volume of the interfacial water, while the amount of the hydrophobic moiety remains constant. Therefore, this strategy provides a novel technique not only for manipulating the separation selectivity by pressure but also for elucidating the mechanism of accumulation or retention of solute compounds in aqueous solutions by a hydrophobic material. We evaluate the contributions of the interfacial water at the surface of an octadecyl bonded silica and the bonded layer itself to the retention of various solute compounds in aqueous solutions on the column packed with the material by SBMLC. The results show that the interfacial water formed at the hydrophobic surface has a key role in retention even though its volume is rather small. The manipulation of the separation selectivity of SBMLC for some organic compounds by pressure is demonstrated.

Chemically Derivatized Semiconductor Photoelectrodes.

ERIC Educational Resources Information Center

Wrighton, Mark S.

1983-01-01

Deliberate modification of semiconductor photoelectrodes to improve durability and enhance rate of desirable interfacial redox processes is discussed for a variety of systems. Modification with molecular-based systems or with metals/metal oxides yields results indicating an important role for surface modification in devices for fundamental study…

Thickness engineering of atomic layer deposited Al2O3 films to suppress interfacial reaction and diffusion of Ni/Au gate metal in AlGaN/GaN HEMTs up to 600 °C in air

NASA Astrophysics Data System (ADS)

Suria, Ateeq J.; Yalamarthy, Ananth Saran; Heuser, Thomas A.; Bruefach, Alexandra; Chapin, Caitlin A.; So, Hongyun; Senesky, Debbie G.

2017-06-01

In this paper, we describe the use of 50 nm atomic layer deposited (ALD) Al2O3 to suppress the interfacial reaction and inter-diffusion between the gate metal and semiconductor interface, to extend the operation limit up to 600 °C in air. Suppression of diffusion is verified through Auger electron spectroscopy (AES) depth profiling and X-ray diffraction (XRD) and is further supported with electrical characterization. An ALD Al2O3 thin film (10 nm and 50 nm), which functions as a dielectric layer, was inserted between the gate metal (Ni/Au) and heterostructure-based semiconductor material (AlGaN/GaN) to form a metal-insulator-semiconductor high electron mobility transistor (MIS-HEMT). This extended the 50 nm ALD Al2O3 MIS-HEMT (50-MIS) current-voltage (Ids-Vds) and gate leakage (Ig,leakage) characteristics up to 600 °C. Both, the 10 nm ALD Al2O3 MIS-HEMT (10-MIS) and HEMT, failed above 350 °C, as evidenced by a sudden increase of approximately 50 times and 5.3 × 106 times in Ig,leakage, respectively. AES on the HEMT revealed the formation of a Ni-Au alloy and Ni present in the active region. Additionally, XRD showed existence of metal gallides in the HEMT. The 50-MIS enables the operation of AlGaN/GaN based electronics in oxidizing high-temperature environments, by suppressing interfacial reaction and inter-diffusion of the gate metal with the semiconductor.

Tuning interfacial exchange interactions via electronic reconstruction in transition-metal oxide heterostructures

DOE PAGES

Li, Binzhi; Chopdekar, Rajesh V.; N'Diaye, Alpha T.; ...

2016-10-10

The impact of interfacial electronic reconstruction on the magnetic characteristics of La0.7Sr0.3CoO3 (LSCO)/La0.7Sr0.3MnO3 (LSMO) superlattices was investigated as a function of layer thickness using a combination of soft x-ray magnetic spectroscopy and bulk magnetometry. We found that the magnetic properties of the LSCO layers are impacted by two competing electronic interactions occurring at the LSCO/substrate and LSMO/LSCO interfaces. For thin LSCO layers (< 5 nm), the heterostructures exist in a highly coupled state where the chemically distinct layers behave as a single magnetic compound with magnetically active Co2+ ions. As the LSCO thickness increases, a high coercivity LSCO layer developsmore » which biases a low coercivity layer, which is composed not only of the LSMO layer, but also an interfacial LSCO layer. These results suggest a new route to tune the magnetic properties of transition metal oxide heterostructures through careful control of the interface structure.« less

Multiscale Interfacial Strategy to Engineer Mixed Metal-Oxide Anodes toward Enhanced Cycling Efficiency.

PubMed

Ma, Yue; Tai, Cheuk-Wai; Li, Shaowen; Edström, Kristina; Wei, Bingqing

2018-06-13

Interconnected macro/mesoporous structures of mixed metal oxide (MMO) are developed on nickel foam as freestanding anodes for Li-ion batteries. The sustainable production is realized via a wet chemical etching process with bio-friendly chemicals. By means of divalent iron doping during an in situ recrystallization process, the as-developed MMO anodes exhibit enhanced levels of cycling efficiency. Furthermore, this atomic-scale modification coherently synergizes with the encapsulation layer across a micrometer scale. During this step, we develop a quasi-gel-state tri-copolymer, i.e., F127-resorcinol-melamine, as the N-doped carbon source to regulate the interfacial chemistry of the MMO electrodes. Electrochemical tests of the modified Fe x Ni 1- x O@NC-NiF anode in both half-cell and full-cell configurations unravel the favorable suppression of the irreversible capacity loss and satisfactory cyclability at the high rates. This study highlights a proof-of-concept modification strategy across multiple scales to govern the interfacial chemical process of the electrodes toward better reversibility.

Controllable positive exchange bias via redox-driven oxygen migration

DOE PAGES

Gilbert, Dustin A.; Olamit, Justin; Dumas, Randy K.; ...

2016-03-21

We report that ionic transport in metal/oxide heterostructures offers a highly effective means to tailor material properties via modification of the interfacial characteristics. However, direct observation of ionic motion under buried interfaces and demonstration of its correlation with physical properties has been challenging. Using the strong oxygen affinity of gadolinium, we design a model system of Gd xFe 1-x/NiCoO bilayer films, where the oxygen migration is observed and manifested in a controlled positive exchange bias over a relatively small cooling field range. The exchange bias characteristics are shown to be the result of an interfacial layer of elemental nickel andmore » cobalt, a few nanometres in thickness, whose moments are larger than expected from uncompensated NiCoO moments. This interface layer is attributed to a redox-driven oxygen migration from NiCoO to the gadolinium, during growth or soon after. Ultimately, these results demonstrate an effective path to tailoring the interfacial characteristics and interlayer exchange coupling in metal/oxide heterostructures.« less

Performance assessment of polymer based electrodes for in vitro electrophysiological sensing: the role of the electrode impedance

NASA Astrophysics Data System (ADS)

Medeiros, Maria C. R.; Mestre, Ana L. G.; Inácio, Pedro M. C.; Santos, José M. L.; Araujo, Inês M.; Bragança, José; Biscarini, Fabio; Gomes, Henrique L.

2016-09-01

Conducting polymer electrodes based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) are used to record extracellular signals from autonomous cardiac contractile cells and glioma cell cultures. The performance of these conducting polymer electrodes is compared with Au electrodes. A small-signal impedance analysis shows that in the presence of an electrolyte, both Au and polymer electrodes establish high capacitive double-layers. However, the polymer/electrolyte interfacial resistance is 3 orders of magnitude lower than the resistance of the metal/electrolyte interface. The polymer low interfacial resistance minimizes the intrinsic thermal noise and increases the system sensitivity. However, when measurements are carried out in current mode a low interfacial resistance partially acts as a short circuit of the interfacial capacitance, this affects the signal shape.

Interfacial reaction of intermetallic compounds of ultrasonic-assisted brazed joints between dissimilar alloys of Ti6Al4V and Al4Cu1Mg.

PubMed

Ma, Zhipeng; Zhao, Weiwei; Yan, Jiuchun; Li, Dacheng

2011-09-01

Ultrasonic-assisted brazing of Al4Cu1Mg and Ti6Al4V using Zn-based filler metal (without and with Si) has been investigated. Before brazing, the Ti6Al4V samples were pre-treated by hot-dip aluminizing and ultrasonic dipping in a molten filler metal bath in order to control the formation of intermetallic compounds between the Ti6Al4V samples and the filler metal. The results show that the TiAl(3) phase was formed in the interface between the Ti6Al4V substrate and the aluminized coating. For the Zn-based filler metal without Si, the Ti6Al4V interfacial area of the brazed joint did not change under the effect of the ultrasonic wave, and only consisted of the TiAl(3) phase. For the Zn-based filler metal with Si, the TiAl(3) phase disappeared and a Ti(7)Al(5)Si(12) phase was formed at the interfacial area of the brazed joints under the effect of the ultrasonic wave. Due to the TiAl(3) phase completely changing to a Ti(7)Al(5)Si(12) phase, the morphology of the intermetallic compounds changed from a block-like shape into a lamellar-like structure. The highest shear strength of 138MPa was obtained from the brazed joint free of the block-like TiAl(3) phase. Copyright © 2011 Elsevier B.V. All rights reserved.

Potential Barrier Lowering and Electrical Transport at the LaAlO3/SrTiO3 Interface

NASA Astrophysics Data System (ADS)

Suzuki, Yuri

2009-03-01

Interfacial phenomena form the basis for modern-day devices and continue to be an area of fundamental interest in condensed matter research. Advances in oxide thin film fabrication have enabled the synthesis of atomically precise oxide interfaces and hence have allowed for controlled investigation of interfacial phenomena in these materials. With the rich variety of functionalities exhibited by transition-metal oxides, a wide array of novel properties may be achieved at oxide heterointerfaces. An exemplary study is the discovery of metallicity at the interface of two band insulators, LaAlO3 (LAO) and SrTiO3 (STO), which has stimulated many subsequent experimental as well as theoretical studies. However, there is still intense debate on the origin of metallicity, specifically whether it arises from electronic reconstruction or oxygen vacancies. Using a combination of vertical transport measurements across and lateral transport measurements along the LAO/STO heterointerface, we demonstrate that significant potential barrier lowering and band bending are the cause of interfacial metallicity. Transport measurements across the heterointerface, indicate that barrier lowering and enhanced band bending extends over 2.5 nm into LAO as well as STO. We explain the origins of high-temperature carrier saturation, lower carrier concentration, and higher mobility in the sample with the thinnest LAO film on a STO substrate. Lateral transport results suggest that parasitic interface scattering centers limit the low-temperature lateral electron mobility of the metallic channel. [4pt] *In collaboration with Franklin Wong, Miaofang Chi, Rajesh Chopdekar, Brittany Nelson-Cheeseman and Nigel Browning.

On the mechanisms of cation injection in conducting bridge memories: The case of HfO{sub 2} in contact with noble metal anodes (Au, Cu, Ag)

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

Saadi, M.; CNRS, LTM, F-38000 Grenoble; El Manar University, LMOP, 2092 Tunis

Resistance switching is studied in HfO{sub 2} as a function of the anode metal (Au, Cu, and Ag) in view of its application to resistive memories (resistive random access memories, RRAM). Current-voltage (I-V) and current-time (I-t) characteristics are presented. For Au anodes, resistance transition is controlled by oxygen vacancies (oxygen-based resistive random access memory, OxRRAM). For Ag anodes, resistance switching is governed by cation injection (Conducting Bridge random access memory, CBRAM). Cu anodes lead to an intermediate case. I-t experiments are shown to be a valuable tool to distinguish between OxRRAM and CBRAM behaviors. A model is proposed to explainmore » the high-to-low resistance transition in CBRAMs. The model is based on the theory of low-temperature oxidation of metals (Cabrera-Mott theory). Upon electron injection, oxygen vacancies and oxygen ions are generated in the oxide. Oxygen ions are drifted to the anode, and an interfacial oxide is formed at the HfO{sub 2}/anode interface. If oxygen ion mobility is low in the interfacial oxide, a negative space charge builds-up at the HfO{sub 2}/oxide interface. This negative space charge is the source of a strong electric field across the interfacial oxide thickness, which pulls out cations from the anode (CBRAM case). Inversely, if oxygen ions migration through the interfacial oxide is important (or if the anode does not oxidize such as Au), bulk oxygen vacancies govern resistance transition (OxRRAM case).« less

GaN as an interfacial passivation layer: tuning band offset and removing fermi level pinning for III-V MOS devices.

PubMed

Zhang, Zhaofu; Cao, Ruyue; Wang, Changhong; Li, Hao-Bo; Dong, Hong; Wang, Wei-Hua; Lu, Feng; Cheng, Yahui; Xie, Xinjian; Liu, Hui; Cho, Kyeongjae; Wallace, Robert; Wang, Weichao

2015-03-11

The use of an interfacial passivation layer is one important strategy for achieving a high quality interface between high-k and III-V materials integrated into high-mobility metal-oxide-semiconductor field-effect transistor (MOSFET) devices. Here, we propose gallium nitride (GaN) as the interfacial layer between III-V materials and hafnium oxide (HfO2). Utilizing first-principles calculations, we explore the structural and electronic properties of the GaN/HfO2 interface with respect to the interfacial oxygen contents. In the O-rich condition, an O8 interface (eight oxygen atoms at the interface, corresponding to 100% oxygen concentration) displays the most stability. By reducing the interfacial O concentration from 100 to 25%, we find that the interface formation energy increases; when sublayer oxygen vacancies exist, the interface becomes even less stable compared with O8. The band offset is also observed to be highly dependent on the interfacial oxygen concentration. Further analysis of the electronic structure shows that no interface states are present at the O8 interface. These findings indicate that the O8 interface serves as a promising candidate for high quality III-V MOS devices. Moreover, interfacial states are present when such interfacial oxygen is partially removed. The interface states, leading to Fermi level pinning, originate from unsaturated interfacial Ga atoms.

Toward control of the metal-organic interfacial electronic structure in molecular electronics: a first-principles study on self-assembled monolayers of pi-conjugated molecules on noble metals.

PubMed

Heimel, Georg; Romaner, Lorenz; Zojer, Egbert; Brédas, Jean-Luc

2007-04-01

Self-assembled monolayers (SAMs) of organic molecules provide an important tool to tune the work function of electrodes in plastic electronics and significantly improve device performance. Also, the energetic alignment of the frontier molecular orbitals in the SAM with the Fermi energy of a metal electrode dominates charge transport in single-molecule devices. On the basis of first-principles calculations on SAMs of pi-conjugated molecules on noble metals, we provide a detailed description of the mechanisms that give rise to and intrinsically link these interfacial phenomena at the atomic level. The docking chemistry on the metal side of the SAM determines the level alignment, while chemical modifications on the far side provide an additional, independent handle to modify the substrate work function; both aspects can be tuned over several eV. The comprehensive picture established in this work provides valuable guidelines for controlling charge-carrier injection in organic electronics and current-voltage characteristics in single-molecule devices.

Scavenging of oxygen from SrTiO3 by metals and its implications for oxide thin film deposition

NASA Astrophysics Data System (ADS)

Posadas, Agham; Kormondy, Kristy; Guo, Wei; Ponath, Patrick; Kremer, Jacqueline; Hadamek, Tobias; Demkov, Alexander

SrTiO3 is a widely used substrate for the growth of other functional oxide thin films. However, SrTiO3 loses oxygen very easily during oxide thin film deposition even under relatively high oxygen pressures. In some cases, there will be an interfacial layer of oxygen-deficient SrTiO3 formed at the interface with the deposited oxide film, depending on the metals present in the film. By depositing a variety of metals layer by layer and measuring the evolution of the core level spectra of both the deposited metal and SrTiO3 using x-ray photoelectron spectroscopy, we show that there are three distinct types of behavior that occur for thin metal films on SrTiO3. We discuss the implications of these types of behavior for the growth of complex oxide thin films on SrTiO3, and which oxide thin films are expected to produce an interfacial oxygen-deficient layer depending on their elemental constituents.

Metal-organic semiconductor interfacial barrier height determination from internal photoemission signal in spectral response measurements

NASA Astrophysics Data System (ADS)

Kumar, Sandeep; Iyer, S. Sundar Kumar

2017-04-01

Accurate and convenient evaluation methods of the interfacial barrier ϕb for charge carriers in metal semiconductor (MS) junctions are important for designing and building better opto-electronic devices. This becomes more critical for organic semiconductor devices where a plethora of molecules are in use and standardised models applicable to myriads of material combinations for the different devices may have limited applicability. In this paper, internal photoemission (IPE) from spectral response (SR) in the ultra-violet to near infra-red range of different MS junctions of metal-organic semiconductor-metal (MSM) test structures is used to determine more realistic MS ϕb values. The representative organic semiconductor considered is [6, 6]-phenyl C61 butyric acid methyl ester, and the metals considered are Al and Au. The IPE signals in the SR measurement of the MSM device are identified and separated before it is analysed to estimate ϕb for the MS junction. The analysis of IPE signals under different bias conditions allows the evaluation of ϕb for both the front and back junctions, as well as for symmetric MSM devices.

Reduction of benzene and naphthalene mass transfer from crude oils by aging-induced interfacial films.

PubMed

Ghoshal, Subhasis; Pasion, Catherine; Alshafie, Mohammed

2004-04-01

Semi-rigid films or skins form at the interface of crude oil and water as a result of the accumulation of asphaltene and resin fractions when the water-immiscible crude oil is contacted with water for a period of time or "aged". The time varying patterns of area-independent mass transfer coefficients of two compounds, benzene and naphthalene, for dissolution from crude oil and gasoline were determined. Aqueous concentrations of the compounds were measured in the eluent from flow-through reactors, where a nondispersed oil phase and constant oil-water interfacial area were maintained. For Brent Blend crude oil and for gasoline amended with asphaltenes and resins, a rapid decrease in both benzene and naphthalene mass transfer coefficients over the first few days of aging was observed. The mass transfer coefficients of the two target solutes were reduced by up to 80% over 35 d although the equilibrium partition coefficients were unchanged. Aging of gasoline, which has negligible amounts of asphaltene and resin, did not result in a change in the solute mass transfer coefficients. The study demonstrates that formation of crude oil-water interfacial films comprised of asphaltenes and resins contribute to time-dependent decreases in rates of release of environmentally relevant solutes from crude oils and may contribute to the persistence of such solutes at crude oil-contaminated sites. It is estimated that the interfacial film has an extremely low film mass transfer coefficient in the range of 10(-6) cm/min.

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.

Metal-semiconductor interfacial reactions - Ni/Si system

NASA Technical Reports Server (NTRS)

Cheung, N. W.; Grunthaner, P. J.; Grunthaner, F. J.; Mayer, J. W.; Ullrich, B. M.

1981-01-01

X-ray photoelectron spectroscopy and channeling measurements with MeV He-4(+) ions have been used to probe the structure of the interface in the Ni/Si system. It is found that reactions occur where Ni is deposited on Si at 10 to the -10th torr: Si atoms are displaced from lattice sites, the Ni atoms are in an Si-rich environment, and the Ni/Si interface is graded in composition. Composition gradients are present at both interfaces in the Si/Ni2/Si/Ni system. For the Ni-Si system, cooling the substrate to 100 K slows down the reaction rate. The temperature dependence of the interfacial reactivity indicates the kinetic nature of metal-semiconductor interfaces.

Atomic layer deposition of insulating nitride interfacial layers for germanium metal oxide semiconductor field effect transistors with high-κ oxide/tungsten nitride gate stacks

NASA Astrophysics Data System (ADS)

Kim, Kyoung H.; Gordon, Roy G.; Ritenour, Andrew; Antoniadis, Dimitri A.

2007-05-01

Atomic layer deposition (ALD) was used to deposit passivating interfacial nitride layers between Ge and high-κ oxides. High-κ oxides on Ge surfaces passivated by ultrathin (1-2nm) ALD Hf3N4 or AlN layers exhibited well-behaved C-V characteristics with an equivalent oxide thickness as low as 0.8nm, no significant flatband voltage shifts, and midgap density of interface states values of 2×1012cm-1eV-1. Functional n-channel and p-channel Ge field effect transistors with nitride interlayer/high-κ oxide/metal gate stacks are demonstrated.

Interplay between Interfacial Structures and Device Performance in Organic Solar Cells: A Case Study with the Low Work Function Metal, Calcium.

PubMed

Ju, Huanxin; Knesting, Kristina M; Zhang, Wei; Pan, Xiao; Wang, Chia-Hsin; Yang, Yaw-Wen; Ginger, David S; Zhu, Junfa

2016-01-27

A better understanding of how interfacial structure affects charge carrier recombination would benefit the development of highly efficient organic photovoltaic (OPV) devices. In this paper, transient photovoltage (TPV) and charge extraction (CE) measurements are used in combination with synchrotron radiation photoemission spectroscopy (SRPES) to gain insight into the correlation between interfacial properties and device performance. OPV devices based on PCDTBT/PC71BM with a Ca interlayer were studied as a reference system to investigate the interfacial effects on device performance. Devices with a Ca interlayer exhibit a lower recombination than devices with only an Al cathode at a given charge carrier density (n). In addition, the interfacial band structures indicate that the strong dipole moment produced by the Ca interlayer can facilitate the extraction of electrons and drive holes away from the cathode/polymer interface, resulting in beneficial reduction in interfacial recombination losses. These results help explain the higher efficiencies of devices made with Ca interlayers compared to that without the Ca interlayer.

Ionic Liquids as the MOFs/Polymer Interfacial Binder for Efficient Membrane Separation.

PubMed

Lin, Rijia; Ge, Lei; Diao, Hui; Rudolph, Victor; Zhu, Zhonghua

2016-11-23

Obtaining strong interfacial affinity between filler and polymer is critical to the preparation of mixed matrix membranes (MMMs) with high separation efficiency. However, it is still a challenge for micron-sized metal organic frameworks (MOFs) to achieve excellent compatibility and defect-free interface with polymer matrix. Thin layer of ionic liquid (IL) was immobilized on micron-sized HKUST-1 to eliminate the interfacial nonselective voids in MMMs with minimized free ionic liquid (IL) in polymer matrix, and then the obtained IL decorated HKUST-1 was incorporated into 4,4'-(hexafluoroisopropylidene)diphthalic anhydride-2,3,5,6-tetramethyl-1,3-phenyldiamine (6FDA-Durene) to fabricate MMMs. Acting as a filler/polymer interfacial binder, the favorable MOF/IL and IL/polymer interaction can facilitate the enhancement of MOF/polymer affinity. Compared to MMM with only HKUST-1 incorporation, MMM with IL decorated HKUST-1 succeeded in restricting the formation of nonselective interfacial voids, leading to an increment in CO 2 selectivity. The IL decoration method can be an effective approach to eliminate interfacial voids in MMMs, extending the filler selection to a wide range of large-sized fillers.

Pseudopotential Computations for Metal/Alumina Interfaces

NASA Astrophysics Data System (ADS)

Zhang, Wenqing

2003-03-01

Metal/alumina interfaces are found, for example, in electronic devices, as thermal barrier coatings in gas turbines, and in coatings to inhibit corrosion and wear. Of particular importance to their performance is their adhesion. Ultrasoft pseudopotentials combined with plane wave methods and density-functional theory have been employed to compute the properties of these relatively complex interfaces, including effects of impurity segregation. Interfacial stoichiometry and impurity content affect interfacial properties importantly. Thermodynamic links between our first principles results and metallurgical variables such as oxygen activity and oxygen partial pressure are established. This allows for a comparison between theoretical predictions and experimental measurements. Good agreement is obtained for predicted interfacial variables such as atomic structure and adhesive bond strengths on comparison with results of sessile drop, fracture, and other experiments on interfaces of Ni, Cu, Al, and Ag with alumina [1-3], including effects of water and sulfur interfacial impurities. Understanding of the nature of the adhesive bonding at the atomic level is obtained by the pseudopotential first principles approach. [1] W.Zhang, and J.R.Smith, and A.G.Evans, Acta Mater., 50,3803(2002). [2] W.Zhang, and J.R.Smith, Phys. Rev. Lett. 85, 3225(2000). [3] W.Zhang, and J.R.Smith, Phys. Rev. B61, 16883(2000).

Phase constitution in the interfacial region of laser penetration brazed magnesium–steel joints

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

Miao, Yugang; Han, Duanfeng, E-mail: handuanfeng@gmail.com; Xu, Xiangfang

2014-07-01

The phase constitution in the interfacial region of laser penetration brazed magnesium–steel joints was investigated using electron microscopy. From the distribution of elements, the transition zone was mainly composed of elements Mg and Fe along with some Al and O. Furthermore, the transition layer consisted mainly of intermetallic compounds and metal oxides. The compounds were identified as Al-rich phases, such as Mg{sub 17}Al{sub 12}, Mg{sub 2}Al{sub 3}, FeAl and Fe{sub 4}Al{sub 13}. More noteworthy was that the thickness of the transition layer was determined by Fe–Al compounds. The presence of FeAl and Fe{sub 4}Al{sub 13} was a result of themore » complex processes that were associated with the interfacial reaction of solid steel and liquid Mg–Al alloy. - Highlights: • A technology of laser penetration brazed Mg alloy and steel has been developed. • The interface of Mg/Fe dissimilar joints was investigated using electron microscopy. • The transition layer consisted of intermetallic compounds and metal oxides. • Moreover, the thickness of transition layer was determined by Fe/Al compounds. • The presence of FeAl and Fe{sub 4}Al{sub 13} was associated with the interfacial reaction.« less

An improved interfacial bonding model for material interface modeling

PubMed Central

Lin, Liqiang; Wang, Xiaodu; Zeng, Xiaowei

2016-01-01

An improved interfacial bonding model was proposed from potential function point of view to investigate interfacial interactions in polycrystalline materials. It characterizes both attractive and repulsive interfacial interactions and can be applied to model different material interfaces. The path dependence of work-of-separation study indicates that the transformation of separation work is smooth in normal and tangential direction and the proposed model guarantees the consistency of the cohesive constitutive model. The improved interfacial bonding model was verified through a simple compression test in a standard hexagonal structure. The error between analytical solutions and numerical results from the proposed model is reasonable in linear elastic region. Ultimately, we investigated the mechanical behavior of extrafibrillar matrix in bone and the simulation results agreed well with experimental observations of bone fracture. PMID:28584343

Metal-organic frameworks at interfaces of hybrid perovskite solar cells for enhanced photovoltaic properties.

PubMed

Shen, Deli; Pang, Aiying; Li, Yafeng; Dou, Jie; Wei, Mingdeng

2018-01-31

In this study, metal-organic frameworks, as an interfacial layer, were introduced into perovskite solar cells (PSCs) for the first time. An interface modified with the metal-organic framework ZIF-8 efficiently enhanced perovskite crystallinity and grain sizes, and the photovoltaic performance of the PSCs was significantly improved, resulting in a maximum PCE of 16.99%.

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

Lee, Taehoon; Jung, Yong Chan; Seong, Sejong

The metal gate electrodes of Ni, W, and Pt have been investigated for their scavenging effect: a reduction of the GeO{sub x} interfacial layer (IL) between HfO{sub 2} dielectric and Ge substrate in metal/HfO{sub 2}/GeO{sub x}/Ge capacitors. All the capacitors were fabricated using the same process except for the material used in the metal electrodes. Capacitance-voltage measurements, scanning transmission electron microscopy, and electron energy loss spectroscopy were conducted to confirm the scavenging of GeO{sub x} IL. Interestingly, these metals are observed to remotely scavenge the interfacial layer, reducing its thickness in the order of Ni, W, and then Pt. Themore » capacitance equivalent thickness of these capacitors with Ni, W, and Pt electrodes are evaluated to be 2.7 nm, 3.0 nm, and 3.5 nm, and each final remnant physical thickness of GeO{sub x} IL layer is 1.1 nm 1.4 nm, and 1.9 nm, respectively. It is suggested that the scavenging effect induced by the metal electrodes is related to the concentration of oxygen vacancies generated by oxidation reaction at the metal/HfO{sub 2} interface.« less

Quasi-ballistic Electronic Thermal Conduction in Metal Inverse Opals.

PubMed

Barako, Michael T; Sood, Aditya; Zhang, Chi; Wang, Junjie; Kodama, Takashi; Asheghi, Mehdi; Zheng, Xiaolin; Braun, Paul V; Goodson, Kenneth E

2016-04-13

Porous metals are used in interfacial transport applications that leverage the combination of electrical and/or thermal conductivity and the large available surface area. As nanomaterials push toward smaller pore sizes to increase the total surface area and reduce diffusion length scales, electron conduction within the metal scaffold becomes suppressed due to increased surface scattering. Here we observe the transition from diffusive to quasi-ballistic thermal conduction using metal inverse opals (IOs), which are metal films that contain a periodic arrangement of interconnected spherical pores. As the material dimensions are reduced from ∼230 nm to ∼23 nm, the thermal conductivity of copper IOs is reduced by more than 57% due to the increase in surface scattering. In contrast, nickel IOs exhibit diffusive-like conduction and have a constant thermal conductivity over this size regime. The quasi-ballistic nature of electron transport at these length scales is modeled considering the inverse opal geometry, surface scattering, and grain boundaries. Understanding the characteristics of electron conduction at the nanoscale is essential to minimizing the total resistance of porous metals for interfacial transport applications, such as the total electrical resistance of battery electrodes and the total thermal resistance of microscale heat exchangers.

Flexible fiber-reinforced composites with improved interfacial adhesion by mussel-inspired polydopamine and poly(methyl methacrylate) coating.

PubMed

Yi, Mi; Sun, Hongyang; Zhang, Hongcheng; Deng, Xuliang; Cai, Qing; Yang, Xiaoping

2016-01-01

To obtain a kind of light-curable fiber-reinforced composite for dental restoration, an excellent interfacial adhesion between the fiber and the acrylate resin matrix is quite essential. Herein, surface modification on glass fibers were carried out by coating them with poly(methyl methacrylate) (PMMA), polydopamine (PDA), or both. The PMMA or PDA coating was performed by soaking fibers in PMMA/acetone solution or dopamine aqueous solution. PDA/PMMA co-coated glass fibers were obtained by further soaking PDA-coated fibers in PMMA/acetone solution. These modified fibers were impregnated with bisphenol A glycidyl methacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) (5:5, w/w) dental resin at a volume fraction of 75%, using unmodified fibers as reference. Light-cured specimens were submitted to evaluations including flexural properties, morphological observation, dynamic mechanical thermal analysis (DMTA) and pull-out test. In comparison with unmodified glass fibers, all the modified glass fibers showed enhancements in flexural strength and modulus of Bis-GMA/TEGDMA resin composites. Results of DMTA and pull-out tests confirmed that surface modification had significantly improved the interfacial adhesion between the glass fiber and the resin matrix. Particularly, the PDA/PMMA co-coated glass fibers displayed the most efficient reinforcement and the strongest interfacial adhesion due to the synergetic effects of PDA and PMMA. It indicated that co-coating method was a promising approach in modifying the interfacial compatibility between inorganic glass fiber and organic resin matrix. Copyright © 2015 Elsevier B.V. All rights reserved.

Minimizing performance degradation induced by interfacial recombination in perovskite solar cells through tailoring of the transport layer electronic properties

NASA Astrophysics Data System (ADS)

Xu, Liang; Molaei Imenabadi, Rouzbeh; Vandenberghe, William G.; Hsu, Julia W. P.

2018-03-01

The performance of hybrid organic-inorganic metal halide perovskite solar cells is investigated using one-dimensional drift-diffusion device simulations. We study the effects of interfacial defect density, doping concentration, and electronic level positions of the charge transport layer (CTL). Choosing CTLs with a favorable band alignment, rather than passivating CTL-perovskite interfacial defects, is shown to be beneficial for maintaining high power-conversion efficiency, due to reduced minority carrier density arising from a favorable local electric field profile. Insights from this study provide theoretical guidance on practical selection of CTL materials for achieving high-performance perovskite solar cells.

Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF 3SO 2) 2N – at High Current Densities

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

Yoo, Hyun Deog; Han, Sang-Don; Bolotin, Igor L.

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety,stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteriesmore » with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl 2. Hence, ethereal solutions of Mg(TFSI) 2 salt with MgCl 2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm -2 and an areal capacity of ~0.4 mAh cm -2, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI - anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.« less

Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF 3SO 2) 2N – at High Current Densities

DOE PAGES

Yoo, Hyun Deog; Han, Sang-Don; Bolotin, Igor L.; ...

2017-06-21

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety,stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteriesmore » with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl 2. Hence, ethereal solutions of Mg(TFSI) 2 salt with MgCl 2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm -2 and an areal capacity of ~0.4 mAh cm -2, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI - anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.« less

Structure and Electronic Properties of Interface-Confined Oxide Nanostructures

DOE PAGES

Liu, Yun; Ning, Yanxiao; Yu, Liang; ...

2017-09-16

The controlled fabrication of nanostructures has often made use of a substrate template to mediate and control the growth kinetics. Electronic substrate-mediated interactions have been demonstrated to guide the assembly of organic molecules or the nucleation of metal atoms but usually at cryogenic temperatures, where the diffusion has been limited. Combining STM, STS, and DFT studies, we report that the strong electronic interaction between transition metals and oxides could indeed govern the growth of low-dimensional oxide nanostructures. As a demonstration, a series of FeO triangles, which are of the same structure and electronic properties but with different sizes (side lengthmore » >3 nm), are synthesized on Pt(111). The strong interfacial interaction confines the growth of FeO nanostructures, leading to a discrete size distribution and a uniform step structure. Given the same interfacial configuration, as-grown FeO nanostructures not only expose identical edge/surface structure but also exhibit the same electronic properties, as manifested by the local density of states and local work functions. We expect the interfacial confinement effect can be generally applied to control the growth of oxide nanostructures on transition metal surfaces. These oxide nanostructures of the same structure and electronic properties are excellent models for studies of nanoscale effects and applications.« less

Structure and Electronic Properties of Interface-Confined Oxide Nanostructures

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

Liu, Yun; Ning, Yanxiao; Yu, Liang

The controlled fabrication of nanostructures has often made use of a substrate template to mediate and control the growth kinetics. Electronic substrate-mediated interactions have been demonstrated to guide the assembly of organic molecules or the nucleation of metal atoms but usually at cryogenic temperatures, where the diffusion has been limited. Combining STM, STS, and DFT studies, we report that the strong electronic interaction between transition metals and oxides could indeed govern the growth of low-dimensional oxide nanostructures. As a demonstration, a series of FeO triangles, which are of the same structure and electronic properties but with different sizes (side lengthmore » >3 nm), are synthesized on Pt(111). The strong interfacial interaction confines the growth of FeO nanostructures, leading to a discrete size distribution and a uniform step structure. Given the same interfacial configuration, as-grown FeO nanostructures not only expose identical edge/surface structure but also exhibit the same electronic properties, as manifested by the local density of states and local work functions. We expect the interfacial confinement effect can be generally applied to control the growth of oxide nanostructures on transition metal surfaces. These oxide nanostructures of the same structure and electronic properties are excellent models for studies of nanoscale effects and applications.« less

Viscoelastic analysis of a dental metal-ceramic system

NASA Astrophysics Data System (ADS)

Özüpek, Şebnem; Ünlü, Utku Cemal

2012-11-01

Porcelain-fused-to-metal (PFM) restorations used in prosthetic dentistry contain thermal stresses which develop during the cooling phase after firing. These thermal stresses coupled with the stresses produced by mechanical loads may be the dominant reasons for failures in clinical situations. For an accurate calculation of these stresses, viscoelastic behavior of ceramics at high temperatures should not be ignored. In this study, the finite element technique is used to evaluate the effect of viscoelasticity on stress distributions of a three-point flexure test specimen, which is the current international standard, ISO 9693, to characterize the interfacial bond strength of metal-ceramic restorative systems. Results indicate that the probability of interfacial debonding due to normal tensile stress is higher than that due to shear stress. This conclusion suggests modification of ISO 9693 bond strength definition from one in terms of the shear stress only to that accounting for both normal and shear stresses.

The Role of Interfacial Water in Protein-Ligand Binding: Insights from the Indirect Solvent Mediated Potential of Mean Force.

PubMed

Cui, Di; Zhang, Bin W; Matubayasi, Nobuyuki; Levy, Ronald M

2018-02-13

Classical density functional theory (DFT) can be used to relate the thermodynamic properties of solutions to the indirect solvent mediated part of the solute-solvent potential of mean force (PMF). Standard, but powerful numerical methods can be used to estimate the solute-solvent PMF from which the indirect part can be extracted. In this work we show how knowledge of the direct and indirect parts of the solute-solvent PMF for water at the interface of a protein receptor can be used to gain insights about how to design tighter binding ligands. As we show, the indirect part of the solute-solvent PMF is equal to the sum of the 1-body (energy + entropy) terms in the inhomogeneous solvation theory (IST) expansion of the solvation free energy. To illustrate the effect of displacing interfacial water molecules with particular direct/indirect PMF signatures on the binding of ligands, we carry out simulations of protein binding with several pairs of congeneric ligands. We show that interfacial water locations that contribute favorably or unfavorably at the 1-body level (energy + entropy) to the solvation free energy of the solute can be targeted as part of the ligand design process. Water locations where the indirect PMF is larger in magnitude provide better targets for displacement when adding a functional group to a ligand core.

MBE Growth of Ferromagnetic Metal/Compound Semiconductor Heterostructures for Spintronics

ScienceCinema

Palmstrom, Chris [University of California, Santa Barbara, California, United States

2017-12-09

Electrical transport and spin-dependent transport across ferromagnet/semiconductor contacts is crucial in the realization of spintronic devices. Interfacial reactions, the formation of non-magnetic interlayers, and conductivity mismatch have been attributed to low spin injection efficiency. MBE has been used to grow epitaxial ferromagnetic metal/GA(1-x)AL(x)As heterostructures with the aim of controlling the interfacial structural, electronic, and magnetic properties. In situ, STM, XPS, RHEED and LEED, and ex situ XRD, RBS, TEM, magnetotransport, and magnetic characterization have been used to develop ferromagnetic elemental and metallic compound/compound semiconductor tunneling contacts for spin injection. The efficiency of the spin polarized current injected from the ferromagnetic contact has been determined by measuring the electroluminescence polarization of the light emitted from/GA(1-x)AL(x)As light-emitting diodes as a function of applied magnetic field and temperature. Interfacial reactions during MBE growth and post-growth anneal, as well as the semiconductor device band structure, were found to have a dramatic influence on the measured spin injection, including sign reversal. Lateral spin-transport devices with epitaxial ferromagnetic metal source and drain tunnel barrier contacts have been fabricated with the demonstration of electrical detection and the bias dependence of spin-polarized electron injection and accumulation at the contacts. This talk emphasizes the progress and achievements in the epitaxial growth of a number of ferromagnetic compounds/III-V semiconductor heterostructures and the progress towards spintronic devices.

Preparation and characterization of PVDF-glass fiber composite membrane reinforced by interfacial UV-grafting copolymerization.

PubMed

Luo, Nan; Xu, Rongle; Yang, Min; Yuan, Xing; Zhong, Hui; Fan, Yaobo

2015-12-01

A novel inorganic-organic composite membrane, namely poly(vinylidene fluoride) PVDF-glass fiber (PGF) composite membrane, was prepared and reinforced by interfacial ultraviolet (UV)-grafting copolymerization to improve the interfacial bonding strength between the membrane layer and the glass fiber. The interfacial polymerization between inorganic-organic interfaces is a chemical cross-linking reaction that depends on the functionalized glass fiber with silane coupling (KH570) as the initiator and the polymer solution with acrylamide monomer (AM) as the grafting block. The Fourier transform infrared spectrometer-attenuated total reflectance (FTIR-ATR) spectra and the energy dispersive X-ray (EDX) pictures of the interface between the glass fiber and polymer matrix confirmed that the AM was grafted to the surface of the glass fiber fabric and that the grafting polymer was successfully embedded in the membrane matrix. The formation mechanisms, permeation, and anti-fouling performance of the PGF composite membrane were measured with different amounts of AM in the doping solutions. The results showed that the grafting composite membrane improved the interfacial bonding strength and permeability, and the peeling strength was improved by 32.6% for PGF composite membranes with an AM concentration at 2wt.%. Copyright © 2015. Published by Elsevier B.V.

Determination of Halide Concentrations at the Interface of Zwitterionic Micelles by Chemical Trapping: Influence of the Orientation of the Dipole and the Nature of the Cation.

PubMed

Cuccovia; Romsted; Chaimovich

1999-12-01

The interfacial concentrations of Cl(-) and Br(-) in aqueous zwitterionic micelles were determined by chemical trapping by analyzing product yields from spontaneous dediazoniation of micelle-bound 2,6-dimethyl-4-hexadecylbenzenediazonium ion. Interfacial concentrations of Cl(-) and Br(-) in 3-(N-hexadecyl-N, N-dimethylammonio) propane sulfonate, HPS, micelles were higher than in bulk solutions prepared with Li(+), Na(+), Rb(+), Cs(+), tetramethylammonium (TMA(+)), Mg(+2), and Ca(+2) salts. In contrast, the interfacial concentrations of Cl(-) and Br(-) were generally lower than in bulk solution in hexadecylphosphoryl choline, HDPC, micelles for all salts except Mg(+2) and Ca(+2). In both HPS and HDPC micelles the interfacial concentration of Br(-) was higher than that of Cl(-), showing that binding is anion selective. The cation had a large effect on the interfacial concentration of halide ions with HDPC micelles decreasing in the order Ca(2+) > Mg(2+) > Li(+) > Na(+) > K(+) > Cs(+) > Rb(+) > TMA(+). These results are the first direct and extensive determination of local halide ion concentration at the surface of zwitterionic micelles, and they demonstrate that chemical trapping methodology will work in membranes at physiologically relevant salt concentrations. Copyright 1999 Academic Press.

Halo Formation During Solidification of Refractory Metal Aluminide Ternary Systems

NASA Astrophysics Data System (ADS)

D'Souza, N.; Feitosa, L. M.; West, G. D.; Dong, H. B.

2018-02-01

The evolution of eutectic morphologies following primary solidification has been studied in the refractory metal aluminide (Ta-Al-Fe, Nb-Al-Co, and Nb-Al-Fe) ternary systems. The undercooling accompanying solid growth, as related to the extended solute solubility in the primary and secondary phases can be used to account for the evolution of phase morphologies during ternary eutectic solidification. For small undercooling, the conditions of interfacial equilibrium remain valid, while in the case of significant undercooling when nucleation constraints occur, there is a departure from equilibrium leading to unexpected phases. In Ta-Al-Fe, an extended solubility of Fe in σ was observed, which was consistent with the formation of a halo of μ phase on primary σ. In Nb-Al-Co, a halo of C14 is formed on primary CoAl, but very limited vice versa. However, in the absence of a solidus projection it was not possible to definitively determine the extended solute solubility in the primary phase. In Nb-Al-Fe when nucleation constraints arise, the inability to initiate coupled growth of NbAl3 + C14 leads to the occurrence of a two-phase halo of C14 + Nb2Al, indicating a large undercooling and departure from equilibrium.

Fibrillization kinetics of insulin solution in an interfacial shearing flow

NASA Astrophysics Data System (ADS)

Balaraj, Vignesh; McBride, Samantha; Hirsa, Amir; Lopez, Juan

2015-11-01

Although the association of fibril plaques with neurodegenerative diseases like Alzheimer's and Parkinson's is well established, in-depth understanding of the roles played by various physical factors in seeding and growth of fibrils is far from well known. Of the numerous factors affecting this complex phenomenon, the effect of fluid flow and shear at interfaces is paramount as it is ubiquitous and the most varying factor in vivo. Many amyloidogenic proteins have been found to denature upon contact at hydrophobic interfaces due to the self-assembling nature of protein in its monomeric state. Here, fibrillization kinetics of insulin solution is studied in an interfacial shearing flow. The transient surface rheological response of the insulin solution to the flow and its effect on the bulk fibrillization process has been quantified. Minute differences in hydrophobic characteristics between two variants of insulin- Human recombinant and Bovine insulin are found to result in very different responses. Results presented will be in the form of fibrillization assays, images of fibril plaques formed, and changes in surface rheological properties of the insulin solution. The interfacial velocity field, measured from images (via Brewster Angle Microscopy), is compared with computations. Supported by NNX13AQ22G, National Aeronautics and Space Administration.

Micro-mechanics modelling of smart materials

NASA Astrophysics Data System (ADS)

Shah, Syed Asim Ali

Metal Matrix ceramic-reinforced composites are rapidly becoming strong candidates as structural materials for many high temperature and engineering applications. Metal matrix composites (MMC) combine the ductile properties of the matrix with a brittle phase of the reinforcement, leading to high stiffness and strength with a reduction in structural weight. The main objective of using a metal matrix composite system is to increase service temperature or improve specific mechanical properties of structural components by replacing existing super alloys.The purpose of the study is to investigate, develop and implement second phase reinforcement alloy strengthening empirical model with SiCp reinforced A359 aluminium alloy composites on the particle-matrix interface and the overall mechanical properties of the material.To predict the interfacial fracture strength of aluminium, in the presence of silicon segregation, an empirical model has been modified. This model considers the interfacial energy caused by segregation of impurities at the interface and uses Griffith crack type arguments to predict the formation energies of impurities at the interface. Based on this, model simulations were conducted at nano scale specifically at the interface and the interfacial strengthening behaviour of reinforced aluminium alloy system was expressed in terms of elastic modulus.The numerical model shows success in making prediction possible of trends in relation to segregation and interfacial fracture strength behaviour in SiC particle-reinforced aluminium matrix composites. The simulation models using various micro scale modelling techniques to the aluminum alloy matrix composite, strengthenedwith varying amounts of silicon carbide particulate were done to predict the material state at critical points with properties of Al-SiC which had been heat treated.In this study an algorithm is developed to model a hard ceramic particle in a soft matrix with a clear distinct interface and a strain based relationship has been proposed for the strengthening behaviour of the MMC at the interface rather than stress based, by successfully completing the numerical modelling of particulate reinforced metal matrix composites.

Fabrication and Evaluation of One-Axis Oriented Lead Zirconate Titanate Films Using Metal-Oxide Nanosheet Interface Layer

NASA Astrophysics Data System (ADS)

Minemura, Yoshiki; Nagasaka, Kohei; Kiguchi, Takanori; Konno, Toyohiko J.; Funakubo, Hiroshi; Uchida, Hiroshi

2013-09-01

Nanosheet Ca2Nb3O20 (ns-CN) layers with pseudo-perovskite-type crystal configuration were applied on the surface of polycrystalline metal substrates to achieve preferential crystal orientation of Pb(Zr,Ti)O3 (PZT) films for the purpose of enhanced ferroelectricity comparable to that of epitaxial thin films. PZT films with tetragonal symmetry (Zr/Ti=0.40:0.60) were fabricated by chemical solution deposition (CSD) on ns-CN-buffered Inconel 625 and SUS 316L substrates, while ns-CN was applied on the the substrates by dip-coating. The preferential crystal growth on the ns-CN layer can be achieved by favorable lattice matching between (001)/(100)PZT and (001)ns-CN planes. The degree of (001) orientation was increased for PZT films on ns-CN/Inconel 625 and ns-CN/SUS 316L substrates, whereas randomly-oriented PZT films with a lower degree of (001) orientation were grown on bare and Inconel 625 films. Enhanced remanent polarization of 60 µC/cm2 was confirmed for the PZT films on ns-CN/metal substrates, ascribed to the preferential alignment of the polar [001] axis normal to the substrate surface, although it also suffered from higher coercive field above 500 kV/cm caused by PZT/metal interfacial reaction.

Nb and Ta layer doping effects on the interfacial energetics and electronic properties of LaAlO3/SrTiO3 heterostructure: first-principles analysis.

PubMed

Nazir, Safdar; Behtash, Maziar; Cheng, Jianli; Luo, Jian; Yang, Kesong

2016-01-28

The two-dimensional electron gas (2DEG) formed at the n-type (LaO)(+1)/(TiO2)(0) interface in the polar/nonpolar LaAlO3/SrTiO3 (LAO/STO) heterostructure (HS) has emerged as a prominent research area because of its great potential for nanoelectronic applications. Due to its practical implementation in devices, desired physical properties such as high charge carrier density and mobility are vital. In this respect, 4d and 5d transition metal doping near the interfacial region is expected to tailor electronic properties of the LAO/STO HS system effectively. Herein, we studied Nb and Ta-doping effects on the energetics, electronic structure, interfacial charge carrier density, magnetic moment, and the charge confinements of the 2DEG at the n-type (LaO)(+1)/(TiO2)(0) interface of LAO/STO HS using first-principles density functional theory calculations. We found that the substitutional doping of Nb(Ta) at Ti [Nb(Ta)@Ti] and Al [Nb(Ta)@Al] sites is energetically more favorable than that at La [Nb(Ta)@La] and Sr [Nb(Ta)@Sr] sites, and under appropriate thermodynamic conditions, the changes in the interfacial energy of HS systems upon Nb(Ta)@Ti and Nb(Ta)@Al doping are negative, implying that the formation of these structures is energetically favored. Our calculations also showed that Nb(Ta)@Ti and Nb(Ta)@Al doping significantly improve the interfacial charge carrier density with respect to that of the undoped system, which is because the Nb(Ta) dopant introduces excess free electrons into the system, and these free electrons reside mainly on the Nb(Ta) ions and interfacial Ti ions. Hence, along with the Ti 3d orbitals, the Nb 4d and Ta 5d orbitals also contribute to the interfacial metallic states; accordingly, the magnetic moments on the interfacial Ti ions increase significantly. As expected, the Nb@Al and Ta@Al doped LAO/STO HS systems show higher interfacial charge carrier density than the undoped and other doped systems. In contrast, Nb@Ti and Ta@Ti doped systems may show higher charge carrier mobility because of the lower electron effective mass.

Environmentally-assisted technique for transferring devices onto non-conventional substrates

DOEpatents

Lee, Chi-Hwan; Kim, Dong Rip; Zheng, Xiaolin

2016-05-10

A device fabrication method includes: (1) providing a growth substrate including an oxide layer; (2) forming a metal layer over the oxide layer; (3) forming a stack of device layers over the metal layer; (4) performing fluid-assisted interfacial debonding of the metal layer to separate the stack of device layers and the metal layer from the growth substrate; and (5) affixing the stack of device layers to a target substrate.

Quantifying the Pathway and Predicting Spontaneous Emulsification during Material Exchange in a Two Phase Liquid System.

PubMed

Spooner, Stephen; Rahnama, Alireza; Warnett, Jason M; Williams, Mark A; Li, Zushu; Sridhar, Seetharaman

2017-10-30

Kinetic restriction of a thermodynamically favourable equilibrium is a common theme in materials processing. The interfacial instability in systems where rate of material exchange is far greater than the mass transfer through respective bulk phases is of specific interest when tracking the transient interfacial area, a parameter integral to short processing times for productivity streamlining in all manufacturing where interfacial reaction occurs. This is even more pertinent in high-temperature systems for energy and cost savings. Here the quantified physical pathway of interfacial area change due to material exchange in liquid metal-molten oxide systems is presented. In addition the predicted growth regime and emulsification behaviour in relation to interfacial tension as modelled using phase-field methodology is shown. The observed in-situ emulsification behaviour links quantitatively the geometry of perturbations as a validation method for the development of simulating the phenomena. Thus a method is presented to both predict and engineer the formation of micro emulsions to a desired specification.

Amine-Modulated/Engineered Interfaces of NiMo Electrocatalysts for Improved Hydrogen Evolution Reaction in Alkaline Solutions.

PubMed

Gao, Wei; Gou, Wangyan; Zhou, Xuemei; Ho, Johnny C; Ma, Yuanyuan; Qu, Yongquan

2018-01-17

The interface between electrolytes and electrocatalysts would largely determine their corresponding activity and stability. Herein, modulating the surface characteristics of NiMo nanoparticles by various adsorbed amines gives the tunability on their interfacial properties and subsequently improves their catalytic performance for hydrogen evolution reaction (HER) in alkaline solutions. Diamines can significantly improve their HER activity by decreasing the charge-transfer resistance and modulating the electronic structures of interfacial active sites. Importantly, among various amines, ethylenediamine facilitates the HER activity of NiMo with a remarkable decrease of 268 mV in the overpotential to reach 10 mA cm -2 as compared with that of the unmodified NiMo in 1.0 M KOH. This method provides a novel strategy of regulating the interfacial properties to strengthen the catalytic performance of electrocatalysts.

Changes in the adsorbate dipole layer with changing d-filling of the metal (II) (Co, Ni, Cu) phthalocyanines on Au(111).

PubMed

Xiao, Jie; Dowben, Peter A

2009-02-04

In combined photoemission and inverse photoemission spectroscopy studies, we observe changes in the metal phthalocyanine molecular orbital offsets with respect to the conducting gold substrate Fermi level, with the changing d-electron filling of the metal (II) (Co, Ni, Cu) phthalocyanines. The implication is that the interfacial dipole layer depends upon the choice of metal (Co, Ni, Cu) centers within the metal (II) phthalocyanines adsorbed on Au(111).

Fischer Indole Synthesis in the Gas Phase, the Solution Phase, and at the Electrospray Droplet Interface.

PubMed

Bain, Ryan M; Ayrton, Stephen T; Cooks, R Graham

2017-07-01

Previous reports have shown that reactions occurring in the microdroplets formed during electrospray ionization can, under the right conditions, exhibit significantly greater rates than the corresponding bulk solution-phase reactions. The observed acceleration under electrospray ionization could result from a solution-phase, a gas-phase, or an interfacial reaction. This study shows that a gas-phase ion/molecule (or ion/ion) reaction is not responsible for the observed rate enhancement in the particular case of the Fischer indole synthesis. The results show that the accelerated reaction proceeds in the microdroplets, and evidence is provided that an interfacial process is involved. Graphical Abstract .

Nonequilibrium thermodynamics and boundary conditions for reaction and transport in heterogeneous media

NASA Astrophysics Data System (ADS)

Gaspard, Pierre; Kapral, Raymond

2018-05-01

Nonequilibrium interfacial thermodynamics is formulated in the presence of surface reactions for the study of diffusiophoresis in isothermal systems. As a consequence of microreversibility and Onsager-Casimir reciprocal relations, diffusiophoresis, i.e., the coupling of the tangential components of the pressure tensor to the concentration gradients of solute species, has a reciprocal effect where the interfacial currents of solutes are coupled to the slip velocity. The presence of surface reactions is shown to modify the diffusiophoretic and reciprocal effects at the fluid-solid interface. The thin-layer approximation is used to describe the solution flowing near a reactive solid interface. Analytic formulas describing the diffusiophoretic and reciprocal effects are deduced in the thin-layer approximation and tested numerically for the Poiseuille flow of a solution between catalytic planar surfaces.

Manipulating the Interfacial Electrical and Optical Properties of Dissimilar Materials with Metallic Nanostructures

DTIC Science & Technology

2016-07-30

27TH STREET STE 4308 AUSTIN , TX 78712 08/03/2016 Final Report DISTRIBUTION A: Distribution approved for public release. Air Force Research ...4308 Austin , TX 78712-1500 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) Air Force Office of...AFRL-AFOSR-VA-TR-2016-0281 MANIPULATING THE INTERFACIAL ELECTRIAL & OPTICAL PROPERTIES OF DISSIMILA Seth Bank UNIVERSITY OF TEXAS AT AUSTIN 101 EAST

Quantitative phase-field lattice-Boltzmann study of lamellar eutectic growth under natural convection

NASA Astrophysics Data System (ADS)

Zhang, A.; Guo, Z.; Xiong, S.-M.

2018-05-01

The influence of natural convection on lamellar eutectic growth was determined by a comprehensive phase-field lattice-Boltzmann study for Al-Cu and CB r4-C2C l6 eutectic alloys. The mass differences resulting from concentration differences led to the fluid flow and a robust parallel and adaptive mesh refinement algorithm was employed to improve the computational efficiency. By means of carefully designed "numerical experiments", the eutectic growth under natural convection was explored and a simple analytical model was proposed to predict the adjustment of the lamellar spacing. Furthermore, by alternating the solute expansion coefficient, initial lamellar spacing, and undercooling, the microstructure evolution was presented and compared with the classical eutectic growth theory. Results showed that both interfacial solute distribution and average curvature were affected by the natural convection, the effect of which could be further quantified by adding a constant into the growth rule proposed by Jackson and Hunt [Jackson and Hunt, Trans. Metall. Soc. AIME 236, 1129 (1966)].

Mechanical reliability and life prediction of coated metallic interconnects within solid oxide fuel cells

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

Xu, Zhijie; Xu, Wei; Stephens, Elizabeth

Metallic cell interconnects (IC) made of ferritic stainless steels, i.e., iron-based alloys, have been increasingly favored in the recent development of planar solid oxide fuel cells (SOFCs) because of their advantages in excellent imperviousness, low electrical resistance, ease in fabrication, and cost effectiveness. Typical SOFC operating conditions inevitably lead to the formation of oxide scales on the surface of ferritic stainless steel, which could cause delamination, buckling, and spallation resulting from the mismatch of the coefficient of thermal expansion and eventually reduce the lifetime of the interconnect components. Various protective coating techniques have been applied to alleviate these drawbacks. Inmore » the present work, a fracture-mechanics-based quantitative modeling framework has been established to predict the mechanical reliability and lifetime of the spinel-coated, surface-modified specimens under an isothermal cooling cycle. Analytical solutions have been formulated to evaluate the scale/substrate interfacial strength and determine the critical oxide thickness in terms of a variety of design factors, such as coating thickness, material properties, and uncertainties. In conclusion, the findings then are correlated with the experimentally measured oxide scale growth kinetics to quantify the predicted lifetime of the metallic interconnects.« less

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering.

PubMed

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-09-21

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal-air batteries. Herein, we report the novel system of nickel-aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

NASA Astrophysics Data System (ADS)

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-09-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal-air batteries. Herein, we report the novel system of nickel-aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles.

Mechanical reliability and life prediction of coated metallic interconnects within solid oxide fuel cells

DOE PAGES

Xu, Zhijie; Xu, Wei; Stephens, Elizabeth; ...

2017-07-03

Metallic cell interconnects (IC) made of ferritic stainless steels, i.e., iron-based alloys, have been increasingly favored in the recent development of planar solid oxide fuel cells (SOFCs) because of their advantages in excellent imperviousness, low electrical resistance, ease in fabrication, and cost effectiveness. Typical SOFC operating conditions inevitably lead to the formation of oxide scales on the surface of ferritic stainless steel, which could cause delamination, buckling, and spallation resulting from the mismatch of the coefficient of thermal expansion and eventually reduce the lifetime of the interconnect components. Various protective coating techniques have been applied to alleviate these drawbacks. Inmore » the present work, a fracture-mechanics-based quantitative modeling framework has been established to predict the mechanical reliability and lifetime of the spinel-coated, surface-modified specimens under an isothermal cooling cycle. Analytical solutions have been formulated to evaluate the scale/substrate interfacial strength and determine the critical oxide thickness in terms of a variety of design factors, such as coating thickness, material properties, and uncertainties. In conclusion, the findings then are correlated with the experimentally measured oxide scale growth kinetics to quantify the predicted lifetime of the metallic interconnects.« less

The Role of Interfacial Electronic Properties on Phonon Transport in Two-Dimensional MoS 2 on Metal Substrates

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

Yan, Zhequan; Chen, Liang; Yoon, Mina

2016-11-08

In this paper, we investigate the role of interfacial electronic properties on the phonon transport in two-dimensional MoS 2 adsorbed on metal substrates (Au and Sc) using first-principles density functional theory and the atomistic Green’s function method. Our study reveals that the different degree of orbital hybridization and electronic charge distribution between MoS 2 and metal substrates play a significant role in determining the overall phonon–phonon coupling and phonon transmission. The charge transfer caused by the adsorption of MoS 2 on Sc substrate can significantly weaken the Mo–S bond strength and change the phonon properties of MoS 2, which resultmore » in a significant change in thermal boundary conductance (TBC) from one lattice-stacking configuration to another for same metallic substrate. In a lattice-stacking configuration of MoS 2/Sc, weakening of the Mo–S bond strength due to charge redistribution results in decrease in the force constant between Mo and S atoms and substantial redistribution of phonon density of states to low-frequency region which affects overall phonon transmission leading to 60% decrease in TBC compared to another configuration of MoS 2/Sc. Strong chemical coupling between MoS 2 and the Sc substrate leads to a significantly (~19 times) higher TBC than that of the weakly bound MoS 2/Au system. Our findings demonstrate the inherent connection among the interfacial electronic structure, the phonon distribution, and TBC, which helps us understand the mechanism of phonon transport at the MoS 2/metal interfaces. Finally, the results provide insights for the future design of MoS 2-based electronics and a way of enhancing heat dissipation at the interfaces of MoS 2-based nanoelectronic devices.« less

Overview: Experimental studies of crystal nucleation: Metals and colloids.

PubMed

Herlach, Dieter M; Palberg, Thomas; Klassen, Ina; Klein, Stefan; Kobold, Raphael

2016-12-07

Crystallization is one of the most important phase transformations of first order. In the case of metals and alloys, the liquid phase is the parent phase of materials production. The conditions of the crystallization process control the as-solidified material in its chemical and physical properties. Nucleation initiates the crystallization of a liquid. It selects the crystallographic phase, stable or meta-stable. Its detailed knowledge is therefore mandatory for the design of materials. We present techniques of containerless processing for nucleation studies of metals and alloys. Experimental results demonstrate the power of these methods not only for crystal nucleation of stable solids but in particular also for investigations of crystal nucleation of metastable solids at extreme undercooling. This concerns the physical nature of heterogeneous versus homogeneous nucleation and nucleation of phases nucleated under non-equilibrium conditions. The results are analyzed within classical nucleation theory that defines the activation energy of homogeneous nucleation in terms of the interfacial energy and the difference of Gibbs free energies of solid and liquid. The interfacial energy acts as barrier for the nucleation process. Its experimental determination is difficult in the case of metals. In the second part of this work we therefore explore the potential of colloidal suspensions as model systems for the crystallization process. The nucleation process of colloids is observed in situ by optical observation and ultra-small angle X-ray diffraction using high intensity synchrotron radiation. It allows an unambiguous discrimination of homogeneous and heterogeneous nucleation as well as the determination of the interfacial free energy of the solid-liquid interface. Our results are used to construct Turnbull plots of colloids, which are discussed in relation to Turnbull plots of metals and support the hypothesis that colloids are useful model systems to investigate crystal nucleation.

Tunable surface plasmon devices

DOEpatents

Shaner, Eric A [Rio Rancho, NM; Wasserman, Daniel [Lowell, MA

2011-08-30

A tunable extraordinary optical transmission (EOT) device wherein the tunability derives from controlled variation of the dielectric constant of a semiconducting material (semiconductor) in evanescent-field contact with a metallic array of sub-wavelength apertures. The surface plasmon resonance wavelength can be changed by changing the dielectric constant of the dielectric material. In embodiments of this invention, the dielectric material is a semiconducting material. The dielectric constant of the semiconducting material in the metal/semiconductor interfacial region is controllably adjusted by adjusting one or more of the semiconductor plasma frequency, the concentration and effective mass of free carriers, and the background high-frequency dielectric constant in the interfacial region. Thermal heating and/or voltage-gated carrier-concentration changes may be used to variably adjust the value of the semiconductor dielectric constant.

Metal/ceramic interface structures and segregation behavior in aluminum-based composites

DOE PAGES

Zhang, Xinming; Hu, Tao; Rufner, Jorgen F.; ...

2015-06-14

Trimodal Al alloy (AA) matrix composites consisting of ultrafine-­grained (UFG) and coarse-­ grained (CG) Al phases and micron-­sized B 4C ceramic reinforcement particles exhibit combinations of strength and ductility that render them useful for potential applications in the aerospace, defense and automotive industries. Tailoring of microstructures with specific mechanical properties requires a detailed understanding of interfacial structures to enable strong interface bonding between ceramic reinforcement and metal matrix, and thereby allow for effective load transfer. Trimodal AA metal matrix composites typically show three characteristics that are noteworthy: nanocrystalline grains in the vicinity of the B4C reinforcement particles; Mg segregation atmore » AA/B 4C interfaces; and the presence of amorphous interfacial layers separating nanocrystalline grains from B 4C particles. Interestingly, however, fundamental information related to the mechanisms responsible for these characteristics as well as information on local compositions and phases are absent in the current literature. Here in this study, we use high-­resolution transmission electron microscopy, energy-­dispersive X-­ray spectroscopy, electron energy-­loss spectroscopy, and precession assisted electron diffraction to gain fundamental insight into the mechanisms that affect the characteristics of AA/B 4C interfaces. Specifically, we determined interfacial structures, local composition and spatial distribution of the interfacial constituents. Near atomic resolution characterization revealed amorphous multilayers and a nanocrystalline region between Al phase and B 4C reinforcement particles. The amorphous multilayers consist of nonstoichiometric Al xO y, while the nanocrystalline region is comprised of MgO nanograins. The experimental results are discussed in terms of the possible underlying mechanisms at AA/B 4C interfaces.« less

Environmentally-assisted technique for transferring devices onto non-conventional substrates

DOEpatents

Lee, Chi-Hwan; Kim, Dong Rip; Zheng, Xiaolin

2014-08-26

A device fabrication method includes: (1) providing a growth substrate including a base and an oxide layer disposed over the base; (2) forming a metal layer over the oxide layer; (3) forming a stack of device layers over the metal layer; (4) performing interfacial debonding of the metal layer to separate the stack of device layers and the metal layer from the growth substrate; and (5) affixing the stack of device layers to a target substrate.

An Unusual Salt Effect in an Interfacial Nucleophilic Substitution Reaction.

PubMed

Li, Shuheng; Mrksich, Milan

2018-06-12

This paper reports a kinetic characterization of the interfacial reaction of N-methylpyrrolidine with a self-assembled monolayer presenting an iodoalkyl group. SAMDI (self-assembled monolayers for matrix-assisted laser desorption/ionization) mass spectrometry was used to determine the extent of reaction for monolayers that were treated with a range of concentrations of the nucleophile for a range of times. These data revealed a second-order rate constant for the reaction that was approximately 100-fold greater than that for the analogous solution-phase reaction. However, addition of sodium iodide to the reaction mixture resulted in a 7-fold decrease in the reaction rate. Addition of bromide and chloride salts also gave slower rate constants for the reaction, but only at 100- and 1000-fold higher concentrations than was observed with iodide, respectively. The corresponding solution-phase reactions, by contrast, had rate constants that were unaffected by the concentration of halide salts. This work provides a well-characterized example illustrating the extent to which the kinetics and properties of an interfacial reaction can depart substantially from their better-understood solution-phase counterparts.

Interfacial magnetic coupling in hetero-structure of Fe/double-perovskite NdBaMn2O6 single crystal

NASA Astrophysics Data System (ADS)

Lin, W. C.; Tsai, C. L.; Ogawa, K.; Yamada, S.; Gandhi, Ashish C.; Lin, J. G.

2018-04-01

The interfacial magnetic coupling between metallic Fe and the double-perovskite NdBaMn2O6 single crystal was investigated in the heterostructure of 4-nm Pd/10-nm Fe/NdBaMn2O6. A considerable magnetic coupling effect was observed in the temperature range coincident with the magnetic phase transition of NdBaMn2O6. When the temperature was elevated above 270 K, NdBaMn2O6 transformed from a state of antiferromagnetic fluctuating domains to a superparamagnetism-like (ferromagnetic fluctuation) state with high magnetic susceptibility. Concurrently, the interfacial magnetic coupling between the Fe layer and the NdBaMn2O6 crystal was observed, as indicated by the considerable squareness reduction and coercivity enhancement in the Fe layer. Moreover, the presence of the Fe layer changed the magnetic structure of NdBaMn2O6 from conventional 4-fold symmetry to 2-fold symmetry. These observations offer applicable insights into the mutual magnetic interaction in the heterostructures of metallic ferromagnetism/perovskite materials.

Spontaneous Self-Formation of 3D Plasmonic Optical Structures.

PubMed

Choi, Inhee; Shin, Yonghee; Song, Jihwan; Hong, SoonGweon; Park, Younggeun; Kim, Dongchoul; Kang, Taewook; Lee, Luke P

2016-08-23

Self-formation of colloidal oil droplets in water or water droplets in oil not only has been regarded as fascinating fundamental science but also has been utilized in an enormous number of applications in everyday life. However, the creation of three-dimensional (3D) architectures by a liquid droplet and an immiscible liquid interface has been less investigated than other applications. Here, we report interfacial energy-driven spontaneous self-formation of a 3D plasmonic optical structure at room temperature without an external force. Based on the densities and interfacial energies of two liquids, we simulated the spontaneous formation of a plasmonic optical structure when a water droplet containing metal ions meets an immiscible liquid polydimethylsiloxane (PDMS) interface. At the interface, the metal ions in the droplet are automatically reduced to form an interfacial plasmonic layer as the liquid PDMS cures. The self-formation of both an optical cavity and integrated plasmonic nanostructure significantly enhances the fluorescence by a magnitude of 1000. Our findings will have a huge impact on the development of various photonic and plasmonic materials as well as metamaterials and devices.

Role of interfacial transition layers in VO2/Al2O3 heterostructures

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

Zhou, Honghui; Chisholm, Matthew F; Yang, Tsung-Han

2011-01-01

Epitaxial VO2 films grown by pulsed laser deposition (PLD) on c-cut sapphire substrates ((0001) Al2O3) were studied by aberration-corrected scanning transmission electron microscopy (STEM). A number of film/substrate orientation relationships were found and are discussed in the context of the semiconductor-metal transition (SMT) characteristics. A structurally and electronically modified buffer layer was revealed on the interface and was attributed to the interface free-energy minimization process of accommodating the symmetry mismatch between the substrate and the film. This interfacial transition layer is expected to affect the SMT behavior when the interfacial region is a significant fraction of the VO2 film thickness.

Nanoscale doping heterogeneity in few-layer WSe2 exfoliated onto noble metals revealed by correlated SPM and TERS imaging

NASA Astrophysics Data System (ADS)

Jariwala, Deep; Krayev, Andrey; Wong, Joeson; Robinson, A. Edward; Sherrott, Michelle C.; Wang, Shuo; Liu, Gang-Yu; Terrones, Mauricio; Atwater, Harry A.

2018-07-01

While extensive research effort has been devoted to the study of the 2D semiconductor–insulator interfaces in transition metal dichalcogenides (TMDCs), there is little knowledge about the electronic quality of the semiconductor–metal interface in the atomically thin limit. Here, we present the first correlated nanoscale mapping of the interface of atomically thin WSe2 with noble metals using co-localized scanning probe microscopy and tip-enhanced optical spectroscopy (TEOS), such as tip-enhanced Raman spectroscopy (TERS). Nanoscale maps of the topography, surface potential, Raman spectra, and the photocurrent amplitude of the WSe2/metal interfaces reveal striking results. Specifically, correlations between surface potential, resonant Raman signatures and photocurrents that indicate the presence of inhomogeneities within interfacial electronic properties, which we attribute to variations in the local doping of the WSe2 likely caused by intrinsic compositional fluctuations or defects. Our results suggest that local electrostatic variations at a lateral scale of 10–100 nm are present even in the highest quality of TMDC crystals and must be considered towards understanding of all interfacial phenomena, particularly in device applications that rely on the buried metal–semiconductor junction interface.

Hydrogen release at metal-oxide interfaces: A first principle study of hydrogenated Al/SiO2 interfaces

NASA Astrophysics Data System (ADS)

Huang, Jianqiu; Tea, Eric; Li, Guanchen; Hin, Celine

2017-06-01

The Anode Hydrogen Release (AHR) mechanism at interfaces is responsible for the generation of defects, that traps charge carriers and can induce dielectric breakdown in Metal-Oxide-Semiconductor Field Effect Transistors. The AHR has been extensively studied at Si/SiO2 interfaces but its characteristics at metal-silica interfaces remain unclear. In this study, we performed Density Functional Theory (DFT) calculations to study the hydrogen release mechanism at the typical Al/SiO2 metal-oxide interface. We found that interstitial hydrogen atoms can break interfacial Alsbnd Si bonds, passivating a Si sp3 orbital. Interstitial hydrogen atoms can also break interfacial Alsbnd O bonds, or be adsorbed at the interface on aluminum, forming stable Alsbnd Hsbnd Al bridges. We showed that hydrogenated Osbnd H, Sisbnd H and Alsbnd H bonds at the Al/SiO2 interfaces are polarized. The resulting bond dipole weakens the Osbnd H and Sisbnd H bonds, but strengthens the Alsbnd H bond under the application of a positive bias at the metal gate. Our calculations indicate that Alsbnd H bonds and Osbnd H bonds are more important than Sisbnd H bonds for the hydrogen release process.

Oxidation/reduction reactions at the metal contact-TlBr interface: an x-ray photoelectron spectroscopy study

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Swanberg, E. L.; Voss, L. F.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Kim, H.; Cirignano, L.; Shah, K.

2014-09-01

TlBr radiation detector operation degrades with time at room temperature and is thought to be due to electromigration of Tl and Br vacancies within the crystal as well as the metal contacts migrating into the TlBr crystal itself due to electrochemical reactions at the metal/TlBr interface. X-ray photoemission spectroscopy (XPS) was used to investigate the metal contact surface/interfacial structure on TlBr devices. Device-grade TlBr was polished and subjected to a 32% HCl etch to remove surface damage prior to Mo or Pt contact deposition. High-resolution photoemission measurements on the Tl 4f, Br 3d, Cl 2p, Mo 3d and Pt 4f core lines were used to evaluate surface chemistry and non-equilibrium interfacial diffusion. Results indicate that anion substitution at the TlBr surface due to the HCl etch forms TlBr1-xClx with consequent formation of a shallow heterojunction. In addition, a reduction of Tl1+ to Tl0 is observed at the metal contacts after device operation in both air and N2 at ambient temperature. Understanding contact/device degradation versus operating environment is useful for improving radiation detector performance.

Oscillatory noncollinear magnetism induced by interfacial charge transfer in superlattices composed of metallic oxides

DOE PAGES

Hoffman, Jason D.; Kirby, Brian J.; Kwon, Jihwan; ...

2016-11-22

Interfaces between correlated complex oxides are promising avenues to realize new forms of magnetism that arise as a result of charge transfer, proximity effects, and locally broken symmetries. We report on the discovery of a noncollinear magnetic structure in superlattices of the ferromagnetic metallic oxide La 2/3Sr 1/3MnO 3 (LSMO) and the correlated metal LaNiO 3 (LNO). The exchange interaction between LSMO layers is mediated by the intervening LNO, such that the angle between the magnetization of neighboring LSMO layers varies in an oscillatory manner with the thickness of the LNO layer. The magnetic field, temperature, and spacer thickness dependencemore » of the noncollinear structure are inconsistent with the bilinear and biquadratic interactions that are used to model the magnetic structure in conventional metallic multilayers. A model that couples the LSMO layers to a helical spin state within the LNO fits the observed behavior. We propose that the spin-helix results from the interaction between a spatially varying spin susceptibility within the LNO and interfacial charge transfer that creates localized Ni 2+ states. In conclusion, our work suggests a new approach to engineering noncollinear spin textures in metallic oxide heterostructures.« less

Atomistic modeling of metallic thin films by modified embedded atom method

NASA Astrophysics Data System (ADS)

Hao, Huali; Lau, Denvid

2017-11-01

Molecular dynamics simulation is applied to investigate the deposition process of metallic thin films. Eight metals, titanium, vanadium, iron, cobalt, nickel, copper, tungsten, and gold, are chosen to be deposited on the aluminum substrate. The second nearest-neighbor modified embedded atom method potential is adopted to predict their thermal and mechanical properties. When quantifying the screening parameters of the potential, the error for Young's modulus and coefficient of thermal expansion between the simulated results and the experimental measurements is less than 15%, demonstrating the reliability of the potential to predict metallic behaviors related to thermal and mechanical properties. A set of potential parameters which governs the interactions between aluminum and other metals in a binary system is also generated from ab initio calculation. The details of interfacial structures between the chosen films and substrate are successfully simulated with the help of these parameters. Our results indicate that the preferred orientation of film growth depends on the film crystal structure, and the inter-diffusion at the interface is correlated the cohesive energy parameter of potential for the binary system. Such finding provides an important basis to further understand the interfacial science, which contributes to the improvement of the mechanical properties, reliability and durability of films.

Interfacial nano-mixing in a miniaturised platform enables signal enhancement and in situ detection of cancer biomarkers.

PubMed

Wuethrich, Alain; Sina, Abu Ali Ibn; Ahmed, Mostak; Lin, Ting-Yun; Carrascosa, Laura G; Trau, Matt

2018-06-14

Interfacial biosensing performs the detection of biomolecules at the bare-metal interface for disease diagnosis by comparing how biological species derived from patients and healthy individuals interact with bare metal surfaces. This technique retrieves clinicopathological information without complex surface functionalisation which is a major limitation of conventional techniques. However, it is still challenging to detect subtle molecular changes by interfacial biosensing, and the detection often requires prolonged sensing times due to the slow diffusion process of the biomolecules towards the sensor surface. Herein, we report on a novel strategy for interfacial biosensing which involves in situ electrochemical detection under the action of an electric field-induced nanoscopic flow at nanometre distance to the sensing surface. This nanomixing significantly increases target adsorption, reduces sensing time, and enables the detection of small molecular changes with enhanced sensitivity. Using a multiplex electrochemical microdevice that enables nanomixing and in situ label-free electrochemical detection, we demonstrate the detection of multiple cancer biomarkers on the same device. We present data for the detection of aberrant phosphorylation in the EGFR protein and hypermethylation in the EN1 gene region. Our method significantly shortens the assay period (from 40 min and 20 min to 3 minutes for protein and DNA, respectively), increases the sensitivity by up to two orders of magnitude, and improves detection specificity.

Interfacial Surgery Determination of Succinonitrile and Succinonitrile-Acetone Alloy Using Surface Light Scattering Spectrometer

NASA Technical Reports Server (NTRS)

Tin, Padetha; Frate, David T.; deGroh, Henry C., III

2001-01-01

The objectives of this ground based research is to measure the liquid/vapor interfacial surface energies of succinonitrile (SCN) and alloys of succinonitrile and acetone using Surface Light Scattering Spectrometer. Liquid/vapor interfacial energy measurements will be made near and above the melting point and are the primary goal of this proposal. A measurement of viscosity also results from the Surface Light Scattering technique employed. Interfacial free energies between the phases enters into many analysis of phase transformation and flow, including nucleation, dendritic growth, interface stability, Ostwald ripening, and Marangoni flow. Succirionitrile (SCN) is useful as a model for the study of metal solidification, although it is an organic material, it has a BCC crystal structure and solidifies dendriticly like a metal. It is also transparent and has a low melting point (58.08 C). Succinonitrile has been and is being used extensively in NASAs Microgravity Materials Science and Fluid Physics programs and as well as in several ground-based and microgravity studies including the Isothermal Dendritic Growth Experiment (IDGE) due to Glicksman and coworkers and subsequently in several theoretical and numerical studies of dendritic growth. Previous measurements of succinonitrile (SCN) and alloys of succinonitrile and acetone surface tensions are extremely limited. We believe the data sought through this proposal have significant basic physical property data value and thus the work proposed will provide needed data in support of NASAs Microgravity program research.

A concise review of nanoscopic aspects of bioleaching bacteria-mineral interactions.

PubMed

Diao, Mengxue; Taran, Elena; Mahler, Stephen; Nguyen, Anh V

2014-10-01

Bioleaching is a technology for the recovery of metals from minerals by means of microorganisms, which accelerate the oxidative dissolution of the mineral by regenerating ferric ions. Bioleaching processes take place at the interface of bacteria, sulfide mineral and leaching solution. The fundamental forces between a bioleaching bacterium and mineral surface are central to understanding the intricacies of interfacial phenomena, such as bacterial adhesion or detachment from minerals and the mineral dissolution. This review focuses on the current state of knowledge in the colloidal aspect of bacteria-mineral interactions, particularly for bioleaching bacteria. Special consideration is given to the microscopic structure of bacterial cells and the atomic force microscopy technique used in the quantification of fundamental interaction forces at nanoscale. Copyright © 2014 Elsevier B.V. All rights reserved.

Anisotropic Damage Mechanics Modeling in Metal Matrix Composites

DTIC Science & Technology

1993-05-15

conducted on a titanium aluminide SiC-reinforced metal matrix composite. Center-cracked plates with laminate layups of (0/90) and (±45). were tested... interfacial damage mechanisms as debonding or delamination. Equations (2.14) and (2.15) represent the damage transformation equations for the stress... titanium aluminide SiC 46 continuous reinforced metal matrix composite. As a means of enforcing quality assurance, all manufacturing and cutting of the

Environmental Applications of Interfacial Materials with Special Wettability

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

Wang, Zhangxin; Elimelech, Menachem; Lin, Shihong

Interfacial materials with special wettability have become a burgeoning research area in materials science in the past decade. The unique surface properties of materials and interfaces generated by biomimetic approaches can be leveraged to develop effective solutions to challenging environmental problems. This critical review presents the concept, mechanisms, and fabrication techniques of interfacial materials with special wettability, and assesses the environmental applications of these materials for oil-water separation, membrane-based water purification and desalination, biofouling control, high performance vapor condensation, and atmospheric water collection. We also highlight the most promising properties of interfacial materials with special wettability that enable innovative environmentalmore » applications and discuss the practical challenges for large-scale implementation of these novel materials.« less

Microfluidic ultralow interfacial tensiometry with magnetic particles.

PubMed

Tsai, Scott S H; Wexler, Jason S; Wan, Jiandi; Stone, Howard A

2013-01-07

We describe a technique that measures ultralow interfacial tensions using paramagnetic spheres in a co-flow microfluidic device designed with a magnetic section. Our method involves tuning the distance between the co-flowing interface and the magnet's center, and observing the behavior of the spheres as they approach the liquid-liquid interface-the particles either pass through or are trapped by the interface. Using threshold values of the magnet-to-interface distance, we make estimates of the two-fluid interfacial tension. We demonstrate the effectiveness of this technique for measuring very low interfacial tensions, O(10(-6)-10(-5)) N m(-1), by testing solutions of different surfactant concentrations, and we show that our results are comparable with measurements made using a spinning drop tensiometer.

Environmental Applications of Interfacial Materials with Special Wettability

DOE PAGES

Wang, Zhangxin; Elimelech, Menachem; Lin, Shihong

2016-02-01

Interfacial materials with special wettability have become a burgeoning research area in materials science in the past decade. The unique surface properties of materials and interfaces generated by biomimetic approaches can be leveraged to develop effective solutions to challenging environmental problems. This critical review presents the concept, mechanisms, and fabrication techniques of interfacial materials with special wettability, and assesses the environmental applications of these materials for oil-water separation, membrane-based water purification and desalination, biofouling control, high performance vapor condensation, and atmospheric water collection. We also highlight the most promising properties of interfacial materials with special wettability that enable innovative environmentalmore » applications and discuss the practical challenges for large-scale implementation of these novel materials.« less

Structural changes in block copolymer micelles induced by cosolvent mixtures†

PubMed Central

Kelley, Elizabeth G.; Smart, Thomas P.; Jackson, Andrew J.; Sullivan, Millicent O.

2013-01-01

We investigated the influence of tetrahydrofuran (THF) addition on the structure of poly(1,2-butadiene-b-ethylene oxide) [PB-PEO] micelles in aqueous solution. Our studies showed that while the micelles remained starlike, the micelle core-corona interfacial tension and micelle size decreased upon THF addition. The detailed effects of the reduction in interfacial tension were probed using contrast variations in small angle neutron scattering (SANS) experiments. At low THF contents (high interfacial tensions), the SANS data were fit to a micelle form factor that incorporated a radial density distribution of corona chains to account for the starlike micelle profile. However, at higher THF contents (low interfacial tensions), the presence of free chains in solution affected the scattering at high q and required the implementation of a linear combination of micelle and Gaussian coil form factors. These SANS data fits indicated that the reduction in interfacial tension led to broadening of the core-corona interface, which increased the PB chain solvent accessibility at intermediate THF solvent fractions. We also noted that the micelle cores swelled with increasing THF addition, suggesting that previous assumptions of the micelle core solvent content in cosolvent mixtures may not be accurate. Control over the size, corona thickness, and extent of solvent accessible PB in these micelles can be a powerful tool in the development of targeting delivery vehicles. PMID:24282441

Structural changes in block copolymer micelles induced by cosolvent mixtures

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

Kelley, Elizabeth G.; Smart, Thomas P.; Jackson, Andrew J.

2012-11-26

We investigated the influence of tetrahydrofuran (THF) addition on the structure of poly(1,2-butadiene-b-ethylene oxide) [PB-PEO] micelles in aqueous solution. Our studies showed that while the micelles remained starlike, the micelle core-corona interfacial tension and micelle size decreased upon THF addition. The detailed effects of the reduction in interfacial tension were probed using contrast variations in small angle neutron scattering (SANS) experiments. At low THF contents (high interfacial tensions), the SANS data were fit to a micelle form factor that incorporated a radial density distribution of corona chains to account for the starlike micelle profile. However, at higher THF contents (lowmore » interfacial tensions), the presence of free chains in solution affected the scattering at high q and required the implementation of a linear combination of micelle and Gaussian coil form factors. These SANS data fits indicated that the reduction in interfacial tension led to broadening of the core-corona interface, which increased the PB chain solvent accessibility at intermediate THF solvent fractions. We also noted that the micelle cores swelled with increasing THF addition, suggesting that previous assumptions of the micelle core solvent content in cosolvent mixtures may not be accurate. Control over the size, corona thickness, and extent of solvent accessible PB in these micelles can be a powerful tool in the development of targeting delivery vehicles.« less

Modeling of the fracture behavior of spot welds using advanced micro-mechanical damage models

NASA Astrophysics Data System (ADS)

Sommer, Silke

2010-06-01

This paper presents the modeling of deformation and fracture behavior of resistance spot welded joints in DP600 steel sheets. Spot welding is still the most commonly used joining technique in automotive engineering. In overloading situations like crash joints are often the weakest link in a structure. For those reasons, crash simulations need reliable and applicable tools to predict the load bearing capacity of spot welded components. Two series of component tests with different spot weld diameters have shown that the diameter of the weld nugget is the main influencing factor affecting fracture mode (interfacial or pull-out fracture), load bearing capacity and energy absorption. In order to find a correlation between nugget diameter, load bearing capacity and fracture mode, the spot welds are simulated with detailed finite element models containing base metal, heat affected zone and weld metal in lap-shear loading conditions. The change in fracture mode from interfacial to pull-out or peel-out fracture with growing nugget diameter under lap-shear loading was successfully modeled using the Gologanu-Leblond model in combination with the fracture criteria of Thomason and Embury. A small nugget diameter is identified to be the main cause for interfacial fracture. In good agreement with experimental observations, the calculated pull-out fracture initiates in the base metal at the boundary to the heat affected zone.

Mean-time-to-failure study of flip chip solder joints on Cu/Ni(V)/Al thin-film under-bump-metallization

NASA Astrophysics Data System (ADS)

Choi, W. J.; Yeh, E. C. C.; Tu, K. N.

2003-11-01

Electromigration of eutectic SnPb flip chip solder joints and their mean-time-to-failure (MTTF) have been studied in the temperature range of 100 to 140 °C with current densities of 1.9 to 2.75×104 A/cm2. In these joints, the under-bump-metallization (UBM) on the chip side is a multilayer thin film of Al/Ni(V)/Cu, and the metallic bond-pad on the substrate side is a very thick, electroless Ni layer covered with 30 nm of Au. When stressed at the higher current densities, the MTTF was found to decrease much faster than what is expected from the published Black's equation. The failure occurred by interfacial void propagation at the cathode side, and it is due to current crowding near the contact interface between the solder bump and the thin-film UBM. The current crowding is confirmed by a simulation of current distribution in the solder joint. Besides the interfacial void formation, the intermetallic compounds formed on the UBM as well as the Ni(V) film in the UBM have been found to dissolve completely into the solder bump during electromigration. Therefore, the electromigation failure is a combination of the interfacial void formation and the loss of UBM. Similar findings in eutectic SnAgCu flip chip solder joints have also been obtained and compared.

Electromigration-induced drift in damascene and plasma-etched Al(Cu). II. Mass transport mechanisms in bamboo interconnects

NASA Astrophysics Data System (ADS)

Proost, Joris; Maex, Karen; Delacy, Luc

2000-01-01

We have discussed electromigration (EM)-induced drift in polycrystalline damascene versus reactive ion etched (RIE) Al(Cu) in part I. For polycrystalline Al(Cu), mass transport is well documented to occur through sequential stages : an incubation period (attributed to Cu depletion beyond a critical length) followed by the Al drift stage. In this work, the drift behavior of bamboo RIE and damascene Al(Cu) is analyzed. Using Blech-type test structures, mass transport in RIE lines was shown to proceed both by lattice and interfacial diffusion. The dominating mechanism depends on the Cu distribution in the line, as was evidenced by comparing as-patterned (lattice EM) and RTP-annealed (interface EM) samples. The interfacial EM only occurs at metallic interfaces. In that case, Cu alloying was observed to retard Al interfacial mass transport, giving rise to an incubation time. Although the activation energy for the incubation time was found similar to the one controlling Al lattice drift, for which no incubation time was observed, lattice EM is preferred over interfacial EM because it is insensitive to enhancing geometrical effects upon scaling. When comparing interfacial electromigration in RIE with bamboo damascene Al(Cu), with the incubation time rate controlling for both, the higher EM threshold observed for damascene was shown to be insufficient to compensate for its significantly increased Cu depletion rate, contrary to the case of polycrystalline Al(Cu) interconnects. Two factors were demonstrated to contribute. First, there are more metallic interfaces, intrinsically related to the use of wetting or barrier layers in recessed features. Second, specific to this study, the additional formation of TiAl3 at the trench sidewalls further enhanced the Cu depletion rate, and reduced the rate-controlling incubation time. A separate drift study on RIE via-type test structures indicated that it is very difficult to suppress interfacial mass transport in favor of lattice EM upon TiAl3 formation.

Processing of monolayer materials via interfacial reactions

DOEpatents

Sutter, Peter Werner; Sutter, Eli Anguelova

2014-05-20

A method of forming and processing of graphene is disclosed based on exposure and selective intercalation of the partially graphene-covered metal substrate with atomic or molecular intercalation species such as oxygen (O.sub.2) and nitrogen oxide (NO.sub.2). The process of intercalation lifts the strong metal-carbon coupling and restores the characteristic Dirac behavior of isolated monolayer graphene. The interface of graphene with metals or metal-decorated substrates also provides for controlled chemical reactions based on novel functionality of the confined space between a metal surface and a graphene sheet.

Fingering patterns in magnetic fluids: Perturbative solutions and the stability of exact stationary shapes

NASA Astrophysics Data System (ADS)

Anjos, Pedro H. A.; Lira, Sérgio A.; Miranda, José A.

2018-04-01

We examine the formation of interfacial patterns when a magnetic liquid droplet (ferrofluid, or a magnetorheological fluid), surrounded by a nonmagnetic fluid, is subjected to a radial magnetic field in a Hele-Shaw cell. By using a vortex-sheet formalism, we find exact stationary solutions for the fluid-fluid interface in the form of n -fold polygonal shapes. A weakly nonlinear, mode-coupling method is then utilized to find time-evolving perturbative solutions for the interfacial patterns. The stability of such nonzero surface tension exact solutions is checked and discussed, by trying to systematically approach the exact stationary shapes through perturbative solutions containing an increasingly larger number of participating Fourier modes. Our results indicate that the exact stationary solutions of the problem are stable, and that a good matching between exact and perturbative shape solutions is achieved just by using a few Fourier modes. The stability of such solutions is substantiated by a linearization process close to the stationary shape, where a system of mode-coupling equations is diagonalized, determining the eigenvalues which dictate the stability of a fixed point.

Novel strip-cast Mg/Al clad sheets with excellent tensile and interfacial bonding properties

PubMed Central

Kim, Jung-Su; Lee, Dong Ho; Jung, Seung-Pill; Lee, Kwang Seok; Kim, Ki Jong; Kim, Hyoung Seop; Lee, Byeong-Joo; Chang, Young Won; Yuh, Junhan; Lee, Sunghak

2016-01-01

In order to broaden industrial applications of Mg alloys, as lightest-weight metal alloys in practical uses, many efforts have been dedicated to manufacture various clad sheets which can complement inherent shortcomings of Mg alloys. Here, we present a new fabrication method of Mg/Al clad sheets by bonding thin Al alloy sheet on to Mg alloy melt during strip casting. In the as-strip-cast Mg/Al clad sheet, homogeneously distributed equi-axed dendrites existed in the Mg alloy side, and two types of thin reaction layers, i.e., γ (Mg17Al12) and β (Mg2Al3) phases, were formed along the Mg/Al interface. After post-treatments (homogenization, warm rolling, and annealing), the interfacial layers were deformed in a sawtooth shape by forming deformation bands in the Mg alloy and interfacial layers, which favorably led to dramatic improvement in tensile and interfacial bonding properties. This work presents new applications to multi-functional lightweight alloy sheets requiring excellent formability, surface quality, and corrosion resistance as well as tensile and interfacial bonding properties. PMID:27245687

Thermal conductance at atomically clean and disordered silicon/aluminum interfaces: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Ih Choi, Woon; Kim, Kwiseon; Narumanchi, Sreekant

2012-09-01

Thermal resistance between layers impedes effective heat dissipation in electronics packaging applications. Thermal conductance for clean and disordered interfaces between silicon (Si) and aluminum (Al) was computed using realistic Si/Al interfaces and classical molecular dynamics with the modified embedded atom method potential. These realistic interfaces, which include atomically clean as well as disordered interfaces, were obtained using density functional theory. At 300 K, the magnitude of interfacial conductance due to phonon-phonon scattering obtained from the classical molecular dynamics simulations was approximately five times higher than the conductance obtained using analytical elastic diffuse mismatch models. Interfacial disorder reduced the thermal conductance due to increased phonon scattering with respect to the atomically clean interface. Also, the interfacial conductance, due to electron-phonon scattering at the interface, was greater than the conductance due to phonon-phonon scattering. This indicates that phonon-phonon scattering is the bottleneck for interfacial transport at the semiconductor/metal interfaces. The molecular dynamics modeling predictions for interfacial thermal conductance for a 5-nm disordered interface between Si/Al were in-line with recent experimental data in the literature.

Novel strip-cast Mg/Al clad sheets with excellent tensile and interfacial bonding properties.

PubMed

Kim, Jung-Su; Lee, Dong Ho; Jung, Seung-Pill; Lee, Kwang Seok; Kim, Ki Jong; Kim, Hyoung Seop; Lee, Byeong-Joo; Chang, Young Won; Yuh, Junhan; Lee, Sunghak

2016-06-01

In order to broaden industrial applications of Mg alloys, as lightest-weight metal alloys in practical uses, many efforts have been dedicated to manufacture various clad sheets which can complement inherent shortcomings of Mg alloys. Here, we present a new fabrication method of Mg/Al clad sheets by bonding thin Al alloy sheet on to Mg alloy melt during strip casting. In the as-strip-cast Mg/Al clad sheet, homogeneously distributed equi-axed dendrites existed in the Mg alloy side, and two types of thin reaction layers, i.e., γ (Mg17Al12) and β (Mg2Al3) phases, were formed along the Mg/Al interface. After post-treatments (homogenization, warm rolling, and annealing), the interfacial layers were deformed in a sawtooth shape by forming deformation bands in the Mg alloy and interfacial layers, which favorably led to dramatic improvement in tensile and interfacial bonding properties. This work presents new applications to multi-functional lightweight alloy sheets requiring excellent formability, surface quality, and corrosion resistance as well as tensile and interfacial bonding properties.

Tunable anomalous hall effect induced by interfacial catalyst in perpendicular multilayers

NASA Astrophysics Data System (ADS)

Zhang, J. Y.; Peng, W. L.; Sun, Q. Y.; Liu, Y. W.; Dong, B. W.; Zheng, X. Q.; Yu, G. H.; Wang, C.; Zhao, Y. C.; Wang, S. G.

2018-04-01

The interfacial structures, playing a critical role on the transport properties and the perpendicular magnetic anisotropy in thin films and multilayers, can be modified by inserting an ultrathin functional layer at the various interfaces. The anomalous Hall effect (AHE) in the multilayers with core structure of Ta/CoFeB/X/MgO/Ta (X: Hf or Pt) is tuned by interfacial catalytic engineering. The saturation anomalous Hall resistance (RAH) is increased by 16.5% with 0.1 nm Hf insertion compared with the reference sample without insertion. However, the RAH value is decreased by 9.0% with 0.1 nm Pt insertion. The interfacial states were characterized by the X-ray photoelectron spectroscopy (XPS). The XPS results indicate that a strong bonding between Hf and O for Hf insertion, but no bonding between Pt and O for Pt insertion. The bonding between metal and oxygen leads to various oxygen migration behavior at the interfaces. Therefore, the opposite behavior about the RAH originates from the different oxygen behavior due to various interfacial insertion. This work provides a new approach to manipulate spin transport property for the potential applications.

Emerging magnetism and anomalous Hall effect in iridate–manganite heterostructures

PubMed Central

Nichols, John; Gao, Xiang; Lee, Shinbuhm; Meyer, Tricia L.; Freeland, John W.; Lauter, Valeria; Yi, Di; Liu, Jian; Haskel, Daniel; Petrie, Jonathan R.; Guo, Er-Jia; Herklotz, Andreas; Lee, Dongkyu; Ward, Thomas Z.; Eres, Gyula; Fitzsimmons, Michael R.; Lee, Ho Nyung

2016-01-01

Strong Coulomb repulsion and spin–orbit coupling are known to give rise to exotic physical phenomena in transition metal oxides. Initial attempts to investigate systems, where both of these fundamental interactions are comparably strong, such as 3d and 5d complex oxide superlattices, have revealed properties that only slightly differ from the bulk ones of the constituent materials. Here we observe that the interfacial coupling between the 3d antiferromagnetic insulator SrMnO3 and the 5d paramagnetic metal SrIrO3 is enormously strong, yielding an anomalous Hall response as the result of charge transfer driven interfacial ferromagnetism. These findings show that low dimensional spin–orbit entangled 3d–5d interfaces provide an avenue to uncover technologically relevant physical phenomena unattainable in bulk materials. PMID:27596572

Interface Engineering of Garnet Solid Electrolytes

NASA Astrophysics Data System (ADS)

Cheng, Lei

Solid lithium ion conductors represent a promising class of materials for next generation high energy density batteries, with the potential for enabling use of high capacity Li metal anodes and providing opportunities for novel lithium-free cathode materials. However, highly resistive interfaces stymie their practical use. This urgent scientific challenge requires mechanistic understanding of ion transport at interfaces, as well as development of novel processes to achieve low interfacial resistances. The goal of this PhD dissertation was to generate fundamental understandings of garnet-structured Al substituted Li7La3Zr2O 12 (LLZO) electrolyte surfaces and interfaces with lithium metal electrodes. Specifically in this research, the topmost surface microstructure, local chemical environment, and surface chemistry were carefully studied. The ceramic processing of garnet is discussed and ways to control the sintering behavior and microstructures were explored and successfully demonstrated. Factors contributing to high interfacial resistance were systematically studied. The source of the high interfacial impedance has been traced to the presence of Li2CO 3 on pellet surfaces resulting from air exposure after processing. In addition, it was discovered that surface grain boundaries are surprisingly fast ion transport pathways and surface microstructure is critically important to lithium ion transport at interfaces. Complex homo- and heterostructured LLZO solid electrolytes with controllable surface and bulk microstructures were successfully fabricated, which allowed the comparison and separation of the contribution from the surface and the bulk. Engineered pellet surfaces allowed us to achieve the lowest interfacial resistance ever reported for this composition, resulting in significantly improved cycling behavior. Lastly, it was found that LLZO surfaces can be effectively stabilized under air exposure conditions, preventing Li2CO3 formation and maintaining low interfacial resistances. This opens new opportunities for garnet solid electrolyte in practical applications.

Identification of the formation of metal-vinylidene interfacial bonds of alkyne-capped platinum nanoparticles by isotopic labeling.

PubMed

Hu, Peiguang; Chen, Limei; Deming, Christopher P; Bonny, Lewis W; Lee, Hsiau-Wei; Chen, Shaowei

2016-10-07

Stable platinum nanoparticles were prepared by the self-assembly of 1-dodecyne and dodec-1-deuteroyne onto bare platinum colloid surfaces. The nanoparticles exhibited consistent core size and optical properties. FTIR and NMR measurements confirmed the formation of Pt-vinylidene (Pt[double bond, length as m-dash]C[double bond, length as m-dash]CH-) interfacial linkages rather than Pt-acetylide (Pt-C[triple bond, length as m-dash]C-) and platinum-hydride (Pt-H) bonds.

Effect of electronic structure of the diamond surface on the strength of the diamond-metal interface

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1981-01-01

A diamond surface undergoes a transformation in its electronic structure by a vacuum anneal at approximately 900 C. The polished surface has no electronic states in the band gap, whereas the annealed surface has both occupied and unoccupied states in the and gap and exhibits some electrical conductivity. The effect of this transformation on the strength of the diamond metal interface was investigated by measuring the static friction force of an atomically clean meta sphere on a diamond flat in ultrahigh vacuum. It was found that low friction (weak bonding) is associated with the diamond surface devoid of gap states whereas high friction (strong bonding) is associated with the diamond surface with gap states. Exposure of the annealed surface to excited hydrogen also leads to weak bonding. The interfacial bond is discussed in terms of interaction of the metal conduction band electrons with the band gap states on the diamond surface. Effects of surface electrical conductivity on the interfacial bond are also be considered.

Tuning Interfacial States Using Organic Molecules as Spin Filters

NASA Astrophysics Data System (ADS)

Deloach, Andrew; Wang, Jingying; Papa, Christopher M.; Myahkostupov, Mykhaylo; Castellano, Felix N.; Dougherty, Daniel B.; Jiang, Wei; Liu, Feng

Organic semiconductors are known to have long spin relaxation times which makes them a good candidate for spintronics. However, an issue with these materials is that at metal-organic interfaces there is a conductivity mismatch problem that suppresses spin injection. To overcome this, orbital mixing at the interface can be tuned with an organic spacer layer to promote the formation of spin polarized interface states. These states act as a ``spin filters'' and have been proposed as an explanation for the large tunneling magnetoresistance seen in devices using tris-(8-hydroxyquinolate)-aluminum(Alq3). Here, we show that the spin polarized interface states can be tuned from metallic to resistive by subtle changes in molecular orbitals. This is done using spin polarized scanning tunneling microscopy with three different tris-(8-hydroxyquinolate) compounds: aluminum, chromium, and iron. Differences in d-orbital mixing results in different mechanisms of interfacial coupling, giving rise to metallic or resistive interface states. Supported by the U.S. DoE award No. DE-SC0010324.

Half-metallicity at the (110) interface between a full Heusler alloy and GaAs

NASA Astrophysics Data System (ADS)

Nagao, Kazutaka; Miura, Yoshio; Shirai, Masafumi

2006-03-01

The electronic properties of Co2CrAl/GaAs interfaces are investigated by using first-principles calculations with density functional theory. It is found that spin polarization tends to remain relatively high at the (110) interface and reaches almost unity for a specific (110) interfacial structure. Furthermore, the nearly-half-metallic interface turns out to be the most stable of the (110) interfacial structures studied here. Spin polarization calculated only from the sp -projected density of states is also examined in order to eliminate the effects stemming from the localized d components. The analysis shows that the high spin polarization at the (110) interface owes little to the localized d component and, therefore, is expected to be fairly relevant to transport properties. Co2CrSi/GaAs , Co2MnSi/GaAs , and Co2MnGe/GaAs heterostructures are also investigated, and similar half-metal-like behavior at (110) interface is observed for all of them.

The effects of Bi4Ti3O12 interfacial ferroelectric layer on the dielectric properties of Au/n-Si structures

NASA Astrophysics Data System (ADS)

Gökçen, Muharrem; Yıldırım, Mert

2015-06-01

Au/n-Si metal-semiconductor (MS) and Au/Bi4Ti3O12/n-Si metal-ferroelectric-semiconductor (MFS) structures were fabricated and admittance measurements were held between 5 kHz and 1 MHz at room temperature so that dielectric properties of these structures could be investigated. The ferroelectric interfacial layer Bi4Ti3O12 decreased the polarization voltage by providing permanent dipoles at metal/semiconductor interface. Depending on different mechanisms, dispersion behavior was observed in dielectric constant, dielectric loss and loss tangent versus bias voltage plots of both MS and MFS structures. The real and imaginary parts of complex modulus of MFS structure take smaller values than those of MS structure, because permanent dipoles in ferroelectric layer cause a large spontaneous polarization mechanism. While the dispersion in AC conductivity versus frequency plots of MS structure was observed at high frequencies, for MFS structure it was observed at lower frequencies.

Reactive metal-oxide interfaces: A microscopic view

NASA Astrophysics Data System (ADS)

Picone, A.; Riva, M.; Brambilla, A.; Calloni, A.; Bussetti, G.; Finazzi, M.; Ciccacci, F.; Duò, L.

2016-03-01

Metal-oxide interfaces play a fundamental role in determining the functional properties of artificial layered heterostructures, which are at the root of present and future technological applications. Magnetic exchange and magnetoelectric coupling, spin filtering, metal passivation, catalytic activity of oxide-supported nano-particles are just few examples of physical and chemical processes arising at metal-oxide hybrid systems, readily exploited in working devices. These phenomena are strictly correlated with the chemical and structural characteristics of the metal-oxide interfacial region, making a thorough understanding of the atomistic mechanisms responsible of its formation a prerequisite in order to tailor the device properties. The steep compositional gradient established upon formation of metal-oxide heterostructures drives strong chemical interactions at the interface, making the metal-oxide boundary region a complex system to treat, both from an experimental and a theoretical point of view. However, once properly mastered, interfacial chemical interactions offer a further degree of freedom for tuning the material properties. The goal of the present review is to provide a summary of the latest achievements in the understanding of metal/oxide and oxide/metal layered systems characterized by reactive interfaces. The influence of the interface composition on the structural, electronic and magnetic properties will be highlighted. Particular emphasis will be devoted to the discussion of ultra-thin epitaxial oxides stabilized on highly oxidizable metals, which have been rarely exploited as oxide supports as compared to the much more widespread noble and quasi noble metallic substrates. In this frame, an extensive discussion is devoted to the microscopic characterization of interfaces between epitaxial metal oxides and the Fe(001) substrate, regarded from the one hand as a prototypical ferromagnetic material and from the other hand as a highly oxidizable metal.

Effects of High and Low Salt Concentration in Electrolytes at Lithium–Metal Anode Surfaces

DOE PAGES

Camacho-Forero, Luis E.; Smith, Taylor W.; Balbuena, Perla B.

2016-12-16

The use of high concentration salts in electrolyte solutions of lithium-sulfur (Li-S) batteries has been shown beneficial for mitigating some effects such as polysulfide shuttle and dendrite growth at the Li metal anode. Such complex solutions have structural, dynamical, and reactivity associated issues that need to be analyzed for a better understanding of the reasons behind such beneficial effects. A passivation interfacial layer known as solid-electrolyte interphase (SEI) is generated during battery cycling as a result of electron transfer from the metal anode causing electrolyte decomposition. Here in this work, we investigate using density functional theory and ab initio molecularmore » dynamics simulations the salt decomposition, solvation effects, interactions among intermediate products and other species, and potential components of the SEI layer as a function of chemical nature and concentration of the salt, for lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI) at 1M and 4M concentrations in dimethoxyethane. It is found that LiTFSI undergoes a less complete reduction and facilitates charge transfer from the anode, whereas LiFSI shows a more complete decomposition forming LiF as one of the main SEI products. In addition, the specific decomposition mechanisms of each salt clearly point to the initial SEI components and the potential main products derived from them. Finally, very complex networks are found among the salt and solvent molecules in their attempt to maximize Li ion solvation that is quantified through the determination of coordination numbers.« less

The AMOS cell - An improved metal-semiconductor solar cell. [Antireflection coated Metal Oxide Semiconductor

NASA Technical Reports Server (NTRS)

Stirn, R. J.; Yeh, Y.-C. M.

1975-01-01

A new fabrication process is being developed which significantly improves the efficiency of metal-semiconductor solar cells. The resultant effect, a marked increase in the open-circuit voltage, is produced by the addition of an interfacial layer oxide on the semiconductor. Cells using gold on n-type gallium arsenide have been made in small areas (0.17 sq cm) with conversion efficiencies of 15% in terrestrial sunlight.

Spontaneous grafting of diazonium salts: chemical mechanism on metallic surfaces.

PubMed

Mesnage, Alice; Lefèvre, Xavier; Jégou, Pascale; Deniau, Guy; Palacin, Serge

2012-08-14

The spontaneous reaction of diazonium salts on various substrates has been widely employed since it consists of a simple immersion of the substrate in the diazonium salt solution. As electrochemical processes involving the same diazonium salts, the spontaneous grafting is assumed to give covalently poly(phenylene)-like bonded films. Resistance to solvents and to ultrasonication is commonly accepted as indirect proof of the existence of a covalent bond. However, the most relevant attempts to demonstrate a metal-C interface bond have been obtained by an XPS investigation of spontaneously grafted films on copper. Similarly, our experiments give evidence of such a bond in spontaneously grafted films on nickel substrates in acetonitrile. In the case of gold substrates, the formation of a spontaneous film was unexpected but reported in the literature in parallel to our observations. Even if no interfacial bond was observed, formation of the films was explained by grafting of aryl cations or radicals on the surface arising from dediazoniation, the film growing later by azo coupling, radical addition, or cationic addition on the grafted phenyl layer. Nevertheless, none of these mechanisms fits our experimental results showing the presence of an Au-N bond. In this work, we present a fine spectroscopic analysis of the coatings obtained on gold and nickel substrates that allow us to propose a chemical structure of such films, in particular, their interface with the substrates. After testing the most probable mechanisms, we have concluded in favor of the involvement of two complementary mechanisms which are the direct reaction of diazonium salts with the gold surface that accounts for the observed Au-N interfacial bonds as well as the formation of aryl cations able to graft on the substrate through Au-C linkages.

Interfacial Reaction and Mechanical Properties of Sn-Bi Solder joints

PubMed Central

Huang, Ying; Zhang, Zhijie

2017-01-01

Sn-Bi solder with different Bi content can realize a low-to-medium-to-high soldering process. To obtain the effect of Bi content in Sn-Bi solder on the microstructure of solder, interfacial behaviors in solder joints with Cu and the joints strength, five Sn-Bi solders including Sn-5Bi and Sn-15Bi solid solution, Sn-30Bi and Sn-45Bi hypoeutectic and Sn-58Bi eutectic were selected in this work. The microstructure, interfacial reaction under soldering and subsequent aging and the shear properties of Sn-Bi solder joints were studied. Bi content in Sn-Bi solder had an obvious effect on the microstructure and the distribution of Bi phases. Solid solution Sn-Bi solder was composed of the β-Sn phases embedded with fine Bi particles, while hypoeutectic Sn-Bi solder was composed of the primary β-Sn phases and Sn-Bi eutectic structure from networked Sn and Bi phases, and eutectic Sn-Bi solder was mainly composed of a eutectic structure from short striped Sn and Bi phases. During soldering with Cu, the increase on Bi content in Sn-Bi solder slightly increased the interfacial Cu6Sn5 intermetallic compound (IMC)thickness, gradually flattened the IMC morphology, and promoted the accumulation of more Bi atoms to interfacial Cu6Sn5 IMC. During the subsequent aging, the growth rate of the IMC layer at the interface of Sn-Bi solder/Cu rapidly increased from solid solution Sn-Bi solder to hypoeutectic Sn-Bi solder, and then slightly decreased for Sn-58Bi solder joints. The accumulation of Bi atoms at the interface promoted the rapid growth of interfacial Cu6Sn5 IMC layer in hypoeutectic or eutectic Sn-Bi solder through blocking the formation of Cu6Sn5 in solder matrix and the transition from Cu6Sn5 to Cu3Sn. Ball shear tests on Sn-Bi as-soldered joints showed that the increase of Bi content in Sn-Bi deteriorated the shear strength of solder joints. The addition of Bi into Sn solder was also inclined to produce brittle morphology with interfacial fracture, which suggests that the addition of Bi increased the shear resistance strength of Sn-Bi solder. PMID:28792440

Direct Contact Heat Exchange Interfacial Phenomena for Liquid Metal Reactors: Part II - Void Fraction

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

Abdulla, S.; Liu, X.; Anderson, M.H.

One concept being considered for steam generation in innovative nuclear reactor applications, involves water coming into direct contact with a circulating molten metal. The vigorous agitation of the two fluids, the direct liquid-liquid contact and the consequent large interfacial area can give rise to large heat transfer coefficients and rapid steam generation. For an optimum design of such direct contact heat exchange and vaporization systems, detailed knowledge is necessary of the various flow regimes, interfacial transport phenomena, heat transfer and operational stability. In order to investigate the interfacial transport phenomena, heat transfer and operational stability of direct liquid-liquid contact, amore » series of experiments are being performed in a 1-d test facility at Argonne National Laboratory and a 2-d experimental facility at UW-Madison. Each of the experimental facilities primarily consist of a liquid-metal melt chamber, heated test section (10 cm diameter tube for 1-d facility and 10 cm 50 cm rectangle for 2-d facility), water injection system and steam suppression tank. This paper is part II which, primarily addresses results and analysis of a set of preliminary experiments and void fraction measurements conducted in the 2-d facility at UW-Madison, part I deals with the heat transfer in the 1-d test facility at Argonne National Laboratory. A real-time high energy X-ray imaging system was developed and utilized to visualize the multiphase flow and measure line-average local void fractions, time-dependent void fraction distribution as well as estimates of the vapor bubble sizes and velocities. These measurements allowed us to determine the volumetric heat transfer coefficient and gain insight into the local heat transfer mechanisms. In this study, the images were captured at frame rates of 100 fps with spatial resolution of about 7 mm with a full-field view of a 15 cm square and five different positions along the test section height. The full-field average void fraction increases rapidly to about 15% in these preliminary tests, with the apparent boiling length of less than 20 cm. The volumetric heat transfer coefficient between the liquid metal and water are compared to the CRIEPI data, the only prior data for direct contact heat exchange for these liquid metal/water systems. (authors)« less

Effect of Post-Braze Heat Treatment on the Microstructure and Shear Strength of Cemented Carbide and Steel Using Ag-Based Alloy

NASA Astrophysics Data System (ADS)

Winardi, Y.; Triyono; Muhayat, N.

2018-03-01

The aim of the present study was to investigate the effect temperature of heat treatment process on the interfacial microstructure and mechanical properties of cemented carbide/carbon steel single lap joint brazed using Ag based alloy filler metal. The brazing process was carried out using torch brazing. Heat treatment process was carried out in induction furnace on the temperature of 700, 725, and 750°C, for 30 minutes. Microstructural examinations and phase analysis were performed using scanning electron microscopy (SEM) equipped with energy dispersion spectrometry (EDS). Shear strength of the joints was measured by the universal testing machine. The results of the microstructural analyses of the brazed area indicate that the increase temperature of treatment lead to the increase of solid solution phase of enrichted Cu. Based on EDS test, the carbon elements spread to all brazed area, which is disseminated by base metals. Shear strength joint is increased with temperature treatment. The highest shear strength of the brazed joint was 214,14 MPa when the heated up at 725°C.

Effect of interfacial stresses in an elastic body with a nanoinclusion

NASA Astrophysics Data System (ADS)

Vakaeva, Aleksandra B.; Grekov, Mikhail A.

2018-05-01

The 2-D problem of an infinite elastic solid with a nanoinclusion of a different from circular shape is solved. The interfacial stresses are acting at the interface. Contact of the inclusion with the matrix satisfies the ideal conditions of cohesion. The generalized Laplace - Young law defines conditions at the interface. To solve the problem, Gurtin - Murdoch surface elasticity model, Goursat - Kolosov complex potentials and the boundary perturbation method are used. The problem is reduced to the solution of two independent Riemann - Hilbert's boundary problems. For the circular inclusion, hypersingular integral equation in an unknown interfacial stress is derived. The algorithm of solving this equation is constructed. The influence of the interfacial stress and the dimension of the circular inclusion on the stress distribution and stress concentration at the interface are analyzed.

Crack problems involving nonhomogeneous interfacial regions in bonded materials

NASA Technical Reports Server (NTRS)

Erdogan, F.

1990-01-01

Consideration is given to two classes of fracture-related solid mechanics problems in which the model leads to some physically anomalous results. The first is the interface crack problem associated with the debonding process in which the corresponding elasticity solution predicts severe oscillations of stresses and the crack surface displacements vary near the crack tip. The second deals with crack intersecting the interface. The nature of the solutions around the crack tips arising from these problems is reviewed. The rationale for introducing a new interfacial zone model is discussed, its analytical consequences within the context of the two crack-problem classes are described, and some examples are presented.

Effect of electrolytes on bubble coalescence in columns observed with visualization techniques.

PubMed

Aguilera, María Eugenia; Ojeda, Antonieta; Rondón, Carolina; López De Ramos, Aura

2002-10-01

Bubble coalescence and the effect of electrolytes on this phenomenon have been previously studied. This interfacial phenomenon has attracted attention for reactor design/operation and enhanced oil recovery. Predicting bubble coalescence may help prevent low yields in reactors and predict crude oil recovery. Because of the importance of bubble coalescence, the objectives of this work were to improve the accuracy of measuring the percentage of coalescing bubbles and to observe the interfacial gas-liquid behavior. An experimental setup was designed and constructed. Bubble interactions were monitored with a visualization setup. The percentage of air bubble coalescence was 100% in distilled water, about 50% in 0.1 M sodium chloride (NaCl) aqueous solution, and 0% in 0.145 M NaCl aqueous solution. A reduction of the contact gas-liquid area was observed in distillate water. The volume of the resulting bubble was the sum of the original bubble volumes. Repulsion of bubbles was observed in NaCl solutions exceeding 0.07 M. The percentage of bubble coalescence diminishes as the concentration of NaCl chloride increases. High-speed video recording is an accurate technique to measure the percentage of bubble coalescence, and represents an important advance in gas-liquid interfacial studies.

Effect of Surface Hydration on Antifouling Properties of Mixed Charged Polymers.

PubMed

Leng, Chuan; Huang, Hao; Zhang, Kexin; Hung, Hsiang-Chieh; Xu, Yao; Li, Yaoxin; Jiang, Shaoyi; Chen, Zhan

2018-05-07

Interfacial water structure on a polymer surface in water (or surface hydration) is related to the antifouling activity of the polymer. Zwitterionic polymer materials exhibit excellent antifouling activity due to their strong surface hydration. It was proposed to replace zwitterionic polymers using mixed charged polymers because it is much easier to prepare mixed charged polymer samples with much lower costs. In this study, using sum frequency generation (SFG) vibrational spectroscopy, we investigated interfacial water structures on mixed charged polymer surfaces in water, and how such structures change while exposing to salt solutions and protein solutions. The 1:1 mixed charged polymer exhibits excellent antifouling property while other mixed charged polymers with different ratios of the positive/negative charges do not. It was found that on the 1:1 mixed charged polymer surface, SFG water signal is dominated by the contribution of the strongly hydrogen bonded water molecules, indicating strong hydration of the polymer surface. The responses of the 1:1 mixed charged polymer surface to salt solutions are similar to those of zwitterionic polymers. Interestingly, exposure to high concentrations of salt solutions leads to stronger hydration of the 1:1 mixed charged polymer surface after replacing the salt solution with water. Protein molecules do not substantially perturb the interfacial water structure on the 1:1 mixed charged polymer surface and do not adsorb to the surface, showing that this mixed charged polymer is an excellent antifouling material.

Pore shape of honeycomb-patterned films: modulation and interfacial behavior.

PubMed

Wan, Ling-Shu; Ke, Bei-Bei; Zhang, Jing; Xu, Zhi-Kang

2012-01-12

The control of the pore size of honeycomb-patterned films has been more or less involved in most work on the topic of breath figures. Modulation of the pore shape was largely ignored, although it is important to applications in replica molding, filtration, particle assembly, and cell culture. This article reports a tunable pore shape for patterned films prepared from commercially available polystyrene (PS). We investigated the effects of solvents including tetrahydrofuran (THF) and chloroform (CF) and hydrophilic additives including poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), poly(ethylene glycol) (PEG), and poly(N-vinyl pyrrolidone) (PVP). Water droplets on/in the polymer solutions were observed and analyzed for simulating the formation and stabilization of breath figures. Interfacial tensions of the studied systems were measured and considered as a main factor to modulate the pore shape. Results indicate that the pores gradually change from near-spherical to ellipsoidal with the increase of additive content when using CF as the solvent; however, only ellipsoidal pores are formed from the THF solution. It is demonstrated that the aggregation of the additives at the water/polymer solution interface is more efficient in the THF solution than that in the CF solution. This aggregation decreases the interfacial tension, stabilizes the condensed water droplets, and shapes the pores of the films. The results may facilitate our understanding of the dynamic breath figure process and provide a new pathway to prepare patterned films with different pore structures.

Interfacial free energy governs single polystyrene chain collapse in water and aqueous solutions.

PubMed

Li, Isaac T S; Walker, Gilbert C

2010-05-12

The hydrophobic interaction is significantly responsible for driving protein folding and self-assembly. To understand it, the thermodynamics, the role of water structure, the dewetting process surrounding hydrophobes, and related aspects have undergone extensive investigations. Here, we examine the hypothesis that polymer-solvent interfacial free energy is adequate to describe the energetics of the collapse of a hydrophobic homopolymer chain at fixed temperature, which serves as a much simplified model for studying the hydrophobic collapse of a protein. This implies that changes in polymer-solvent interfacial free energy should be directly proportional to the force to extend a collapsed polymer into a bad solvent. To test this hypothesis, we undertook single-molecule force spectroscopy on a collapsed, single, polystyrene chain in water-ethanol and water-salt mixtures where we measured the monomer solvation free energy from an ensemble average conformations. Different proportions within the binary mixture were used to create solvents with different interfacial free energies with polystyrene. In these mixed solvents, we observed a linear correlation between the interfacial free energy and the force required to extend the chain into solution, which is a direct measure of the solvation free energy per monomer on a single chain at room temperature. A simple analytical model compares favorably with the experimental results. This knowledge supports a common assumption that explicit water solvent may not be necessary for cases whose primary concerns are hydrophobic interactions and hydrophobic hydration.

pH-Induced interfacial properties of Chaplin E from Streptomyces coelicolor.

PubMed

Dokouhaki, Mina; Hung, Andrew; Prime, Emma L; Qiao, Greg G; Day, Li; Gras, Sally L

2017-12-01

Chaplin E, or Chp E, is a surface active peptide secreted by Streptomyces coelicolor that adopts different structures depending on solution pH but the effect of these structures on the interfacial properties of Chp E is not known. In experiments paired with simulations, Chp E was found to display pH-dependent interfacial assembly and surface activity. At pH 3.0, Chp E formed an ordered non-amyloidal interfacial film with high surface activity; while at pH 10.0, Chp E self-assembled into a heterogeneous film containing randomly arranged fibrils at the interface that was less surface active compared to the film formed at pH 3.0. In simulations at pH 10.0, Chp E molecules showed a higher propensity for dimerization within the solution phase, lower rate of adsorption to the interface and tighter inter-molecular associations at the interface, consistent with the lower surface activity and smaller interfacial area coverage per molecule measured at this pH compared to at pH 3.0. A model is presented for the role of Chp E in the developmental differentiation of Streptomyces coelicolor, where Chp E contributes to changes in surface tension at low pH and the formation of fibrils on the surface of aerial hyphae at high pH. Our data also suggest Chp E could be a promising surface active agent with functional activity that can be controlled by pH. Copyright © 2017 Elsevier B.V. All rights reserved.

Electrical characteristics for Sn-Ag-Cu solder bump with Ti/Ni/Cu under-bump metallization after temperature cycling tests

NASA Astrophysics Data System (ADS)

Shih, T. I.; Lin, Y. C.; Duh, J. G.; Hsu, Tom

2006-10-01

Lead-free solder bumps have been widely used in current flip-chip technology (FCT) due to environmental issues. Solder joints after temperature cycling tests were employed to investigate the interfacial reaction between the Ti/Ni/Cu under-bump metallization and Sn-Ag-Cu solders. The interfacial morphology and quantitative analysis of the intermetallic compounds (IMCs) were obtained by electron probe microanalysis (EPMA) and field emission electron probe microanalysis (FE-EPMA). Various types of IMCs such as (Cu1-x,Agx)6Sn5, (Cu1-y,Agy)3Sn, and (Ag1-z,Cuz)3Sn were observed. In addition to conventional I-V measurements by a special sample preparation technique, a scanning electron microscope (SEM) internal probing system was introduced to evaluate the electrical characteristics in the IMCs after various test conditions. The electrical data would be correlated to microstructural evolution due to the interfacial reaction between the solder and under-bump metallurgy (UBM). This study demonstrated the successful employment of an internal nanoprobing approach, which would help further understanding of the electrical behavior within an IMC layer in the solder/UBM assembly.

Effect of surface microstructure on electrochemical performance of garnet solid electrolytes.

PubMed

Cheng, Lei; Chen, Wei; Kunz, Martin; Persson, Kristin; Tamura, Nobumichi; Chen, Guoying; Doeff, Marca

2015-01-28

Cubic garnet phases based on Al-substituted Li7La3Zr2O12 (LLZO) have high ionic conductivities and exhibit good stability versus metallic lithium, making them of particular interest for use in next-generation rechargeable battery systems. However, high interfacial impedances have precluded their successful utilization in such devices until the present. Careful engineering of the surface microstructure, especially the grain boundaries, is critical to achieving low interfacial resistances and enabling long-term stable cycling with lithium metal. This study presents the fabrication of LLZO heterostructured solid electrolytes, which allowed direct correlation of surface microstructure with the electrochemical characteristics of the interface. Grain orientations and grain boundary distributions of samples with differing microstructures were mapped using high-resolution synchrotron polychromatic X-ray Laue microdiffraction. The electrochemical characteristics are strongly dependent upon surface microstructure, with small grained samples exhibiting much lower interfacial resistances and better cycling behavior than those with larger grain sizes. Low area specific resistances of 37 Ω cm(2) were achieved; low enough to ensure stable cycling with minimal polarization losses, thus removing a significant obstacle toward practical implementation of solid electrolytes in high energy density batteries.

Probing and Manipulating the Interfacial Defects of InGaAs Dual-Layer Metal Oxides at the Atomic Scale.

PubMed

Wu, Xing; Luo, Chen; Hao, Peng; Sun, Tao; Wang, Runsheng; Wang, Chaolun; Hu, Zhigao; Li, Yawei; Zhang, Jian; Bersuker, Gennadi; Sun, Litao; Pey, Kinleong

2018-01-01

The interface between III-V and metal-oxide-semiconductor materials plays a central role in the operation of high-speed electronic devices, such as transistors and light-emitting diodes. The high-speed property gives the light-emitting diodes a high response speed and low dark current, and they are widely used in communications, infrared remote sensing, optical detection, and other fields. The rational design of high-performance devices requires a detailed understanding of the electronic structure at this interface; however, this understanding remains a challenge, given the complex nature of surface interactions and the dynamic relationship between the morphology evolution and electronic structures. Herein, in situ transmission electron microscopy is used to probe and manipulate the structural and electrical properties of ZrO 2 films on Al 2 O 3 and InGaAs substrate at the atomic scale. Interfacial defects resulting from the spillover of the oxygen-atom conduction-band wavefunctions are resolved. This study unearths the fundamental defect-driven interfacial electric structure of III-V semiconductor materials and paves the way to future high-speed and high-reliability devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison and extension of free dendritic growth models through application to silver-15 mass percent copper alloy

NASA Astrophysics Data System (ADS)

Onel, Selis

Modeling free dendritic growth in supercooled alloys is a critical requirement in controlling the microstructure of materials during rapid solidification processing of materials. Recent models developed to predict the growth of a dendrite in a highly supercooled melt adopt modifications that account for the interface kinetics and thermodynamics at high interface velocities, but the assumptions necessary to simplify the mathematical problem impose inherent restrictions. The assumption of straight phase boundaries adopted in early models often loses validity at high supercoolings, where phase boundaries are often curved. The use of equations with Henrian restrictions, such as the Baker-Cahn equation for the interfacial driving force and the Aziz equation for solute trapping confine these models to dilute solutions. Turnbull's collision-limited linear kinetic equation for interface growth may not apply to large interfacial driving forces. Therefore, a useful application and modification of free dendritic growth models require a thorough understanding of their limitations in producing consistent results. One of the objectives of this research is to numerically compare the free dendritic growth models derived from the earlier LGK model developed by Lipton et al. The subsequent LKT model by Lipton et al., the TLK model by Trivedi et al., and the BCT model by Boettinger et al., together with a modification of the TLK model, and the DA model by DiVenuti and Ando are compared through application to an Ag-15 mass % Cu alloy. In addition, a new model to extend the DA model is developed by incorporating a thermodynamic solution model for the calculation of the interfacial driving force, thereby eliminating the Baker-Cahn equation that limits the use of the correct BCT and DA models to dilute solutions. Direct computation of the interfacial driving force by calculating a metastable phase diagram for the Ag-Cu system using a temperature dependent subregular solution model is carried out. Comparison of the results of the new model with the DA model confirms that the Baker-Cahn equation is applicable at low solute concentrations. As a future research direction, the new model can be extended to apply to higher concentration alloys by using a new solute trapping equation to further eliminate the dilute solution limitations.

Geometric confinement effects on the metal-insulator transition temperature and stress relaxation in VO2 thin films grown on silicon

NASA Astrophysics Data System (ADS)

Viswanath, Changhyun Ko, B.; Yang, Zheng; Ramanathan, Shriram

2011-03-01

VO2 undergoes a sharp metal-insulator transition at ˜67 °C with several orders of change in conductivity and optical transmittance. Understanding and control of the properties of vanadium oxide layers grown on technologically relevant substrates such as Si (100) single crystals is therefore of great interest. In this work, we show tunability of metal-insulator transition temperature as well as recoverable stress in VO2 thin films grown on Si substrate by introducing nanoscale atomic layer deposited HfO2 interfacial layers with no degradation in the resistance ratio. For a confined VO2 film, the metal-insulator transition temperature is suppressed by ˜16 °C and the recoverable stress is 150 MPa, compared to 400 MPa for a bare film. These observations are further correlated with in situ variable temperature measurement of stress changes occurring during the phase transition. Structural and microstructural studies on the various samples have been carried out by x ray diffraction and cross-sectional transmission electron microscopy. The strategy of tuning the metal-insulator transition characteristics by nanoscale interfacial dielectrics is of broader relevance in design of programmable materials and integration into solid state devices for electronics.

Effects of Metallic Nanoparticles on Interfacial Intermetallic Compounds in Tin-Based Solders for Microelectronic Packaging

NASA Astrophysics Data System (ADS)

Haseeb, A. S. M. A.; Arafat, M. M.; Tay, S. L.; Leong, Y. M.

2017-10-01

Tin (Sn)-based solders have established themselves as the main alternative to the traditional lead (Pb)-based solders in many applications. However, the reliability of the Sn-based solders continues to be a concern. In order to make Sn-based solders microstructurally more stable and hence more reliable, researchers are showing great interest in investigating the effects of the incorporation of different nanoparticles into them. This paper gives an overview of the influence of metallic nanoparticles on the characteristics of interfacial intermetallic compounds (IMCs) in Sn-based solder joints on copper substrates during reflow and thermal aging. Nanocomposite solders were prepared by mechanically blending nanoparticles of nickel (Ni), cobalt (Co), zinc (Zn), molybdenum (Mo), manganese (Mn) and titanium (Ti) with Sn-3.8Ag-0.7Cu and Sn-3.5Ag solder pastes. The composite solders were then reflowed and their wetting characteristics and interfacial microstructural evolution were investigated. Through the paste mixing route, Ni, Co, Zn and Mo nanoparticles alter the morphology and thickness of the IMCs in beneficial ways for the performance of solder joints. The thickness of Cu3Sn IMC is decreased with the addition of Ni, Co and Zn nanoparticles. The thickness of total IMC layer is decreased with the addition of Zn and Mo nanoparticles in the solder. The metallic nanoparticles can be divided into two groups. Ni, Co, and Zn nanoparticles undergo reactive dissolution during solder reflow, causing in situ alloying and therefore offering an alternative route of alloy additions to solders. Mo nanoparticles remain intact during reflow and impart their influence as discrete particles. Mechanisms of interactions between different types of metallic nanoparticles and solder are discussed.

Shear strength of metal - SiO2 contacts

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1978-01-01

The strength of the bond between metals and SiO2 is studied by measuring the static coefficient of friction of metals contacting alpha-quartz in ultrahigh vacuum. It was found that copper with either chemisorbed oxygen, nitrogen or sulphur exhibited higher contact strength on stoichiometric SiO2 than did clean copper. Since the surface density of states induced by these species on copper is similar, it appears that the strength of the interfacial bond can be related to the density of states on the metal surface.

Shear strength of metal - SiO2 contacts

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1978-01-01

The strength of the bond between metals and SiO2 was studied by measuring the static coefficient of friction of metals contacting alpha-quartz in ultrahigh vacuum. It was found that copper with either chemisorbed oxygen, nitrogen, or sulphur exhibited higher contact strength on stoichiometric SiO2 than did clean copper. Since the surface density of states induced by these species on copper is similar, it appears that the strength of the interfacial bond can be related to the density of states on the metal surface.

Molecular-orbital model for metal-sapphire interfacial strength

NASA Technical Reports Server (NTRS)

Johnson, K. H.; Pepper, S. V.

1982-01-01

Self-consistent-field X-Alpha scattered-wave cluster molecular-orbital models have been constructed for transition and noble metals (Fe, Ni, Cu, and Ag) in contact with a sapphire (Al2O3) surface. It is found that a chemical bond is established between the metal d-orbital electrons and the nonbonding 2p-orbital electrons of the oxygen anions on the Al2O3 surface. An increasing number of occupied metal-sapphire antibonding molecular orbitals explains qualitatively the observed decrease of contact shear strength through the series Fe, Ni, Cu, and Ag.

Effects of image charges, interfacial charge discreteness, and surface roughness on the zeta potential of spherical electric double layers.

PubMed

Gan, Zecheng; Xing, Xiangjun; Xu, Zhenli

2012-07-21

We investigate the effects of image charges, interfacial charge discreteness, and surface roughness on spherical electric double layer structures in electrolyte solutions with divalent counterions in the setting of the primitive model. By using Monte Carlo simulations and the image charge method, the zeta potential profile and the integrated charge distribution function are computed for varying surface charge strengths and salt concentrations. Systematic comparisons were carried out between three distinct models for interfacial charges: (1) SURF1 with uniform surface charges, (2) SURF2 with discrete point charges on the interface, and (3) SURF3 with discrete interfacial charges and finite excluded volume. By comparing the integrated charge distribution function and the zeta potential profile, we argue that the potential at the distance of one ion diameter from the macroion surface is a suitable location to define the zeta potential. In SURF2 model, we find that image charge effects strongly enhance charge inversion for monovalent interfacial charges, and strongly suppress charge inversion for multivalent interfacial charges. For SURF3, the image charge effect becomes much smaller. Finally, with image charges in action, we find that excluded volumes (in SURF3) suppress charge inversion for monovalent interfacial charges and enhance charge inversion for multivalent interfacial charges. Overall, our results demonstrate that all these aspects, i.e., image charges, interfacial charge discreteness, their excluding volumes, have significant impacts on zeta potentials of electric double layers.

Water-gas shift reaction on alumina-supported Pt-CeO x catalysts prepared by supercritical fluid deposition

DOE PAGES

Deal, Jacob W.; Le, Phong; Corey, C. Blake; ...

2016-08-25

Alumina-supported platinum catalysts, both with and without ceria, were prepared by supercritical fluid deposition and evaluated for activity for water-gas shift reaction. The organometallic precursor, platinum(II) acetylacetonate, was deposited from solution in supercritical carbon dioxide. Analysis of the catalysts by high resolution scanning transmission electron microscopy indicated that platinum was present in the form of highly dispersed metal nanoparticles. Pretreatment of the alumina-supported ceria in hydrogen prior to the deposition of the platinum precursor resulted in more platinum nucleated on ceria than non-pretreated alumina-supported ceria but varied in both particle size and structure. The ceria-containing catalyst that was not pretreatedmore » exhibited a more uniform particle size, and the Pt particles were encapsulated in crystalline ceria. Reaction rate measurements showed that the catalyst was more active for water-gas shift, with reaction rates per mass of platinum that exceeded most literature values for water-gas shift reaction on Pt-CeO x catalysts. The high activity was attributed to the significant fraction of platinum/ceria interfacial contact. We found that these results show the promise of supercritical fluid deposition as a scalable means of synthesizing highly active supported metal catalysts that offer efficient utilization of precious metals.« less

Interfacial layers in high-temperature-oxidized NiCrAl

NASA Technical Reports Server (NTRS)

Larson, L. A.; Browning, R.; Poppa, H.; Smialek, J.

1983-01-01

The utility of Auger electron spectroscopy combined with ball cratering for depth analysis of oxide and diffusion layers produced in a Ni-14Cr-24Al alloy by oxidation in air at 1180 C for 25 hr is demonstrated. During postoxidation cooling, the oxide layers formed by this alloy spalled profusely. The remaining very thin oxide was primarily Cr2O3 with a trace of Ni. The underlying metal substrate exhibited gamma/gamma-prime and beta phases with a metallic interfacial layer which was similar to the bulk gamma/gamma-prime phase but slightly enriched in Cr and Al. These data are compared to electron microprobe results from a nominally identical alloy. The diffusion layer thickness is modelled with a simple mass balance equation and compared to recent results on the diffusion process in NiCrAl alloys.

Fundamental tribological properties of ion-beam-deposited boron nitride films

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa

1989-01-01

The adhesion, friction, and micromechanical properties of ion-beam-deposited boron nitride (BN) films are reviewed. The BN films are examined in contact with BN metals and other harder materials. For simplicity of discussion, the tribological properties of concern in the processes are separated into two parts. First, the pull-off force (adhesion) and the shear force required to break the interfacial junctions between contacting surfaces are discussed. The effects of surface films, hardness of metals, and temperature on tribological response with respect to adhesion and friction are considered. The second part deals with the abrasion of the BN films. Elastic, plastic, and fracture behavior of the BN films in solid-state contact are discussed. The scratch technique of determining the critical load needed to fracture interfacial adhesive bonds of BN films deposited on substrates is also addressed.

Fundamental tribological properties of ion-beam-deposited boron nitride films

NASA Technical Reports Server (NTRS)

Miyoshi, K.

1990-01-01

The adhesion, friction, and micromechanical properties of ion-beam-deposited boron nitride (BN) films are reviewed. The BN films are examined in contact with BN metals and other harder materials. For simplicity of discussion, the tribological properties of concern in the processes are separated into two parts. First, the pull-off force (adhesion) and the shear force required to break the interfacial junctions between contacting surfaces are discussed. The effects of surface films, hardness of metals, and temperature on tribological response with respect to adhesion and friction are considered. The second part deals with the abrasion of the BN films. Elastic, plastic, and fracture behavior of the BN films in solid-state contact are discussed. The scratch technique of determining the critical load needed to fracture interfacial adhesive bonds of BN films deposited on substrates is also addressed.

Shunt attachment and method for interfacing current collection systems

DOEpatents

Denney, P.E.; Iyer, N.C.; Hannan, W.F. III.

1992-12-08

A composite brush to shunt attachment wherein a volatile component of a composite but mostly metallic brush, used for current collection purposes, does not upon welding or brazing, adversely affect the formation of the interfacial bond with a conductive shunt which carries the current from the zone of the brush. The brush to shunt attachment for a brush material of copper-graphite composite and a shunt of copper, or substituting silver for copper as an alternative, is made through a hot isostatic pressing (HIP). The HIP process includes applying high pressure and temperature simultaneously at the brush to shunt interface, after it has been isolated or canned in a metal casing in which the air adjacent to the interface has been evacuated and the interfacial area has been sealed before the application of pressure and temperature. 6 figs.

Shunt attachment and method for interfacing current collection systems

DOEpatents

Denney, Paul E.; Iyer, Natraj C.; Hannan, III, William F.

1992-01-01

A composite brush to shunt attachment wherein a volatile component of a composite but mostly metallic brush, used for current collection purposes, does not upon welding or brazing, adversely affect the formation of the interfacial bond with a conductive shunt which carries the current from the zone of the brush. The brush to shunt attachment for a brush material of copper-graphite composite and a shunt of copper, or substituting silver for copper as an alternative, is made through a hot isostatic pressing (HIP). The HIP process includes applying high pressure and temperature simultaneously at the brush to shunt interface, after it has been isolated or canned in a metal casing in which the air adjacent to the interface has been evacuated and the interfacial area has been sealed before the application of pressure and temperature.

Emerging magnetism and anomalous Hall effect in iridate–manganite heterostructures

DOE PAGES

Nichols, John; Gao, Xiang; Lee, Shinbuhm; ...

2016-09-06

We know strong Coulomb repulsion and spin–orbit coupling to give rise to exotic physical phenomena in transition metal oxides. Initial attempts to investigate systems, where both of these fundamental interactions are comparably strong, such as 3d and 5d complex oxide superlattices, have revealed properties that only slightly differ from the bulk ones of the constituent materials. Furthermore, we observe that the interfacial coupling between the 3d antiferromagnetic insulator SrMnO 3 and the 5d paramagnetic metal SrIrO 3 is enormously strong, yielding an anomalous Hall response as the result of charge transfer driven interfacial ferromagnetism. Our findings show that low dimensionalmore » spin–orbit entangled 3d–5d interfaces provide an avenue to uncover technologically relevant physical phenomena unattainable in bulk materials.« less

Building Organic/Inorganic Hybrid Interphases for Fast Interfacial Transport in Rechargeable Metal Batteries.

PubMed

Zhao, Qing; Tu, Zhengyuan; Wei, Shuya; Zhang, Kaihang; Choudhury, Snehashis; Liu, Xiaotun; Archer, Lynden A

2018-01-22

We report a facile in situ synthesis that utilizes readily accessible SiCl 4 cross-linking chemistry to create durable hybrid solid-electrolyte interphases (SEIs) on metal anodes. Such hybrid SEIs composed of Si-interlinked OOCOR molecules that host LiCl salt exhibit fast charge-transfer kinetics and as much as five-times higher exchange current densities, in comparison to their spontaneously formed analogues. Electrochemical analysis and direct optical visualization of Li and Na deposition in symmetric Li/Li and Na/Na cells show that the hybrid SEI provides excellent morphological control at high current densities (3-5 mA cm -2 ) for Li and even for notoriously unstable Na metal anodes. The fast interfacial transport attributes of the SEI are also found to be beneficial for Li-S cells and stable electrochemical cycling was achieved in galvanostatic studies at rates as high as 2 C. Our work therefore provides a promising approach towards rational design of multifunctional, elastic SEIs that overcome the most serious limitations of spontaneously formed interphases on high-capacity metal anodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Top-Down Strategy toward SnSb In-Plane Nanoconfined 3D N-Doped Porous Graphene Composite Microspheres for High Performance Na-Ion Battery Anode.

PubMed

Qin, Jian; Wang, Tianshuai; Liu, Dongye; Liu, Enzuo; Zhao, Naiqin; Shi, Chunsheng; He, Fang; Ma, Liying; He, Chunnian

2018-03-01

Engineering of 3D graphene/metal composites with ultrasmall sized metal and robust metal-graphene interfacial interaction for energy storage application is still a challenge and rarely reported. In this work, a facile top-down strategy is developed for the preparation of SnSb-in-plane nanoconfined 3D N-doped porous graphene networks for sodium ion battery anodes, which are composed of several tens of interconnected empty N-graphene boxes in-plane firmly embedded with ultrasmall SnSb nanocrystals. The all-around encapsulation (plane-to-plane contact) architecture that provides a large interface between N-graphene and SnSb nanocrystal not only effectively enhances the electron conductivity and structural integrity of the overall electrode, but also offers excess interfacial sodium storage, thus leading to much enhanced high-rate sodium storage capacity and stability, which has been proven by both experimental results and first-principles simulations. Moreover, this top-down strategy can enable new paths to the low-cost and high-yield synthesis of 3D graphene/metal composites for applications in energy-related fields and beyond. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

PubMed Central

Li, Yutao; Zhou, Weidong; Chen, Xi; Lü, Xujie; Cui, Zhiming; Xin, Sen; Xue, Leigang; Jia, Quanxi; Goodenough, John B.

2016-01-01

A solid electrolyte with a high Li-ion conductivity and a small interfacial resistance against a Li metal anode is a key component in all-solid-state Li metal batteries, but there is no ceramic oxide electrolyte available for this application except the thin-film Li-P oxynitride electrolyte; ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites in a short time. Here, we introduce a solid electrolyte LiZr2(PO4)3 with rhombohedral structure at room temperature that has a bulk Li-ion conductivity σLi = 2 × 10−4 S⋅cm−1 at 25 °C, a high electrochemical stability up to 5.5 V versus Li+/Li, and a small interfacial resistance for Li+ transfer. It reacts with a metallic lithium anode to form a Li+-conducting passivation layer (solid-electrolyte interphase) containing Li3P and Li8ZrO6 that is wet by the lithium anode and also wets the LiZr2(PO4)3 electrolyte. An all-solid-state Li/LiFePO4 cell with a polymer catholyte shows good cyclability and a long cycle life. PMID:27821751

Improvement of interfacial and electrical properties of Al2O3/ n-Ga0.47In0.53As for III-V impact ionization MOSFETs

NASA Astrophysics Data System (ADS)

Lechaux, Y.; Fadjie, A.; Bollaert, S.; Talbo, V.; Mateos, J.; González, T.; Vasallo, B. G.; Wichmann, N.

2015-10-01

In this work, Metal - Oxide - Semiconductor Capacitors (MOSCaps) based on Al2O3/ n-Ga0.47In0.53As interface have been studied. In order to have high MOSFETs performance, it is necessary to improve the semiconductor - oxide interface quality. It is observed that the (NH4)2S passivation shows lower interface trap density in the order of 6×1011cm-2.eV-1. Also, it is observed that O2 plasma densification after a passivation in a NH4OH solution improves the electrical behaviour of the charge control. Low interface trap density in the order of 1×1012cm-2.eV-1 was obtained for different treatments presented in this work.

Governing Influence of Thermodynamic and Chemical Equilibria on the Interfacial Properties in Complex Fluids.

PubMed

Harikrishnan, A R; Dhar, Purbarun; Gedupudi, Sateesh; Das, Sarit K

2018-04-12

We propose a comprehensive analysis and a quasi-analytical mathematical formalism to predict the surface tension and contact angles of complex surfactant-infused nanocolloids. The model rests on the foundations of the interaction potentials for the interfacial adsorption-desorption dynamics in complex multicomponent colloids. Surfactant-infused nanoparticle-laden interface problems are difficult to deal with because of the many-body interactions and interfaces involved at the meso-nanoscales. The model is based on the governing role of thermodynamic and chemical equilibrium parameters in modulating the interfacial energies. The influence of parameters such as the presence of surfactants, nanoparticles, and surfactant-capped nanoparticles on interfacial dynamics is revealed by the analysis. Solely based on the knowledge of interfacial properties of independent surfactant solutions and nanocolloids, the same can be deduced for complex surfactant-based nanocolloids through the proposed approach. The model accurately predicts the equilibrium surface tension and contact angle of complex nanocolloids available in the existing literature and present experimental findings.

A stable organic-inorganic hybrid layer protected lithium metal anode for long-cycle lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Zhu, Jinhui; Yang, Jun; Zhou, Jingjing; Zhang, Tao; Li, Lei; Wang, Jiulin; Nuli, Yanna

2017-10-01

A stable organic-inorganic hybrid layer (OIHL) is direct fabricated on lithium metal surface by the interfacial reaction of lithium metal foil with 1-chlorodecane and oxygen/carbon dioxide mixed gas. This favorable OIHL is approximately 30 μm thick and consists of lithium alkyl carbonate and lithium chloride. The lithium-oxygen batteries with OIHL protected lithium metal anode exhibit longer cycle life (340 cycles) than those with bare lithium metal anode (50 cycles). This desirable performance can be ascribed to the robust OIHL which prevents the growth of lithium dendrites and the corrosion of lithium metal.

Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects

DOE PAGES

Pascal, Tod A.; Villaluenga, Irune; Wujcik, Kevin H.; ...

2017-03-14

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ~30° below the expectedmore » freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.« less

Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt-Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy.

PubMed

Flynn, Brendan T; Oleksak, Richard P; Thevuthasan, Suntharampillai; Herman, Gregory S

2018-01-31

A method to understand the role of interfacial chemistry on the modulation of Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. In situ X-ray photoelectron spectroscopy was used to characterize the interfacial chemistries that modulate barrier heights in this system. The primary changes were a significant chemical reduction of indium, from In 3+ to In 0 , that occurs during deposition of Pt on to the a-IGZO surface in ultrahigh vacuum. Postannealing and controlling the background ambient O 2 pressure allows further tuning of the reduction of indium and the corresponding Schottky barrier heights from 0.17 to 0.77 eV. Understanding the detailed interfacial chemistries at Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metal-semiconductor field-effect transistors.

Static gas-liquid interfacial direct current discharge plasmas using ionic liquid cathode

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

Kaneko, T.; CREST/JST, Tokyo 102-0075; Baba, K.

Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we have succeeded in creating the static and stable gas (plasmas)-liquid (ionic liquids) interfacial field using a direct current discharge under a low gas pressure condition. It is clarified that the ionic liquid works as a nonmetal liquid electrode, and furthermore, a secondary electron emission coefficient of the ionic liquid is larger than that of conventional metal electrodes. The plasma potential structure of the gas-liquid interfacial region, and resultant interactions between the plasma and the ionic liquid are revealed by changingmore » a polarity of the electrode in the ionic liquid. By utilizing the ionic liquid as a cathode electrode, the positive ions in the plasma region are found to be irradiated to the ionic liquid. This ion irradiation causes physical and chemical reactions at the gas-liquid interfacial region without the vaporization of the ionic liquid.« less

Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects.

PubMed

Pascal, Tod A; Villaluenga, Irune; Wujcik, Kevin H; Devaux, Didier; Jiang, Xi; Wang, Dunyang Rita; Balsara, Nitash; Prendergast, David

2017-04-12

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ∼30° below the expected freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.

Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

DOE PAGES

Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; ...

2016-05-30

All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte – electrode interfaces will be critical to improve performance. In this paper, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grewmore » in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. Finally, the stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.« less

Thickness dependence of the interfacial Dzyaloshinskii–Moriya interaction in inversion symmetry broken systems

PubMed Central

Cho, Jaehun; Kim, Nam-Hui; Lee, Sukmock; Kim, June-Seo; Lavrijsen, Reinoud; Solignac, Aurelie; Yin, Yuxiang; Han, Dong-Soo; van Hoof, Niels J. J.; Swagten, Henk J. M.; Koopmans, Bert; You, Chun-Yeol

2015-01-01

In magnetic multilayer systems, a large spin-orbit coupling at the interface between heavy metals and ferromagnets can lead to intriguing phenomena such as the perpendicular magnetic anisotropy, the spin Hall effect, the Rashba effect, and especially the interfacial Dzyaloshinskii–Moriya (IDM) interaction. This interfacial nature of the IDM interaction has been recently revisited because of its scientific and technological potential. Here we demonstrate an experimental technique to straightforwardly observe the IDM interaction, namely Brillouin light scattering. The non-reciprocal spin wave dispersions, systematically measured by Brillouin light scattering, allow not only the determination of the IDM energy densities beyond the regime of perpendicular magnetization but also the revelation of the inverse proportionality with the thickness of the magnetic layer, which is a clear signature of the interfacial nature. Altogether, our experimental and theoretical approaches involving double time Green's function methods open up possibilities for exploring magnetic hybrid structures for engineering the IDM interaction. PMID:26154986

Dopant-Modulating Mechanism of Lithium Adsorption and Diffusion at the Graphene /Li2S Interface

NASA Astrophysics Data System (ADS)

Guo, Lichao; Li, Jiajun; Wang, Huayu; Zhao, Naiqin; Shi, Chunsheng; Ma, Liying; He, Chunnian; He, Fang; Liu, Enzuo

2018-02-01

Graphene modification is one of the most effective routes to enhance the electrochemical properties of the transition-metal sulfide anode for Li-ion batteries and the Li2S cathode for Li-S batteries. Boron, nitrogen, oxygen, phosphorus, and sulfur doping greatly affect the electrochemical properties of Li2S /graphene . Here, we investigate the interfacial binding energy, lithium adsorption energy, interface diffusion barrier, and electronic structure by first-principles calculations to unveil the diverse effects of different dopants during interfacial lithiation reactions. The interfacial lithium storage follows the pseudocapacitylike mechanism with intercalation character. Two different mechanisms are revealed to enhance the interfacial lithium adsorption and diffusion, which are the electron-deficiency host doping and the vacancylike structure evolutions with bond breaking. The synergistic effect between different dopants with diverse doping effects is also proposed. The results give a theoretical basis for the materials design with doped graphene as advanced materials modification for energy storage.

POISON SPIDER FIELD CHEMICAL FLOOD PROJECT, WYOMING

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

Douglas Arnell; Malcolm Pitts; Jie Qi

2004-11-01

A reservoir engineering and geologic study concluded that approximate 7,852,000 bbls of target oil exits in Poison Spider. Field pore volume, OOIP, and initial oil saturation are defined. Potential injection water has a total dissolved solids content of 1,275 mg/L with no measurable divalent cations. If the Lakota water consistently has no measurable cations, the injection water does not require softening to dissolve alkali. Produced water total dissolved solids were 2,835 mg/L and less than 20 mg/L hardness as the sum of divalent cations. Produced water requires softening to dissolve chemicals. Softened produced water was used to dissolve chemicals inmore » these evaluations. Crude oil API gravity varies across the field from 19.7 to 22.2 degrees with a dead oil viscosity of 95 to 280 cp at 75 F. Interfacial tension reductions of up to 21,025 fold (0.001 dyne/cm) were developed with fifteen alkaline-surfactant combinations at some alkali concentration. An additional three alkaline-surfactant combinations reduced the interfacial tension greater than 5,000 fold. NaOH generally produced the lowest interfacial tension values. Interfacial tension values of less than 0.021 dyne/cm were maintained when the solutions were diluted with produced water to about 60%. Na{sub 2}CO{sub 3} when mixed with surfactants did not reduce interfacial tension values to levels at which incremental oil can be expected. NaOH without surfactant interfacial tension reduction is at a level where some additional oil might be recovered. Most of the alkaline-surfactant-polymer solutions producing ultra low interfacial tension gave type II- phase behavior. Only two solutions produced type III phase behavior. Produced water dilution resulted in maintenance of phase type for a number of solutions at produced water dilutions exceeding 80% dilution. The average loss of phase type occurred at 80% dilution. Linear corefloods were performed to determine relative permeability end points, chemical-rock compatibility, polymer injectivity, dynamic chemical retention by rock, and recommended injected polymer concentration. Average initial oil saturation was 0.796 Vp. Produced water injection recovered 53% OOIP leaving an average residual oil saturation of 0.375 Vp. Poison Spider rock was strongly water-wet with a mobility ratio for produced water displacing the 280 cp crude oil of 8.6. Core was not sensitive to either alkali or surfactant injection. Injectivity increased 60 to 80% with alkali plus surfactant injection. Low and medium molecular weight polyacrylamide polymers (Flopaam 3330S and Flopaam 3430S) dissolved in either an alkaline-surfactant solution or softened produced water injected and flowed through Poison Spider rock. Recommended injected polyacrylamide concentration is 2,100 mg/L for both polymers for a unit mobility ratio. Radial corefloods were performed to evaluate oil recovery efficiency of different chemical solutions. Waterflood oil recovery averaged 46.4 OOIP and alkaline-surfactant-polymer flood oil recovery averaged an additional 18.1% OIP for a total of 64.6% OOIP. Oil cut change due to injection of a 1.5 wt% Na{sub 2}CO{sub 3} plus 0.05 wt% Petrostep B-100 plus 0.05 wt% Stepantan AS1216 plus 2100 mg/L Flopaam 3430S was from 2% to a peak of 23.5%. Additional study might determine the impact on oil recovery of a lower polymer concentration. An alkaline-surfactant-polymer flood field implementation outline report was written.« less

A Deterministic Interfacial Cyclic Oxidation Spalling Model. Part 1; Model Development and Parametric Response

NASA Technical Reports Server (NTRS)

Smialek, James L.

2002-01-01

An equation has been developed to model the iterative scale growth and spalling process that occurs during cyclic oxidation of high temperature materials. Parabolic scale growth and spalling of a constant surface area fraction have been assumed. Interfacial spallation of the only the thickest segments was also postulated. This simplicity allowed for representation by a simple deterministic summation series. Inputs are the parabolic growth rate constant, the spall area fraction, oxide stoichiometry, and cycle duration. Outputs include the net weight change behavior, as well as the total amount of oxygen and metal consumed, the total amount of oxide spalled, and the mass fraction of oxide spalled. The outputs all follow typical well-behaved trends with the inputs and are in good agreement with previous interfacial models.

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

Zhou, Shenggao, E-mail: sgzhou@suda.edu.cn, E-mail: bli@math.ucsd.edu; Sun, Hui; Cheng, Li-Tien

Recent years have seen the initial success of a variational implicit-solvent model (VISM), implemented with a robust level-set method, in capturing efficiently different hydration states and providing quantitatively good estimation of solvation free energies of biomolecules. The level-set minimization of the VISM solvation free-energy functional of all possible solute-solvent interfaces or dielectric boundaries predicts an equilibrium biomolecular conformation that is often close to an initial guess. In this work, we develop a theory in the form of Langevin geometrical flow to incorporate solute-solvent interfacial fluctuations into the VISM. Such fluctuations are crucial to biomolecular conformational changes and binding process. Wemore » also develop a stochastic level-set method to numerically implement such a theory. We describe the interfacial fluctuation through the “normal velocity” that is the solute-solvent interfacial force, derive the corresponding stochastic level-set equation in the sense of Stratonovich so that the surface representation is independent of the choice of implicit function, and develop numerical techniques for solving such an equation and processing the numerical data. We apply our computational method to study the dewetting transition in the system of two hydrophobic plates and a hydrophobic cavity of a synthetic host molecule cucurbit[7]uril. Numerical simulations demonstrate that our approach can describe an underlying system jumping out of a local minimum of the free-energy functional and can capture dewetting transitions of hydrophobic systems. In the case of two hydrophobic plates, we find that the wavelength of interfacial fluctuations has a strong influence to the dewetting transition. In addition, we find that the estimated energy barrier of the dewetting transition scales quadratically with the inter-plate distance, agreeing well with existing studies of molecular dynamics simulations. Our work is a first step toward the inclusion of fluctuations into the VISM and understanding the impact of interfacial fluctuations on biomolecular solvation with an implicit-solvent approach.« less

Convective and interfacial instabilities during solidification of succinonitrile containing ethanol

NASA Technical Reports Server (NTRS)

Schaefer, R. J.; Coriell, S. R.

1982-01-01

Even though slow convective flow is difficult to detect in solidifying metals, it can readily be observed in transparent materials by observing the motion of small neutrally buoyant particles. Succinonitrile, which solidifies with an unfaceted solid/liquid interface and has well characterized physical properties, is considered an excellent material for such studies. For studies of solute-induced convection, ethanol is a useful addition to succinonitrile since it has a lower density and a somewhat similar molecular structure. Samples of high purity and ethanol-doped succinonitrile are unidirectionally solidified in a vertical temperature gradient. Latex mimcrospheres 2 microns in diameter are suspended in the liquid to reveal the convective flow. Convective and morphological stability is observed as a function of solute concentration and growth velocity. These measurements are compared with theoretical calculations that predict the transition from stability to instability as a function of solidification conditions. The predicted transitions occur at low concentrations and solidification velocities; for this reason, extreme care must be taken in order to eliminate the effects of impurities or thermally induced convection.

Aerosol Particle Interfacial Thermodynamics and Phase Partitioning Measurements Using Biphasic Microfluidics

NASA Astrophysics Data System (ADS)

Dutcher, Cari; Metcalf, Andrew

2015-03-01

Secondary organic aerosol particles are nearly ubiquitous in the atmosphere and yet there remain large uncertainties in their formation processes and ambient properties. These particles are complex microenvironments, which can contain multiple interfaces due to internal aqueous-organic phase partitioning and to the external liquid-vapor surface. Interfacial properties affect the ambient aerosol morphology, or internal structure of the particle, which in turn can affect the way a particle interacts with an environment of condensable clusters and organic vapors. To improve our ability to accurately predict ambient aerosol morphology, we must improve our knowledge of aerosol interfaces and their interactions with the ambient environment. Unfortunately, many techniques employed to measure interfacial properties do so in bulk solutions or in the presence of a ternary (e.g. solid) phase. In this talk, a novel method using biphasic microscale flows will be introduced for generating, trapping, and perturbing complex interfaces at atmospherically relevant conditions. These microfluidic experiments utilize high-speed imaging to monitor interfacial phenomena at the microscale and are performed with phase contrast and fluorescence microscopy on a temperature-controlled inverted microscope stage. From these experiments, interfacial thermodynamic properties such as surface or interfacial tension, rheological properties such as interfacial moduli, and kinetic properties such as mass transfer coefficients can be measured or inferred.

Interfacial Control of Ferromagnetism in Ultrathin La0.67Ca0.33MnO3 Sandwiched between CaRu1-xTixO3 (x = 0-0.8) Epilayers.

PubMed

Chen, Binbin; Chen, Pingfan; Xu, Haoran; Jin, Feng; Guo, Zhuang; Lan, Da; Wan, Siyuan; Gao, Guanyin; Chen, Feng; Wu, Wenbin

2016-12-21

Controlling functionalities in oxide heterostructures remains challenging for the rather complex interfacial interactions. Here, by modifying the interface properties with chemical doping, we achieve a nontrivial control over the ferromagnetism in ultrathin La 0.67 Ca 0.33 MnO 3 (LCMO) layer sandwiched between CaRu 1-x Ti x O 3 [CRTO(x)] epilayers. The Ti doping suppresses the interfacial electron transfer from CRTO(x) to LCMO side; as a result, a steadily decreased Curie temperature with increasing x, from 262 K at x = 0 to 186 K at x = 0.8, is observed for the structures with LCMO fixed at 3.2 nm. Moreover, for more insulating CRTO(x ≥ 0.5), the electron confinement induces an interfacial Mn-e g (x 2 -y 2 ) orbital order in LCMO which further attenuates the ferromagnetism. Also, in order to characterize the heterointerfaces, for the first time the doping- and thickness-dependent metal-insulator transitions in CRTO(x) films are examined. Our results demonstrate that the LCMO/CRTO(x) heterostructure could be a model system for investigating the interfacial multiple interactions in correlated oxides.

Defect-driven interfacial electronic structures at an organic/metal-oxide semiconductor heterojunction.

PubMed

Winget, Paul; Schirra, Laura K; Cornil, David; Li, Hong; Coropceanu, Veaceslav; Ndione, Paul F; Sigdel, Ajaya K; Ginley, David S; Berry, Joseph J; Shim, Jaewon; Kim, Hyungchui; Kippelen, Bernard; Brédas, Jean-Luc; Monti, Oliver L A

2014-07-16

The electronic structure of the hybrid interface between ZnO and the prototypical organic semiconductor PTCDI is investigated via a combination of ultraviolet and X-ray photoelectron spectroscopy (UPS/XPS) and density functional theory (DFT) calculations. The interfacial electronic interactions lead to a large interface dipole due to substantial charge transfer from ZnO to 3,4,9,10-perylenetetracarboxylicdiimide (PTCDI), which can be properly described only when accounting for surface defects that confer ZnO its n-type properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Miniature bulge test and energy release rate in HIPed aluminum/aluminum interfacial fracture

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

Liu, C.; Lovato, M. L.; Clarke, K. D.

We summarize the development of a technique of using miniature bulge test combined with three-dimensional digital image correlation (3D-DIC) for measuring energy release rate or fracture toughness of bimaterial interface of thin metal foils. Furthermore, the energy release rate associated with the HIPed aluminum/aluminum interfacial delamination is determined experimentally using the proposed technique. Detailed discussions of the schemes of preparing and conducting the bulge test, and computing various quantities required for the determination of the energy release rate are presented.

Miniature bulge test and energy release rate in HIPed aluminum/aluminum interfacial fracture

DOE PAGES

Liu, C.; Lovato, M. L.; Clarke, K. D.; ...

2017-10-13

We summarize the development of a technique of using miniature bulge test combined with three-dimensional digital image correlation (3D-DIC) for measuring energy release rate or fracture toughness of bimaterial interface of thin metal foils. Furthermore, the energy release rate associated with the HIPed aluminum/aluminum interfacial delamination is determined experimentally using the proposed technique. Detailed discussions of the schemes of preparing and conducting the bulge test, and computing various quantities required for the determination of the energy release rate are presented.

Fiber pushout and interfacial shear in metal-matrix composites

NASA Technical Reports Server (NTRS)

Koss, Donald A.; Hellmann, John R.; Kallas, M. N.

1993-01-01

Recent thin-slice pushout tests have suggested that MMC matrix-fiber interface failure processes depend not only on such intrinsic factors as bond strength and toughness, and matrix plasticity, but such extrinsic factors as specimen configuration, thermally-induced residual stresses, and the mechanics associated with a given test. After detailing the contrasts in fiber-pullout and fiber-pushout mechanics, attention is given to selected aspects of thin-slice fiber pushout behavior illustrative of the physical nature of interfacial shear response and its dependence on both intrinsic and extrinsic factors.

Ionic Effects on Supercritical CO2-Brine Interfacial Tensions: Molecular Dynamics Simulations and a Universal Correlation with Ionic Strength, Temperature, and Pressure.

PubMed

Zhao, Lingling; Ji, Jiayuan; Tao, Lu; Lin, Shangchao

2016-09-13

For geological CO2 storage in deep saline aquifers, the interfacial tension (IFT) between supercritical CO2 and brine is critical for the storage security and design of the storage capacitance. However, currently, no predictive model exists to determine the IFT of supercritical CO2 against complex electrolyte solutions involving various mixed salt species at different concentrations and compositions. In this paper, we use molecular dynamics (MD) simulations to investigate the effect of salt ions on the incremental IFT at the supercritical CO2-brine interface with respect to that at the reference supercritical CO2-water interface. Supercritical CO2-NaCl solution, CO2-CaCl2 solution and CO2-(NaCl+CaCl2) mixed solution systems are simulated at 343 K and 20 MPa under different salinities and salt compositions. We find that the valence of the cations is the primary contributor to the variation in IFT, while the Lennard-Jones potentials for the cations pose a smaller impact on the IFT. Interestingly, the incremental IFT exhibits a general linear correlation with the ionic strength in the above three electrolyte systems, and the slopes are almost identical and independent of the solution types. Based on this finding, a universal predictive formula for IFTs of CO2-complex electrolyte solution systems is established, as a function of ionic strength, temperature, and pressure. The predicted IFTs using the established formula agree perfectly (with a high statistical confidence level of ∼96%) with a wide range of experimental data for CO2 interfacing with different electrolyte solutions, such as those involving MgCl2 and Na2SO4. This work provides an efficient and accurate route to directly predict IFTs in supercritical CO2-complex electrolyte solution systems for practical engineering applications, such as geological CO2 sequestration in deep saline aquifers and other interfacial systems involving complex electrolyte solutions.

Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

PubMed

DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

2017-10-11

Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal < Pt ox . Pt iso species exhibited a 2-fold greater turnover frequency for CO oxidation than 1 nm Pt metal clusters but share an identical reaction mechanism. We propose the active catalytic sites are cationic interfacial Pt atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

Nanophotonic Hot Electron Solar-Blind Ultraviolet Detectors with a Metal-Oxide-Semiconductor Structure

NASA Astrophysics Data System (ADS)

Wang, Zhiyuan

Solar-blind ultraviolet detection refers to photon detection specifically in the wavelength range of 200 nm to 320 nm. Without background noises from solar radiation, it has broad applications from homeland security to environmental monitoring. In this thesis, we design and fabricate a nanophotonic metal-oxide-semiconductor device for solar-blind UV detection. Instead of using semiconductors as the active absorber, we use metal Sn nano- grating structures to absorb UV photons and generate hot electrons for internal photoemission across the Sn/SiO 2 interfacial barrier, thereby generating photocurrent between metal and semiconductor region upon UV excitation. The large metal/oxide interfacial energy barrier enables solar-blind UV detection by blocking the less energetic electrons excited by visible photons. With optimized design, 85% UV absorption and hot electron excitation can be achieved within the mean free path of 20 nm from the metal/oxide interface. This feature greatly enhances hot electron transport across the interfacial barrier to generate photocurrent. Various fabrication techniques have been developed for preparing nano gratings. For nominally 20 nm-thick deposited Sn, the self- formed pseudo-periodic nanostructure help achieve 75% UV absorption from lambda=200 nm to 300 nm. With another layer of nominally 20 nm-thick Sn, similar UV absorption is maintained while conductivity is improved, which is beneficial for overall device efficiency. The Sn/SiO2/Si MOS devices show good solar-blind character while achieving 13% internal quantum efficiency for 260 nm UV with only 20 nm-thick Sn and some devices demonstrate much higher (even >100%) internal quantum efficiency. While a more accurate estimation of device effective area is needed for proving our calculation, these results indeed show a great potential for this type of hot-electron-based photodetectors and for Sn nanostructure as an effective UV absorber. The simple geometry of the self- assembled Sn nano-gratings and MOS structure make this novel type of device easy to fabricate and integrate with Si ROICs compared to existing solar-blind UV detection schemes. The presented device structure also breaks through the conventional notion that photon absorption by metal is always a loss in solid-state photodetectors, and it can potentially be extended to other active metal photonic devices.

Role of segregation and precipitates on interfacial strengthening mechanisms in metal matrix composites when subjected to thermo-mechanical processing

NASA Astrophysics Data System (ADS)

Myriounis, Dimitrios

Metal Matrix ceramic-reinforced composites are rapidly becoming strong candidates as structural materials for many high temperatures and aerospace applications. Metal matrix composites combine the ductile properties of the matrix with a brittle phase of the reinforcement, leading to high stiffness and strength with a reduction in structural weight. The main objective of using a metal matrix composite system is to increase service temperature or improve specific mechanical properties of structural components by replacing existing superalloys.The satisfactory performance of metal matrix composites depends critically on their integrity, the heart of which is the quality of the matrix-reinforcement interface. The nature of the interface depends on the processing of the metal matrix composite component. At the micro-level the development of local stress concentration gradients around the ceramic reinforcement, as the metal matrix attempts to deform during processing, can be very different to the nominal conditions and play a crucial role in important microstructural events such as segregation and precipitation at the matrix-reinforcement interface. These events dominate the cohesive strength and subsequent mechanical properties of the interface.At present the relationship between the strength properties of metal matrix composites and the details of the thermo-mechanical forming processes is not well understood.The purpose of the study is to investigate several strengthening mechanisms and the effect of thermo-mechanical processing of SiCp reinforced A359 aluminium alloy composites on the particle-matrix interface and the overall mechanical properties of the material. From experiments performed on composite materials subjected to various thermo-mechanical conditions and by observation using SEM microanalysis and mechanical testing, data were obtained, summarised and mathematically/statistically analysed upon their significance.The Al/SiCp composites studied, processed in specific thermo-mechanical conditions in order to attain higher values of interfacial fracture strength, due to precipitation hardening and segregation mechanisms, also exhibited enhanced bulk mechanical and fracture resistant properties.An analytical model to predict the interfacial fracture strength in the presence of material segregation was also developed during this research effort. Its validity was determined based on the data gathered from the experiments.The tailoring of the properties due to the microstructural modification of the composites was examined in relation to the experimental measurements obtained, which define the macroscopical behaviour of the material.

Discrete Self-Similarity in Interfacial Hydrodynamics and the Formation of Iterated Structures.

PubMed

Dallaston, Michael C; Fontelos, Marco A; Tseluiko, Dmitri; Kalliadasis, Serafim

2018-01-19

The formation of iterated structures, such as satellite and subsatellite drops, filaments, and bubbles, is a common feature in interfacial hydrodynamics. Here we undertake a computational and theoretical study of their origin in the case of thin films of viscous fluids that are destabilized by long-range molecular or other forces. We demonstrate that iterated structures appear as a consequence of discrete self-similarity, where certain patterns repeat themselves, subject to rescaling, periodically in a logarithmic time scale. The result is an infinite sequence of ridges and filaments with similarity properties. The character of these discretely self-similar solutions as the result of a Hopf bifurcation from ordinarily self-similar solutions is also described.

Tuning Magnetic Order in Transition Metal Oxide Thin Films

NASA Astrophysics Data System (ADS)

Grutter, Alexander John

In recent decades, one of the most active and promising areas of condensed matter research has been that of complex oxides. With the advent of new growth techniques such as pulsed laser deposition and molecular beam epitaxy, a wealth of new magnetic and electronic ground states have emerged in complex oxide heterostructures. The wide variety of ground states in complex oxides is well known and generally attributed to the unprecedented variety of valence, structure, and bonding available in these systems. The tunability of this already diverse playground of states and interactions is greatly multiplied in thin films and heterostructures by the addition of parameters such as substrate induced strain and interfacial electronic reconstruction. Thus, recent studies have shown emergent properties such as the stabilization of ferromagnetism in a paramagnetic system, conductivity at the interface of two insulators, and even exchange bias at the interface between a paramagnet and a ferromagnet. Despite these steps forward, there remains remarkable disagreement on the mechanisms by which these emergent phenomena are stabilized. The contributions of strain, stoichiometry, defects, intermixing, and electronic reconstruction are often very difficult to isolate in thin films and superlattices. This thesis will present model systems for isolating the effects of strain and interfacial electronic interactions on the magnetic state of complex oxides from alternative contributions. We will focus first on SrRuO3, an ideal system in which to isolate substrate induced strain effects. We explore the effects of structural distortions in the simplest case of growth on (100) oriented substrates. We find that parameters including saturated magnetic moment and Curie temperature are all highly tunable through substrate induced lattice distortions. We also report the stabilization of a nonmagnetic spin-zero configuration of Ru4+ in tetragonally distorted films under tensile strain. Through growth on (110) and (111) oriented substrates we explore the effects of different distortion symmetries on SrRuO3 and demonstrate the first reported strain induced transition to a high-spin state of Ru 4+. Finally, we examine the effects of strain on SrRuO3 thin films and demonstrate a completely reversible universal out-of-plane magnetic easy axis on films grown on different substrate orientations. Having demonstrated the ability to tune nearly every magnetic parameter of SrRuO 3 through strain, we turn to magnetic properties at interfaces. We study the emergent interfacial ferromagnetism in superlattices of the paramagnetic metal CaRuO3 and the antiferromagnetic insulator CaMnO3 and demonstrate that the interfacial ferromagnetic layer in this system is confined to a single unit cell of CaMnO3 at the interface. We discuss the remarkable oscillatory dependence of the saturated magnetic moment on the thickness of the CaMnO3 layers and explore mechanisms by which this oscillation may be stabilized. We find long range coherence of the antiferromagnetism of the CaMnO3 layers across intervening layers of paramagnetic CaRuO3. Finally, we utilize the system of LaNiO3/CaMnO3 to separate the effects of intermixing and interfacial electronic reconstruction and conclusively demonstrate intrinsic interfacial ferromagnetism at the interface between a paramagnetic metal and an antiferromagnetic insulator. We find that the emergent ferromagnetism is stabilized through interfacial double exchange and that the leakage of conduction electrons from the paramagnetic metal to the antiferromagnetic insulator is critical to establishing the ferromagnetic ground state.

The Interfacial Thermal Conductance of Epitaxial Metal-Semiconductor Interfaces

NASA Astrophysics Data System (ADS)

Ye, Ning

Understanding heat transport at nanometer and sub-nanometer lengthscales is critical to solving a wide range of technological challenges related to thermal management and energy conversion. In particular, finite Interfacial Thermal Conductance (ITC) often dominates transport whenever multiple interfaces are closely spaced together or when heat originates from sources that are highly confined by interfaces. Examples of the former include superlattices, thin films, quantum cascade lasers, and high density nanocomposites. Examples of the latter include FinFET transistors, phase-change memory, and the plasmonic transducer of a heat-assisted magnetic recording head. An understanding of the physics of such interfaces is still lacking, in part because experimental investigations to-date have not bothered to carefully control the structure of interfaces studied, and also because the most advanced theories have not been compared to the most robust experimental data. This thesis aims to resolve this by investigating ITC between a range of clean and structurally well-characterized metal-semiconductor interfaces using the Time-Domain Thermoreflectance (TDTR) experimental technique, and by providing theoretical/computational comparisons to the experimental data where possible. By studying the interfaces between a variety of materials systems, each with unique aspects to their tunability, I have been able to answer a number of outstanding questions regarding the importance of interfacial quality (epitaxial/non-epitaxial interfaces), semiconductor doping, matching of acoustic and optical phonon band structure, and the role of phonon transport mechanisms apart from direct elastic transmission on ITC. In particular, we are able to comment on the suitability of the diffuse mismatch model (DMM) to describe the transport across epitaxial interfaces. To accomplish this goal, I studied interfacial thermal transport across CoSi2, TiSi2, NiSi and PtSi - Si(100) and Si(111), (silicides-silicon), interfaces with varying levels of disorder (epitaxial and non-epitaxial). The ITC values of silicides-silicon interfaces observed in this study are higher than those of other metallic interfaces to Si found in literature. Most surprisingly, it is experimentally found that ITC values are independent of interfacial quality and substrate orientation. Computationally, it is found that the non-equilibrium atomistic Green's Function technique (NEGF), which is specically designed to simulate coherent elastic phonon transport across interfaces, significantly underpredicts ITC values for CoSi2-Si interfaces, suggesting that energy transport does not occur purely by coherent transmission of phonons, even for epitaxial interfaces. In contrast, the Diffuse Mismatch Model closely mimics the experimentally observed ITC values for CoSi 2-Si, NiSi-Si and TiSi2-Si interfaces, and only slightly overestimating the same for PtSi-Si interfaces. Furthermore, the results also show that ITC is independent of degenerate doping up to doping levels of ≈1 x 1019 cm-3, indicating there is no significant direct electronic transport or transport effects which depend on long-range metal-semiconductor band alignment. Then, I study the effect of phonon band structure on ITC through measurements of epitaxial NiAl1-xGax-GaAs interfaces for varying levels of alloy composition, which independently tunes the mass of the metal's heavy atom without much affect on the lattice structure or interatomic force constants. The ITC values are found to linearly increase with increasing Ga content, consistent with the disappearance of a phonon band gap in NiAl 1-xGax films with increasing Ga content, which enhances the phonon transmission coefficients due to a better density of states overlap between the two (NiAl1-xGax, GaAs) materials. Finally, I study a unique subset of epitaxial rocksalt interfaces between the Group IV metal nitrides (TiN, ZrN, and HfN) to MgO substrates as well as ScN layers. Prior to the currrent study, TiN-MgO was the only measured interface of this type, and maintained the record for the highest reported ITC for a metal-semiconductor interface. By varying the Group IV metal, the mass of the metal's light atom was independently tuned, allowing the ability to tune the acoustic phonon frequencies in the metal without significant effect to optical phonon band structure. We find that the ITC of all the studied interfaces are quite high, significantly exceeding the DMM predictions, and in the case of XN-ScN interfaces even exceed the radiative limit for elastic phonon transport. The results imply that mechanisms such as anharmonic phonon transmission, strong cross-interfacial electron phonon coupling, or direct electric transmission are required to explain the transport. The TiN-ScN interface conductance is the highest room temperature metal-dielectric conductance ever reported.

Performance of CAD/CAM fabricated fiber posts in oval-shaped root canals: An in vitro study.

PubMed

Tsintsadze, Nino; Juloski, Jelena; Carrabba, Michele; Tricarico, Marella; Goracci, Cecilia; Vichi, Alessandro; Ferrari, Marco; Grandini, Simone

2017-10-01

To assess the push-out strength, the cement layer thickness and the interfacial nanoleakage of prefabricated fiber posts, CAD/CAM fiber posts and metal cast posts cemented into oval-shaped root canals. Oval-shaped post spaces were prepared in 30 single-rooted premolars. Roots were randomly assigned to three groups (n=10), according to the post type to be inserted: Group 1: Prefabricated fiber post (D.T. Light-Post X-RO Illusion); Group 2: Cast metal post; Group 3: CAD/CAM-fabricated fiber post (experimental fiber blocks). In Group 3, post spaces were sprayed with scan powder (VITA), scanned with an inEos 4.2 scanner, and fiber posts were milled using an inLab MC XL CAD/CAM milling unit. All posts were cemented using Gradia Core dual-cure resin cement in combination with Gradia core self-etching bond (GC). After 24 hours, the specimens were sectioned perpendicular to the long axis into six 1 mm-thick sections, which were differentiated by the root level. Sections from six roots per group were used to measure the cement thickness and subsequently for the thin-slice push-out test, whereas the sections from the remaining four teeth were assigned to interfacial nanoleakage test. The cement thickness around the posts was measured in micrometers (µm) on the digital images acquired with a digital microscope using the Digimizer software. Thin-slice push-out test was conducted using a universal testing machine at the crosshead speed of 0.5 mm/minute and the bond strength was expressed in megaPascals (MPa). The interfacial nanoleakage was observed under light microscope and quantified by scoring the depth of silver nitrate penetration along the post-cement-dentin interfaces. The obtained results were statistically analyzed by Kruskal-Wallis ANOVA, followed by the Dunn's Multiple Range test for post hoc comparisons. The level of significance was set at P< 0.05. Statistically significant differences were found among the groups in push-out bond strength, cement thickness and interfacial nanoleakage (P< 0.05). CAD/CAM-fabricated fiber posts achieved retention that was comparable to that of cast metal posts and significantly higher than that of prefabricated fiber posts. The cement layer thickness around CAD/CAM-fabricated fiber posts was significantly lower than around prefabricated fiber posts, but higher than that around cast metal posts. Root level was not a significant factor for push-out strength in any of the groups, whereas it significantly affected cement layer thickness only in the prefabricated fiber post group. No differences were observed in interfacial nanoleakage between CAD/CAM fabricated and prefabricated fiber posts, while nanoleakage recorded in cast metal posts was significantly lower. CAD/CAM fabricated fiber posts could represent a valid alternative to traditionally used posts in the restoration of endodontically-treated teeth with oval or wide root canals, offering the advantages of better esthetics, retention, and cement thickness values that are comparable to cast post and cores.

Understanding the influence of capillary waves on solvation at the liquid-vapor interface

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

Rane, Kaustubh, E-mail: rane@csi.tu-darmstadt.de; Vegt, Nico F. A. van der

2016-03-21

This work investigates the question if surface capillary waves (CWs) affect interfacial solvation thermodynamic properties that determine the propensity of small molecules toward the liquid-vapor interface. We focus on (1) the evaluation of these properties from molecular simulations in a practical manner and (2) understanding them from the perspective of theories in solvation thermodynamics, especially solvent reorganization effects. Concerning the former objective, we propose a computational method that exploits the relationship between an external field acting on the liquid-vapor interface and the magnitude of CWs. The system considered contains the solvent, an externally applied field (f) and the solute moleculemore » fixed at a particular location. The magnitude of f is selected to induce changes in CWs. The difference between the solvation free energies computed in the presence and in the absence of f is then shown to quantify the contribution of CWs to interfacial solvation. We describe the implementation of this method in the canonical ensemble by using a Lennard-Jones solvent and a non-ionic solute. Results are shown for three types of solutes that differ in the nature of short-ranged repulsive (hard-core) interactions. Overall, we observe that CWs have a negligible or very small effect on the interfacial solvation free energy of a solute molecule fixed near the liquid-vapor interface for the above systems. We also explain how the effects of pinning or dampening of CWs caused by a fixed solute are effectively compensated and do not contribute to the solvation free energy.« less

Interfacial Water at Protein Surfaces: Wide-Line NMR and DSC Characterization of Hydration in Ubiquitin Solutions

PubMed Central

Tompa, Kálmán; Bánki, Péter; Bokor, Mónika; Kamasa, Pawel; Lasanda, György; Tompa, Péter

2009-01-01

Wide-line 1H-NMR and differential scanning calorimetry measurements were done in aqueous solutions and on lyophilized samples of human ubiquitin between −70°C and +45°C. The measured properties (size, thermal evolution, and wide-line NMR spectra) of the protein-water interfacial region are substantially different in the double-distilled and buffered-water solutions of ubiquitin. The characteristic transition in water mobility is identified as the melting of the nonfreezing/hydrate water. The amount of water in the low-temperature mobile fraction is 0.4 g/g protein for the pure water solution. The amount of mobile water is higher and its temperature dependence more pronounced for the buffered solution. The specific heat of the nonfreezing/hydrate water was evaluated using combined differential scanning calorimetry and NMR data. Considering the interfacial region as an independent phase, the values obtained are 5.0–5.8 J·g−1·K−1, and the magnitudes are higher than that of pure/bulk water (4.2 J·g−1·K−1). This unexpected discrepancy can only be resolved in principle by assuming that hydrate water is in tight H-bond coupling with the protein matrix. The specific heat for the system composed of the protein molecule and its hydration water is 2.3 J·g−1·K−1. It could be concluded that the protein ubiquitin and its hydrate layer behave as a highly interconnected single phase in a thermodynamic sense. PMID:19348762

Characterizing Radio Emission From Extensive Air Showers with the SLAC-T510 Experiment, with Applications to ANITA

NASA Astrophysics Data System (ADS)

McGuire, Felicia Ann

Essential to metal-oxide-semiconductor field-effect transistor (MOSFET) scaling is the reduction of the supply voltage to mitigate the power consumption and corresponding heat dissipation. Conventional dielectric materials are subject to the thermal limit imposed by the Boltzmann factor in the subthreshold swing, which places an absolute minimum on the supply voltage required to modulate the current. Furthermore, as technology approaches the 5 nm node, electrostatic control of a silicon channel becomes exceedingly difficult, regardless of the gating technique. This notion of "the end of silicon scaling" has rapidly increased research into more scalable channel materials as well as new methods of transistor operation. Among the many promising options are two-dimensional (2D) FETs and negative capacitance (NC) FETs. 2D-FETs make use of atomically thin semiconducting channels that have enabled demonstrated scalability beyond what silicon can offer. NC-FETs demonstrate an effective negative capacitance arising from the integration of a ferroelectric into the transistor gate stack, allowing sub-60 mV/dec switching. While both of these devices provide significant advantages, neither can accomplish the ultimate goal of a FET that is both low-voltage and scalable. However, an appropriate fusion of the 2D-FET and NC-FET into a 2D NC-FET has the potential of enabling a steep-switching device that is dimensionally scalable beyond the 5 nm technology node. In this work, the motivation for and operation of 2D NC-FETs is presented. Experimental realization of 2D NC-FETs using 2D transition metal dichalcogenide molybdenum disulfide (MoS2) as the channel is shown with two different ferroelectric materials: 1) a solution-processed, polymeric poly(vinylidene difluoride trifluoroethylene) ferroelectric and 2) an atomic layer deposition (ALD) grown hafnium zirconium oxide (HfZrO2) ferroelectric. Each ferroelectric was integrated into the gate stack of a 2D-FET having either a top-gate (polymeric ferroelectric) or bottom-gate (HfZrO2 ferroelectric) configuration. HfZrO 2 devices with metallic interfacial layers (between ferroelectric and dielectric) and thinner ferroelectric layers were found to reduce both the hysteresis and the threshold voltage. Detailed characterization of the devices was performed and, most significantly, the 2D NC-FETs with HfZrO2 reproducibly yielded subthreshold swings well below the thermal limit with over more than four orders of magnitude in drain current modulation. HfZrO 2 devices without metallic interfacial layers were utilized to explore the impact of ferroelectric thickness, dielectric thickness, and dielectric composition on device performance. The impact of an interfacial metallic layer on the device operation was investigated in devices with HfZrO2 and shown to be crucial at enabling sub-60 mV/dec switching and large internal voltage gains. The significance of dielectric material choice on device performance was explored and found to be a critical factor in 2D NC-FET transistor operation. These successful results pave the way for future integration of this new device structure into existing technology markets.

Forced Spreading of Aqueous Solutions on Zwitterionic Sulfobetaine Surfaces for Rapid Evaporation and Solute Separation.

PubMed

Wu, Cyuan-Jhang; Singh, Vickramjeet; Sheng, Yu-Jane; Tsao, Heng-Kwong

2017-08-01

Solute separation of aqueous mixtures is mainly dominated by water vaporization. The evaporation rate of an aqueous drop grows with increasing the liquid-gas interfacial area. The spontaneous spreading behavior of a water droplet on a total wetting surface provides huge liquid-gas interfacial area per unit volume; however, it is halted by the self-pinning phenomenon upon addition of nonvolatile solutes. In this work, it is shown that the solute-induced self-pinning can be overcome by gravity, leading to anisotropic spreading much faster than isotropic spreading. The evaporation rate of anisotropic spreading on a zwitterionic sulfobetaine surface is 25 times larger as that on a poly(methyl methacrylate) surface. Dramatic enhancement of evaporation is demonstrated by simultaneous formation of fog atop liquid film. During anisotropic spreading, the solutes are quickly precipitated out within 30 s, showing the rapid solute-water separation. After repeated spreading process for the dye-containing solution, the mean concentration of the collection is doubled, revealing the concentration efficiency as high as 100%. Gravity-enhanced spreading on total wetting surfaces at room temperature is easy to scale-up with less energy consumption, and thus it has great potentials for the applications of solute separation and concentration.

Intermolecular network analysis of the liquid and vapor interfaces of pentane and water: microsolvation does not trend with interfacial properties.

PubMed

Ghadar, Yasaman; Clark, Aurora E

2014-06-28

Liquid:vapor and liquid:liquid interfaces exhibit complex organizational structure and dynamics at the molecular level. In the case of water and organic solvents, the hydrophobicity of the organic, its conformational flexibility, and compressibility, all influence interfacial properties. This work compares the interfacial tension, width, molecular conformations and orientations at the vapor and aqueous liquid interfaces of two solvents, n-pentane and neopentane, whose varying molecular shapes can lead to significantly different interfacial behavior. Particular emphasis has been dedicated toward understanding how the hydrogen bond network of water responds to the pentane relative to the vapor interface and the sensitivity of the network to the individual pentane isomer and system temperature. Interfacial microsolvation of the immiscible solvents has been examined using graph theoretical methods that quantify the structure and dynamics of microsolvated species (both H2O in C5H12 and C5H12 in H2O). At room temperature, interfacial water at the pentane phase boundary is found to have markedly different organization and dynamics than at the vapor interface (as indicated by the hydrogen bond distributions and hydrogen bond persistence in solution). While the mesoscale interfacial properties (e.g. interfacial tension) are sensitive to the specific pentane isomer, the distribution and persistence of microsolvated species at the interface is nearly identical for both systems, irrespective of temperature (between 273 K and 298 K). This has important implications for understanding how properties defined by the interfacial organization are related to the underlying solvation reactions that drive formation of the phase boundary.

Numerical Calculation of Gravity-Capillary Interfacial Waves of Finite Amplitude,

DTIC Science & Technology

1980-02-26

corresponding to n=2. The erical scheme appears to be more efficient than the numerical work of Schwartz and Vanden-Broeck shows Padd table method since the...waves are studied. A generalization of Wilton’s ripples for interfacial waves is presented. I. INTRODUCTION that all variables become dimensionless. We...then recast these series irrotational. Thus, we define stream functions # and as Padd apDroxlmants. High accuracy solutions were 02 and potential

Recent Advances in Colloidal and Interfacial Phenomena Involving Liquid Crystals

PubMed Central

Bai, Yiqun; Abbott, Nicholas L.

2011-01-01

This article describes recent advances in several areas of research involving the interfacial ordering of liquid crystals (LCs). The first advance revolves around the ordering of LCs at bio/chemically functionalized surfaces. Whereas the majority of past studies of surface-induced ordering of LCs have involved surfaces of solids that present a limited diversity of chemical functional groups (surfaces at which van der Waals forces dominate surface-induced ordering), recent studies have moved to investigate the ordering of LCs on chemically complex surfaces. For example, surfaces decorated with biomolecules (e.g. oligopeptides and proteins) and transition metal ions have been investigated, leading to an understanding of the roles that metal-ligand coordination interactions, electrical double-layers, acid-base interactions, and hydrogen bonding can have on the interfacial ordering of LCs. The opportunity to create chemically-responsive LCs capable of undergoing ordering transitions in the presence of targeted molecular events (e.g., ligand exchange around a metal center) has emerged from these fundamental studies. A second advance has focused on investigations of the ordering of LCs at interfaces with immiscible isotropic fluids, particularly water. In contrast to prior studies of surface-induced ordering of LCs on solid surfaces, LC- aqueous interfaces are deformable and molecules at these interfaces exhibit high levels of mobility and thus can reorganize in response to changes in interfacial environment. A range of fundamental investigations involving these LC-aqueous interfaces have revealed that (i) the spatial and temporal characteristics of assemblies formed from biomolecular interactions can be reported by surface-driven ordering transitions in the LCs, (ii) the interfacial phase behaviour of molecules and colloids can be coupled to (and manipulated via) the ordering (and nematic elasticity) of LCs, and (iii) confinement of LCs leads to unanticipated size-dependent ordering (particularly in the context of LC emulsion droplets). The third and final advance addressed in this article involves interactions between colloids mediated by LCs. Recent experiments involving microparticles deposited at the LC-aqueous interface have revealed that LC-mediated interactions can drive interfacial assemblies of particles through reversible ordering transitions (e.g., from one-dimensional chains to two-dimensional arrays with local hexagonal symmetry). In addition, recent single nanoparticle measurements suggest that the ordering of LCs about nanoparticles differs substantially from micrometer-sized particles and that the interactions between nanoparticles mediated by the LCs are far weaker than predicted by theory (sufficiently weak that the interactions are reversible and thus enable self-assembly). Finally, LC-mediated interactions between colloidal particles have also been shown to lead to the formation of colloid-in-LC gels that possess mechanical properties relevant to the design of materials to interface with living biological systems. Overall, these three topics serve to illustrate the broad opportunities that exist to do fundamental interfacial science and discovery-oriented research involving LCs. PMID:21090596

In situ nano- to microscopic imaging and growth mechanism of electrochemical dissolution (e.g., corrosion) of a confined metal surface

PubMed Central

Merola, C.; Cheng, H.-W.; Schwenzfeier, K.; Kristiansen, K.; Chen, Y.-J.; Dobbs, H. A.; Valtiner, M.

2017-01-01

Reactivity in confinement is central to a wide range of applications and systems, yet it is notoriously difficult to probe reactions in confined spaces in real time. Using a modified electrochemical surface forces apparatus (EC-SFA) on confined metallic surfaces, we observe in situ nano- to microscale dissolution and pit formation (qualitatively similar to previous observation on nonmetallic surfaces, e.g., silica) in well-defined geometries in environments relevant to corrosion processes. We follow “crevice corrosion” processes in real time in different pH-neutral NaCl solutions and applied surface potentials of nickel (vs. Ag|AgCl electrode in solution) for the mica–nickel confined interface of total area ∼0.03 mm2. The initial corrosion proceeds as self-catalyzed pitting, visualized by the sudden appearance of circular pits with uniform diameters of 6–7 μm and depth ∼2–3 nm. At concentrations above 10 mM NaCl, pitting is initiated at the outer rim of the confined zone, while below 10 mM NaCl, pitting is initiated inside the confined zone. We compare statistical analysis of growth kinetics and shape evolution of individual nanoscale deep pits with estimates from macroscopic experiments to study initial pit growth and propagation. Our data and experimental techniques reveal a mechanism that suggests initial corrosion results in formation of an aggressive interfacial electrolyte that rapidly accelerates pitting, similar to crack initiation and propagation within the confined area. These results support a general mechanism for nanoscale material degradation and dissolution (e.g., crevice corrosion) of polycrystalline nonnoble metals, alloys, and inorganic materials within confined interfaces. PMID:28827338

Assessing the influence of humic acids on the weathering of galena and its environmental implications.

PubMed

Liu, Qingyou; Li, Heping; Jin, Guoheng; Zheng, Kai; Wang, Luying

2018-08-30

Galena weathering often occurs in nature and releases metal ions during the process. Humic acid (HA), a critical particle of natural organic matter, binds metal ions, thus affecting metal transfer and transformation. In this work, an electrochemical method combined with spectroscopic techniques was adopted to investigate the interfacial processes involved in galena weathering under acidic and alkaline conditions, as well as in the presence of HA. The results show that the initial step of galena weathering involved the transformation Pb 2+ and S°, regardless of whether the solution was acidic or alkaline. Under acidic conditions, S° and Pb 2+ further transform into anglesite, and HA adsorbs on the galena surface, inhibiting the transformation of sulfur. HA and Pb (II) ions form bridging complexes. Under alkaline conditions without HA, the sulfur produced undergoes no transformation, whereas Pb 2+ will transform into PbO. The presence of HA changes the galena weathering mechanism via ionization effect, and Pb 2+ is ultimately converted into anglesite. Higher acidity in acidic conditions or higher alkalinity in alkaline conditions causes galena corrosion when the electrolyte does not contain HA. Conversely, higher pH always accelerates galena corrosion when the electrolyte contains HA, whether the electrolyte is acidic or alkaline. At the same acidity/alkalinity, increasing the concentration of HA inhibits galena weathering. Galena will release 134.7 g m -2 ·y -1 Pb 2+ to solution at pH 2.5, and the amount decreases to 28.09 g m -2 ·y -1 in the presence of 1000 mg/L HA. This study provides an in situ electrochemical method for the assessment of galena weathering. Copyright © 2018 Elsevier Inc. All rights reserved.

Electrochemical behavior of 45S5 bioactive ceramic coating on Ti6Al4V alloy for dental applications

NASA Astrophysics Data System (ADS)

Machado López, M. M.; Espitia Cabrera, M. I.; Faure, J.; Contreras García, M. E.

2016-04-01

Titanium and its alloys are widely used as implant materials because of their mechanical properties and non-toxic behavior. Unfortunately, they are not bioinert, which means that they can release ions and can only fix the bone by mechanical anchorage, this can lead to the encapsulation of dense fibrous tissue in the body. The bone fixation is required in clinical conditions treated by orthopedic and dental medicine. The proposal is to coat metallic implants with bioactive materials to establish good interfacial bonds between the metal substrate and bone by increasing bioactivity. Bioactive glasses, ceramics specifically 45 S5 Bioglass, have drawn attention as a serious functional biomaterial because osseointegration capacity. The EPD method of bioglass gel precursor was proposed in the present work as a new method to obtain 45S5/Ti6A14V for dental applications. The coatings, were thermally treated at 700 and 800°C and presented the 45 S5 bioglass characteristic phases showing morphology and uniformity with no defects, quantification percentages by EDS of Si, Ca, Na, P and O elements in the coating scratched powders, showed a good proportional relationship demonstrating the obtention of the 45S5 bioglass. The corrosion tests were carried out in Hank's solution. By Tafel extrapolation, Ti6Al4V alloy showed good corrosion resistance in Hank's solution media, by the formation of a passivation layer on the metal surface, however, in the system 45S5/Ti6Al4V there was an increase in the corrosion resistance; icon-, Ecorr and corrosion rate decreased, the mass loss and the rate of release of ions, were lower in this system than in the titanium alloy without coating.

Directing Reaction Pathways through Controlled Reactant Binding at Pd-TiO2 Interfaces.

PubMed

Zhang, Jing; Wang, Bingwen; Nikolla, Eranda; Medlin, J Will

2017-06-01

Recent efforts to design selective catalysts for multi-step reactions, such as hydrodeoxygenation (HDO), have emphasized the preparation of active sites at the interface between two materials having different properties. However, achieving precise control over interfacial properties, and thus reaction selectivity, has remained a challenge. Here, we encapsulated Pd nanoparticles (NPs) with TiO 2 films of regulated porosity to gain a new level of control over catalyst performance, resulting in essentially 100 % HDO selectivity for two biomass-derived alcohols. This catalyst also showed exceptional reaction specificity in HDO of furfural and m-cresol. In addition to improving HDO activity by maximizing the interfacial contact between the metal and metal oxide sites, encapsulation by the nanoporous oxide film provided a significant selectivity boost by restricting the accessible conformations of aromatics on the surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioactive glass coatings for orthopedic metallic implants

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

Lopez-Esteban, Sonia; Saiz, Eduardo; Fujino, Sigheru

2003-06-30

The objective of this work is to develop bioactive glass coatings for metallic orthopedic implants. A new family of glasses in the SiO2-Na2O-K2O-CaO-MgO-P2O5 system has been synthesized and characterized. The glass properties (thermal expansion, softening and transformation temperatures, density and hardness) are in line with the predictions of established empirical models. The optimized firing conditions to fabricate coatings on Ti-based and Co-Cr alloys have been determined and related to the glass properties and the interfacial reactions. Excellent adhesion to alloys has been achieved through the formation of 100-200 nm thick interfacial layers (Ti5Si3 on Ti-based alloys and CrOx on Co-Cr).more » Finally, glass coatings, approximately 100 mu m thick, have been fabricated onto commercial Ti alloy-based dental implants.« less

Building Nanoporous Metal-Organic Frameworks "Armor" on Fibers for High-Performance Composite Materials.

PubMed

Yang, Xiaobin; Jiang, Xu; Huang, Yudong; Guo, Zhanhu; Shao, Lu

2017-02-15

The nanoporous metal-organic frameworks (MOFs) "armor" is in situ intergrown onto the surfaces of carbon fibers (CFs) by nitric acid oxidization to supply nucleation sites and serves as a novel interfacial linker between the fiber and polymer matrix and a smart cushion to release interior and exterior applied forces. Simultaneous enhancements of the interfacial and interlaminar shear strength as well as the tensile strength of CFs were achieved. With the aid of an ultrasonic "cleaning" process, the optimized surface energy and tensile strength of CFs with a MOF "armor" are 83.79 mN m -1 and 5.09 GPa, for an increase of 102% and 11.6%, respectively. Our work finds that the template-induced nucleation of 3D MOF onto 1D fibers is a general and promising approach toward advanced composite materials for diverse applications to meet scientific and technical demands.

Showcasing electrode-electrolyte interfacial potential as a vital parameter in the hydrogen generation by metal oxides electrodes

NASA Astrophysics Data System (ADS)

Niveditha, C. V.; Nizamudeen, A. C.; Ramanarayanan, Rajita; Jabeen Fatima, M. J.; Swaminathan, Sindhu

2018-03-01

This investigation presents a new insight by experimentally demonstrating electrode-electrolyte interface potential that is flat band potential as a determinant in photoelectrochemical splitting of water. Two different metal oxides namely n type, nitrogen doped titania and p type copper oxides have been synthesized for the study. The flat band potential values of these oxide systems were obtained from Mott-Schottky analysis. The obtained flat band potential is used as a marker to fix the working potential in water splitting experiment. To obtain optimum photocurrent a potential more positive than flatband is applied to n-type N-TiO2 and vice-versa for p-type Cu2O. The findings are well supported by I-t curves derived from chronoamperometric measurements. Finally the mechanisms behind interfacial potential dynamics have been discussed in this work.

Calculation of Stress Intensity Factors for Interfacial Cracks in Fiber Metal Laminates

NASA Technical Reports Server (NTRS)

Wang, John T.

2009-01-01

Stress intensity factors for interfacial cracks in Fiber Metal Laminates (FML) are computed by using the displacement ratio method recently developed by Sun and Qian (1997, Int. J. Solids. Struct. 34, 2595-2609). Various FML configurations with single and multiple delaminations subjected to different loading conditions are investigated. The displacement ratio method requires the total energy release rate, bimaterial parameters, and relative crack surface displacements as input. Details of generating the energy release rates, defining bimaterial parameters with anisotropic elasticity, and selecting proper crack surface locations for obtaining relative crack surface displacements are discussed in the paper. Even though the individual energy release rates are nonconvergent, mesh-size-independent stress intensity factors can be obtained. This study also finds that the selection of reference length can affect the magnitudes and the mode mixity angles of the stress intensity factors; thus, it is important to report the reference length used with the calculated stress intensity factors.

Porphyrins at interfaces

NASA Astrophysics Data System (ADS)

Auwärter, Willi; Écija, David; Klappenberger, Florian; Barth, Johannes V.

2015-02-01

Porphyrins and other tetrapyrrole macrocycles possess an impressive variety of functional properties that have been exploited in natural and artificial systems. Different metal centres incorporated within the tetradentate ligand are key for achieving and regulating vital processes, including reversible axial ligation of adducts, electron transfer, light-harvesting and catalytic transformations. Tailored substituents optimize their performance, dictating their arrangement in specific environments and mediating the assembly of molecular nanoarchitectures. Here we review the current understanding of these species at well-defined interfaces, disclosing exquisite insights into their structural and chemical properties, and also discussing methods by which to manipulate their intramolecular and organizational features. The distinct characteristics arising from the interfacial confinement offer intriguing prospects for molecular science and advanced materials. We assess the role of surface interactions with respect to electronic and physicochemical characteristics, and describe in situ metallation pathways, molecular magnetism, rotation and switching. The engineering of nanostructures, organized layers, interfacial hybrid and bio-inspired systems is also addressed.

Reprint of "Theoretical description of metal/oxide interfacial properties: The case of MgO/Ag(001)"

NASA Astrophysics Data System (ADS)

Prada, Stefano; Giordano, Livia; Pacchioni, Gianfranco; Goniakowski, Jacek

2017-02-01

We compare the performances of different DFT functionals applied to ultra-thin MgO(100) films supported on the Ag(100) surface, a prototypical system of a weakly interacting oxide/metal interface, extensively studied in the past. Beyond semi-local DFT-GGA approximation, we also use the hybrid DFT-HSE approach to improve the description of the oxide electronic structure. Moreover, to better account for the interfacial adhesion, we include the van de Waals interactions by means of either the semi-empirical force fields by Grimme (DFT-D2 and DFT-D2*) or the self-consistent density functional optB88-vdW. We compare and discuss the results on the structural, electronic, and adhesion characteristics of the interface as obtained for pristine and oxygen-deficient Ag-supported MgO films in the 1-4 ML thickness range.

Theoretical description of metal/oxide interfacial properties: The case of MgO/Ag(001)

NASA Astrophysics Data System (ADS)

Prada, Stefano; Giordano, Livia; Pacchioni, Gianfranco; Goniakowski, Jacek

2016-12-01

We compare the performances of different DFT functionals applied to ultra-thin MgO(100) films supported on the Ag(100) surface, a prototypical system of a weakly interacting oxide/metal interface, extensively studied in the past. Beyond semi-local DFT-GGA approximation, we also use the hybrid DFT-HSE approach to improve the description of the oxide electronic structure. Moreover, to better account for the interfacial adhesion, we include the van de Waals interactions by means of either the semi-empirical force fields by Grimme (DFT-D2 and DFT-D2*) or the self-consistent density functional optB88-vdW. We compare and discuss the results on the structural, electronic, and adhesion characteristics of the interface as obtained for pristine and oxygen-deficient Ag-supported MgO films in the 1-4 ML thickness range.

Molecular dynamics study of structure and vibrational spectra at zwitterionoic lipid/aqueous KCl, NaCl, and CaCl2 solution interfaces

NASA Astrophysics Data System (ADS)

Ishiyama, Tatsuya; Shirai, Shinnosuke; Okumura, Tomoaki; Morita, Akihiro

2018-06-01

Molecular dynamics (MD) simulations of KCl, NaCl, and CaCl2 solution/dipalmytoylphosphatidylcholine lipid interfaces were performed to analyze heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectra in relation to the interfacial water structure. The present MD simulation well reproduces the experimental spectra and elucidates a specific cation effect on the interfacial structure. The K+, Na+, and Ca2+ cation species penetrate in the lipid layer more than the anions in this order, due to the electrostatic interaction with negative polar groups of lipid, and the electric double layer between the cations and anions cancels the intrinsic orientation of water at the water/lipid interface. These mechanisms explain the HD-VSFG spectrum of the water/lipid interface and its spectral perturbation by adding the ions. The lipid monolayer reverses the order of surface preference of the cations at the solution/lipid interface from that at the solution/air interface.

Two-Fluid Models and Interfacial Area Transport in Microgravity Condition

NASA Technical Reports Server (NTRS)

Ishii, Mamoru; Sun, Xiao-Dong; Vasavada, Shilp

2004-01-01

The objective of the present study is to develop a two-fluid model formulation with interfacial area transport equation applicable for microgravity conditions. The new model is expected to make a leapfrog improvement by furnishing the constitutive relations for the interfacial interaction terms with the interfacial area transport equation, which can dynamically model the changes of the interfacial structures. In the first year of this three-year project supported by the U.S. NASA, Office of Biological and Physics Research, the primary focus is to design and construct a ground-based, microgravity two-phase flow simulation facility, in which two immiscible fluids with close density will be used. In predicting the two-phase flow behaviors in any two-phase flow system, the interfacial transfer terms are among the most essential factors in the modeling. These interfacial transfer terms in a two-fluid model specify the rate of phase change, momentum exchange, and energy transfer at the interface between the two phases. For the two-phase flow under the microgravity condition, the stability of the fluid particle interface and the interfacial structures are quite different from those under normal gravity condition. The flow structure may not reach an equilibrium condition and the two fluids may be loosely coupled such that the inertia terms of each fluid should be considered separately by use of the two-fluid model. Previous studies indicated that, unless phase-interaction terms are accurately modeled in the two-fluid model, the complex modeling does not necessarily warrant an accurate solution.

ZnO buffer layer for metal films on silicon substrates

DOEpatents

Ihlefeld, Jon

2014-09-16

Dramatic improvements in metallization integrity and electroceramic thin film performance can be achieved by the use of the ZnO buffer layer to minimize interfacial energy between metallization and adhesion layers. In particular, the invention provides a substrate metallization method utilizing a ZnO adhesion layer that has a high work of adhesion, which in turn enables processing under thermal budgets typically reserved for more exotic ceramic, single-crystal, or metal foil substrates. Embodiments of the present invention can be used in a broad range of applications beyond ferroelectric capacitors, including microelectromechanical systems, micro-printed heaters and sensors, and electrochemical energy storage, where integrity of metallized silicon to high temperatures is necessary.

Understanding the role of ion interactions in soluble salt flotation with alkylammonium and alkylsulfate collectors.

PubMed

Ozdemir, Orhan; Du, Hao; Karakashev, Stoyan I; Nguyen, Anh V; Celik, M S; Miller, Jan D

2011-03-15

There is anecdotal evidence for the significant effects of salt ions on the flotation separation of minerals using process water of high salt content. Examples include flotation of soluble salt minerals such as potash, trona and borax in brine solutions using alkylammonium and alkylsulfate collectors such as dodecylamine hydrochloride and sodium dodecylsulfate. Although some of the effects are expected, some do not seem to be encompassed by classical theories of colloid science. Several experimental and modeling techniques for determining solution viscosity, surface tension, bubble-particle attachment time, contact angle, and molecular dynamics simulation have been used to provide further information on air-solution and solid-solution interfacial phenomena, especially with respect to the interfacial water structure due to the presence of dissolved ions. In addition atomic force microscopy, and sum frequency generation vibrational spectroscopy have been used to provide further information on surface states. These studies indicate that the ion specificity effect is the most significant factor influencing flotation in brine solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

Hydrogen Sensors Using Nitride-Based Semiconductor Diodes: The Role of Metal/Semiconductor Interfaces

PubMed Central

Irokawa, Yoshihiro

2011-01-01

In this paper, I review my recent results in investigating hydrogen sensors using nitride-based semiconductor diodes, focusing on the interaction mechanism of hydrogen with the devices. Firstly, effects of interfacial modification in the devices on hydrogen detection sensitivity are discussed. Surface defects of GaN under Schottky electrodes do not play a critical role in hydrogen sensing characteristics. However, dielectric layers inserted in metal/semiconductor interfaces are found to cause dramatic changes in hydrogen sensing performance, implying that chemical selectivity to hydrogen could be realized. The capacitance-voltage (C–V) characteristics reveal that the work function change in the Schottky metal is not responsible mechanism for hydrogen sensitivity. The interface between the metal and the semiconductor plays a critical role in the interaction of hydrogen with semiconductor devises. Secondly, low-frequency C–V characterization is employed to investigate the interaction mechanism of hydrogen with diodes. As a result, it is suggested that the formation of a metal/semiconductor interfacial polarization could be attributed to hydrogen-related dipoles. In addition, using low-frequency C–V characterization leads to clear detection of 100 ppm hydrogen even at room temperature where it is hard to detect hydrogen by using conventional current-voltage (I–V) characterization, suggesting that low-frequency C–V method would be effective in detecting very low hydrogen concentrations. PMID:22346597

Recrystallization characteristics and interfacial oxides on the compression bonding interface

NASA Astrophysics Data System (ADS)

Xie, Bijun; Sun, Mingyue; Xu, Bin; Li, Dianzhong

2018-05-01

Up to now, the mechanism of interface bonding is still not fully understood. This work presents interfacial characteristics of 316LN stainless steel bonding joint after cold compression bonding with subsequent annealing. EBSD analysis shows that fine recrystallization grains preferentially appear near the bonding interface and grow towards both sides of the interface. Transmission electron microscopy reveals that initial cold compression bonding disintegrates the native oxide scales and brings pristine metal from both sides of the interface come into intimate contact, while the broken oxide particles are remained at the original interface. The results indicate that partial bonding can be achieved by cold compression bonding with post-annealing treatment and recrystallization firstly occurs along the bonding interface. However, the interfacial oxides impede the recrystallization grains step over the interface and hinder the complete healing of the bonding interface.

Present understanding of the stability of Li-stuffed garnets with moisture, carbon dioxide, and metallic lithium

NASA Astrophysics Data System (ADS)

Hofstetter, Kyle; Samson, Alfred Junio; Narayanan, Sumaletha; Thangadurai, Venkataraman

2018-06-01

Fast lithium-ion conducting garnet-type metal oxides are promising membranes for next-generation all-solid-state Li batteries and beyond Li-ion batteries, including Li-air and Li-S batteries, due to their high total Li-ion conductivity and excellent chemical stability against reaction with elemental Li. Several studies have been reported on structure-chemical composition-ionic conductivity property in Li-stuffed garnet-type metal oxides. Here, an overview of the chemical and electrochemical stability of lithium-based garnets against moisture/humidity, aqueous solutions, carbon dioxide, sulfur, and metallic lithium are analyzed. Moisture and aqueous stability studies focus on understanding the crystal structure stability, the proton exchange capacity as a function of Li content in Li-stuffed garnets, and how the protonated species affect the crystal structure and mass transport properties. H+/Li+ exchange was found to be in the range of 2-100%. Stability concerning Li-ion conductivity and morphology under carbon dioxide are discussed. Interfacial chemical stability with lithium metal characterized by electrochemical stability window, Li dendrite formation and area specific resistance (ASR) for the reaction Li ⇌ Li+ +e- are presented. Recent attempts to suppress dendrite formation and to reduce ASR via surface modification are also highlighted. Li and Li-stuffed garnet interface ASR values are shown to be as high as >2000 Ω cm2 and as low as 1 Ω cm2 at room temperature for surface modified Li-stuffed samples. Furthermore, recent studies on Li-S battery utilizing chemically stable Li - garnet electrolyte are also discussed.

A novel broadband impedance method for detection of cell-derived microparticles

PubMed Central

Lvovich, Vadim; Srikanthan, Sowmya; Silverstein, Roy L.

2010-01-01

A novel label-free method is presented to detect and quantify cell-derived microparticles (MPs) by the electrochemical potential-modulated electrochemical impedance spectroscopy (EIS). MPs are present in elevated concentrations during pathological conditions and play a major role in the establishment and pathogenesis of many diseases. Considering this, accurate detection and quantification of MPs is very important in clinical diagnostics and therapeutics. A combination of bulk solution electrokinetic sorting and interfacial impedance responses allows achieving detection limits as low as several MPs per µL. By fitting resulting EIS spectra with an equivalent electrical circuit, the bulk solution electrokinetic and interfacial impedance responses were characterized. In the bulk solution two major relaxations were prominent - β-relaxation in low MHz region due to the MP capacitive membrane bridging, and α-relaxation at ∼ 10 kHz due to counter ions diffusion. At low frequencies (10-0.1 Hz) at electrochemical potentials exceeding −100 mV, a facile interfacial Faradaic process of oxidation in MPs coupled with diffusion and non Faradaic double layer charging dominate, probably due to oxidation of phospholipids and/or proteins on the MP surface and MP lysis. Buffer influence on the MP detection demonstrated that that a relatively low conductivity Tyrode’s buffer background solution is preferential for the MP electrokinetic separation and characterization. This study also demonstrated that standard laboratory methods such as flow cytometry underestimate MP concentrations, especially those with smaller average sizes, by as much as a factor of 2 to 40. PMID:20729061

How Does a SILAR CdSe Film Grow? Tuning the Deposition Steps to Suppress Interfacial Charge Recombination in Solar Cells.

PubMed

Becker, Matthew A; Radich, James G; Bunker, Bruce A; Kamat, Prashant V

2014-05-01

Successive ionic layer adsorption and reaction (SILAR) is a popular method of depositing the metal chalcogenide semiconductor layer on the mesoscopic metal oxide films for designing quantum-dot-sensitized solar cells (QDSSCs) or extremely thin absorber (ETA) solar cells. While this deposition method exhibits higher loading of the light-absorbing semiconductor layer than direct adsorption of presynthesized colloidal quantum dots, the chemical identity of these nanostructures and the evolution of interfacial structure are poorly understood. We have now analyzed step-by-step SILAR deposition of CdSe films on mesoscopic TiO2 nanoparticle films using X-ray absorption near-edge structure analysis and probed the interfacial structure of these films. The film characteristics interestingly show dependence on the order in which the Cd and Se are deposited, and the CdSe-TiO2 interface is affected only during the first few cycles of deposition. Development of a SeO2 passivation layer in the SILAR-prepared films to form a TiO2/SeO2/CdSe junction facilitates an increase in photocurrents and power conversion efficiencies of quantum dot solar cells when these films are integrated as photoanodes in a photoelectrochemical solar cell.

Growth Kinetics of Magnesio-Aluminate Spinel in Al/Mg Lamellar Composite Interface

NASA Astrophysics Data System (ADS)

Fouad, Yasser; Rabeeh, Bakr Mohamed

The synthesis of Mg-Al2O3 double layered interface is introduced via the application of hot isostatic pressing, HIPing, in Al-Mg foils. Polycrystalline spinel layers are grown experimentally at the interfacial contacts between Al-Mg foils. The growth behavior of the spinel layers along with the kinetic parameters characterizing interface motion and long-range diffusion is established. Low melting depressant (LMD), Zn, and alloying element segregation tends to form micro laminated and/or Nano structure interphase in a lamellar composite solid state processing. Nano composite ceramic interphase materials offer interesting mechanical properties not achievable in other materials, such as superplastic flow and metal-like machinability. Microstructural characterization, mechanical characterization is also established via optical microscopy scanning electron microscopy, energy dispersive X-ray spectroscopy and tensile testing. Chemical and mechanical bonding via inter diffusion processing with alloy segregation are dominant for interphase kinetics. Mechanical characterization with interfacial shear strength is also introduced. HIPing processing is successfully applied on 6082 Al-alloy and AZ31 magnesium alloy for either particulate or micro-laminated interfacial composite processing. The interphase kinetic established through localized micro plasticity, metal flow, alloy segregation and delocalized Al oxide and Mg oxide. The kinetic of interface/interphase induce new nontraditional crack mitigation a long with new bridging and toughening mechanisms.

Self-assembled growth and structural analysis of inclined GaN nanorods on nanoimprinted m-sapphire using catalyst-free metal-organic chemical vapor deposition

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

Lee, Kyuseung; Chae, Sooryong; Jang, Jongjin

2016-04-15

In this study, self-assembled inclined (1-10-3)-oriented GaN nanorods (NRs) were grown on nanoimprinted (10-10) m-sapphire substrates using catalyst-free metal-organic chemical vapor deposition. According to X-ray phi-scans, the inclined GaN NRs were tilted at an angle of ∼57.5° to the [10-10]{sub sapp} direction. Specifically, the GaN NRs grew in a single inclined direction to the [11-20]{sub sapp}. Uni-directionally inclined NRs were formed through the one-sided (10-11)-faceted growth of the interfacial a-GaN plane layer. It was confirmed that a thin layer of a-GaN was formed on r-facet nanogrooves of the m-sapphire substrate by nitridation. The interfacial a-GaN nucleation affected both the inclinedmore » angle and the growth direction of the inclined GaN NRs. Using X-ray diffraction and selective area electron diffraction, the epitaxial relationship between the inclined (1-10-3) GaN NRs and interfacial a-GaN layer on m-sapphire substrates was systematically investigated. Moreover, the inclined GaN NRs were observed to be mostly free of stacking fault-related defects using high-resolution transmission electron microscopy.« less

Moisture-Induced Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

NASA Technical Reports Server (NTRS)

Smialek, James L.

2005-01-01

Thermal expansion mismatch stresses and interfacial sulfur activity are the major factors producing primary Al2O3 scale spallation on high temperature alloys. However, moisture-induced delayed spallation appears as a secondary, but often dramatic, illustration of an additional mechanistic detail. A historical review of delayed failure of alumina scales and TBC s on superalloys is presented herein. Similarities with metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al+3H2O=Al(OH)3+3H(+)+3e(-), is the operative mechanism. This proposal was tested by standard cathodic hydrogen charging in 1N H2SO4, applied to Rene N5 pre-oxidized at 1150 C for 1000 1-hr cycles, and monitored by weight change, induced current, and microstructure. Here cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the electrolyte alone produced neither scale spallation nor alloy dissolution. These experiments thus highlight the detrimental effects of hydrogen charging on alumina scale adhesion. It is proposed that interfacial hydrogen embrittlement is produced by moist air and is the root cause of both moisture-induced, delayed scale spallation and desktop TBC failures.

Sulfur Impurities and the Microstructure of Alumina Scales

NASA Technical Reports Server (NTRS)

Smialek, James L.

1997-01-01

The relationship between the microstructure of alumina scales, adhesion, and sulfur content was examined through a series of nickel alloys oxidized in 1100 to 1200 deg. C cyclic or isothermal exposures in air. In cyclic tests of undoped NiCrAl, adhesion was produced when the sulfur content was reduced, without any change in scale microstructure. Although interfacial voids were not observed in cyclic tests of NiCrAl, they were promoted by long-term isothermal exposures, by sulfur doping, and in most exposures of NiAl. Two single crystal superalloys, PWA 1480 and Rene' N5, were also tested, either in the as-received condition or after the sulfur content had been reduced to less than 1 ppmw by hydrogen annealing. The unannealed alloys always exhibited spalling to bare metal, but interfacial voids were not observed consistently. Desulfurized PWA 1480 and Rene' N5 exhibited remarkable adhesion and no voidage for either isothermal or cyclic exposures. The most consistent microstructural feature was that, for the cases where voids did form, the scale undersides exhibited corresponding areas with ridged oxide grain boundaries. Voids were not required for spallation nor were other microstructural features essential for adhesion. These observations are consistent with the model whereby scale spallation is controlled primarily by interfacial sulfur segregation and the consequent degradation of oxide-metal bonding.

Electrode redox reactions with polarizable molecules.

PubMed

Matyushov, Dmitry V

2018-04-21

A theory of redox reactions involving electron transfer between a metal electrode and a polarizable molecule in solution is formulated. Both the existence of molecular polarizability and its ability to change due to electron transfer distinguish this problem from classical theories of interfacial electrochemistry. When the polarizability is different between the oxidized and reduced states, the statistics of thermal fluctuations driving the reactant over the activation barrier becomes non-Gaussian. The problem of electron transfer is formulated as crossing of two non-parabolic free energy surfaces. An analytical solution for these free energy surfaces is provided and the activation barrier of electrode electron transfer is given in terms of two reorganization energies corresponding to the oxidized and reduced states of the molecule in solution. The new non-Gaussian theory is, therefore, based on two theory parameters in contrast to one-parameter Marcus formulation for electrode reactions. The theory, which is consistent with the Nernst equation, predicts asymmetry between the cathodic and anodic branches of the electrode current. They show different slopes at small electrode overpotentials and become curved at larger overpotentials. However, the curvature of the Tafel plot is reduced compared to the Marcus-Hush model and approaches the empirical Butler-Volmer form with different transfer coefficients for the anodic and cathodic currents.

Electrode redox reactions with polarizable molecules

NASA Astrophysics Data System (ADS)

Matyushov, Dmitry V.

2018-04-01

A theory of redox reactions involving electron transfer between a metal electrode and a polarizable molecule in solution is formulated. Both the existence of molecular polarizability and its ability to change due to electron transfer distinguish this problem from classical theories of interfacial electrochemistry. When the polarizability is different between the oxidized and reduced states, the statistics of thermal fluctuations driving the reactant over the activation barrier becomes non-Gaussian. The problem of electron transfer is formulated as crossing of two non-parabolic free energy surfaces. An analytical solution for these free energy surfaces is provided and the activation barrier of electrode electron transfer is given in terms of two reorganization energies corresponding to the oxidized and reduced states of the molecule in solution. The new non-Gaussian theory is, therefore, based on two theory parameters in contrast to one-parameter Marcus formulation for electrode reactions. The theory, which is consistent with the Nernst equation, predicts asymmetry between the cathodic and anodic branches of the electrode current. They show different slopes at small electrode overpotentials and become curved at larger overpotentials. However, the curvature of the Tafel plot is reduced compared to the Marcus-Hush model and approaches the empirical Butler-Volmer form with different transfer coefficients for the anodic and cathodic currents.

Ultrafast dynamics and Raman imaging of metal complexes of tetrasulphonated phthalocyanines in human cancerous and noncancerous breast tissues

NASA Astrophysics Data System (ADS)

Abramczyk, H.; Jarota, A.; Brozek-Pluska, B.; Tondusson, M.; Freysz, E.; Musial, J.; Kordek, R.

2013-03-01

A promising material in medicine, electronics, optoelectronics, electrochemistry, catalysis and photophysics, Al(III) phthalocyanine chloride tetrasulfonic acid (AlPcS4) is investigated at biological interfaces of human breast tissue by means of time-resolved spectroscopy. The nature of fast processes and pathways of the competing relaxation mechanisms from the initially excited electronic states of a photosensitizer at biological interfaces have been studied. Comparison between the results in the biological environment of the breast tissues and in aqueous solutions demonstrates that the photochemical mechanisms become dramatically different. The presented results provide a basis for a substantial revision of the commonly accepted assumption that photochemistry of the bulk properties of photosensitizers in solutions can be translated to the interfacial region. First, in solution the dynamics of the photosensitizer is much slower than that at the biological interface. Second, the dynamics of the photosensitizer in the cancerous tissue is dramatically slower than that in noncancerous tissue. Our results provide evidence that molecular structures responsible for harvesting of the light energy in biological tissue find their ways for a recovery through some special features of the potential energy surfaces such as conical intersections, which facilitate the rate of radiationless transitions and maintain the photostability in the biological systems.

Quantifying Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction.

PubMed

Ryu, Jaeyune; Wuttig, Anna; Surendranath, Yogesh

2018-05-15

We quantify changes in the interfacial pH local to the electrochemical double layer during electrocatalysis, using a concurrent non-faradaic probe reaction. In the absence of electrocatalysis, nanostructured Pt/C surfaces mediate the reaction of H2 with cis-2-butene-1,4-diol to form a mixture of 1,4-butanediol and n-butanol with a selectivity that is linearly dependent on the bulk solution pH. We show that kinetic branching occurs from a common surface-bound intermediate, ensuring that this probe reaction is uniquely sensitive to the interfacial pH within molecular length scales of the surface. We use the pH-dependent selectivity of this reaction to track changes in interfacial pH during concurrent hydrogen oxidation electrocatalysis and find that the local pH can vary dramatically, > 3 units, relative to the bulk value even at modest current densities in well-buffered electrolytes. This work highlights the key role that interfacial pH variation plays in modulating inner-sphere electrocatalysis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding Interfacial Alignment in Solution Coated Conjugated Polymer Thin Films

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

Qu, Ge; Zhao, Xikang; Newbloom, Gregory M.

Domain alignment in conjugated polymer thin films can significantly enhance charge carrier mobility. However, the alignment mechanism during meniscus-guided solution coating remains unclear. Furthermore, interfacial alignment has been rarely studied despite its direct relevance and critical importance to charge transport. In this study, we uncover a significantly higher degree of alignment at the top interface of solution coated thin films, using a donor–acceptor conjugated polymer, poly(diketopyrrolopyrrole-co-thiopheneco- thieno[3,2- b]thiophene-co-thiophene) (DPP2T-TT), as the model system. At the molecular level, we observe in-plane π–π stacking anisotropy of up to 4.8 near the top interface with the polymer backbone aligned parallel to the coatingmore » direction. The bulk of the film is only weakly aligned with the backbone oriented transverse to coating. At the mesoscale, we observe a well-defined fibril-like morphology at the top interface with the fibril long axis pointing toward the coating direction. Significantly smaller fibrils with poor orientational order are found on the bottom interface, weakly aligned orthogonal to the fibrils on the top interface. The high degree of alignment at the top interface leads to a charge transport anisotropy of up to 5.4 compared to an anisotropy close to 1 on the bottom interface. We attribute the formation of distinct interfacial morphology to the skin-layer formation associated with high Peclet number, which promotes crystallization on the top interface while suppressing it in the bulk. As a result, we further infer that the interfacial fibril alignment is driven by the extensional flow on the top interface arisen from increasing solvent evaporation rate closer to the meniscus front.« less

Understanding Interfacial Alignment in Solution Coated Conjugated Polymer Thin Films

DOE PAGES

Qu, Ge; Zhao, Xikang; Newbloom, Gregory M.; ...

2017-08-01

Domain alignment in conjugated polymer thin films can significantly enhance charge carrier mobility. However, the alignment mechanism during meniscus-guided solution coating remains unclear. Furthermore, interfacial alignment has been rarely studied despite its direct relevance and critical importance to charge transport. In this study, we uncover a significantly higher degree of alignment at the top interface of solution coated thin films, using a donor–acceptor conjugated polymer, poly(diketopyrrolopyrrole-co-thiopheneco- thieno[3,2- b]thiophene-co-thiophene) (DPP2T-TT), as the model system. At the molecular level, we observe in-plane π–π stacking anisotropy of up to 4.8 near the top interface with the polymer backbone aligned parallel to the coatingmore » direction. The bulk of the film is only weakly aligned with the backbone oriented transverse to coating. At the mesoscale, we observe a well-defined fibril-like morphology at the top interface with the fibril long axis pointing toward the coating direction. Significantly smaller fibrils with poor orientational order are found on the bottom interface, weakly aligned orthogonal to the fibrils on the top interface. The high degree of alignment at the top interface leads to a charge transport anisotropy of up to 5.4 compared to an anisotropy close to 1 on the bottom interface. We attribute the formation of distinct interfacial morphology to the skin-layer formation associated with high Peclet number, which promotes crystallization on the top interface while suppressing it in the bulk. As a result, we further infer that the interfacial fibril alignment is driven by the extensional flow on the top interface arisen from increasing solvent evaporation rate closer to the meniscus front.« less

Solenoid valve design minimizes vibration and sliding wear problem

NASA Technical Reports Server (NTRS)

Gillon, W. A., Jr.

1968-01-01

Two-way cryogenic solenoid valve resists damage from vibration and metallic interfacial sliding. The new system features a flat-faced armature guided by a flexure disk which eliminates sliding surfaces and is less subject to contamination and wear.

Studies on the structural, optical and dielectric properties of samarium coordinated with salicylic acid single crystal

NASA Astrophysics Data System (ADS)

Singh, Harjinder; Slathia, Goldy; Gupta, Rashmi; Bamzai, K. K.

2018-04-01

Samarium coordinated with salicylic acid was successfully grown as a single crystal by low temperature solution technique using mixed solvent of methanol and water in equal ratio. Structural characterization was carried out by single crystal X-ray diffraction analysis and it crystallizes in centrosymmetric space group P121/c1. FTIR and UV-Vis-NIR spectroscopy confirmed the compound formation and help to determine the mode of binding of the ligand to the rare earth-metal ion. Dielectric constant and dielectric loss have been measured over the frequency range 100 Hz - 30MHz. The decrease in dielectric constant with increases in frequency is due to the transition from interfacial polarization to dipolar polarization. The small value of dielectric constant at higher frequency ensures that the crystal is good candidate for NLO devices. Dielectric loss represents the resistive nature of the material.

Controllable rotating behavior of individual dielectric microrod in a rotating electric field.

PubMed

Liu, Weiyu; Ren, Yukun; Tao, Ye; Li, Yanbo; Chen, Xiaoming

2017-06-01

We report herein controllable rotating behavior of an individual dielectric microrod driven by a background rotating electric field. By disposing or removing structured floating microelectrode, the rigid rod suspended in electrolyte solution accordingly exhibits cofield or antifield rotating motion. In the absence of the ideally polarizable metal surface, the dielectric rod rotates opposite to propagation of electric field, with the measured rotating rate much larger than predicted by Maxwell-Wager interfacial polarization theory incorporating surface conduction of fixed bond charge. Surprisingly, with floating electrode embedded, a novel kind of cofield rotation mode occurs in the presence of induced double-layer polarization, due to the action of hydrodynamic torque from rotating induced-charge electroosmosis. This method of achieving switchable spin modes of dielectric particles would direct implications in constructing flexible electrokinetic framework for analyzing 3D profile of on-chip biomicrofluidic samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile, general and template-free construction of monodisperse yolk-shell metal@carbon nanospheres.

PubMed

Xu, Fei; Lu, Yuheng; Ma, Junhao; Huang, Zhike; Su, Quanfei; Fu, Ruowen; Wu, Dingcai

2017-11-07

Herein, we report a general and template-free protocol to construct novel yolk-shell metal@carbon nanospheres based on confined interfacial copolymerization, which greatly simplifies the synthetic route, yields uniform nanospheres with controllable diameters, and results in highly porous carbon shells. The yolk-shell Au@carbon shows improved adsorption capacity and high catalytic ability due to the synergistic effect of Au and the porous carbon shell.

Mechanical strength and tribological behavior of ion-beam deposited boron nitride films on non-metallic substrates

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa; Buckley, Donald H.; Pouch, John J.; Alterovitz, Samuel A.; Sliney, Harold E.

1987-01-01

An investigation was conducted to examine the mechanical strength and tribological properties of boron nitride (BN) films ion-beam deposited on silicon (Si), fused silica (SiO2), gallium arsenide (GaAs), and indium phosphide (InP) substrates in sliding contact with a diamond pin under a load. The results of the investigation indicate that BN films on nonmetallic substrates, like metal films on metallic substrates, deform elastically and plastically in the interfacial region when in contact with a diamond pin. However, unlike metal films and substrates, BN films on nonmetallic substrates can fracture when they are critically loaded. Not only does the yield pressure (hardness) of Si and SiO2 substrates increase by a factor of 2 in the presence of a BN film, but the critical load needed to fracture increases as well. The presence of films on the brittle substrates can arrest crack formation. The BN film reduces adhesion and friction in the sliding contact. BN adheres to Si and SiO2 and forms a good quality film, while it adheres poorly to GaAs and InP. The interfacial adhesive strengths were 1 GPa for a BN film on Si and appreciably higher than 1 GPa for a BN film on SiO2.

Use of Tween Polymer To Enhance the Compatibility of the Li/Electrolyte Interface for the High-Performance and High-Safety Quasi-Solid-State Lithium-Sulfur Battery.

PubMed

Liu, Jie; Qian, Tao; Wang, Mengfan; Zhou, Jinqiu; Xu, Na; Yan, Chenglin

2018-06-07

Lithium metal batteries have attracted increasing attention recently due to their particular advantages in energy density. However, as for their practical application, the development of solid-state lithium metal batteries is restricted because of the poor Li/electrolyte interface, low Li-ion conductivity, and irregular growth of Li dendrites. To address the above issues, we herein report a high Li-ion conductivity and compatible polymeric interfacial layer by grafting tween-20 on active lithium metal. Sequential oxyethylene groups in tween-grafted Li (TG-Li) improve the ion conductivity and the compatibility of the Li/electrolyte interface, which enables low overpotentials and stable performance over 1000 cycles. Consequently, the poly(ethylene oxide)-based solid-state lithium-sulfur battery with TG-Li exhibits a high reversible capacity of 1051.2 mA h g -1 at 0.2 C (1 C = 1675 mA h g -1 ) and excellent stability for 500 cycles at 2 C. The decreasing concentration of the sulfur atom with increasing Ar + sputtering depth indicates that the polymer interfacial layer works well in suppressing polysulfide reduction to Li 2 S/Li 2 S 2 on the metallic Li surface even after long-term cycling.

Mechanical strength and tribological behavior of ion-beam-deposited boron nitride films on non-metallic substrates

NASA Technical Reports Server (NTRS)

Miyoshi, Kazuhisa; Pouch, John J.; Alterovitz, Samuel A.; Sliney, Harold E.; Buckley, Donald H.

1987-01-01

An investigation was conducted to examine the mechanical strength and tribological properties of boron nitride (BN) films ion-beam deposited on silicon (Si), fused silica (SiO2), gallium arsenide (GaAs), and indium phosphide (InP) substrates in sliding contact with a diamond pin under a load. The results of the investigation indicate that BN films on nonmetallic substrates, like metal films on metallic substrates, deform elastically and plastically in the interfacial region when in contact with a diamond pin. However, unlike metal films and substrates, BN films on nonmetallic substrates can fracture when they are critically loaded. Not only does the yield pressure (hardness) of Si and SiO2 substrates increase by a factor of 2 in the presence of a BN film, but the critical load needed to fracture increases as well. The presence of films on the brittle substrates can arrest crack formation. The BN film reduces adhesion and friction in the sliding contact. BN adheres to Si and SiO2 and forms a good quality film, while it adheres poorly to GaAs and InP. The interfacial adhesive strengths were 1 GPa for a BN film on Si and appreciably higher than 1 GPa for a BN film on SiO2.

Resolving metal-molecule interfaces at single-molecule junctions

NASA Astrophysics Data System (ADS)

Komoto, Yuki; Fujii, Shintaro; Nakamura, Hisao; Tada, Tomofumi; Nishino, Tomoaki; Kiguchi, Manabu

2016-05-01

Electronic and structural detail at the electrode-molecule interface have a significant influence on charge transport across molecular junctions. Despite the decisive role of the metal-molecule interface, a complete electronic and structural characterization of the interface remains a challenge. This is in no small part due to current experimental limitations. Here, we present a comprehensive approach to obtain a detailed description of the metal-molecule interface in single-molecule junctions, based on current-voltage (I-V) measurements. Contrary to conventional conductance studies, this I-V approach provides a correlated statistical description of both, the degree of electronic coupling across the metal-molecule interface, and the energy alignment between the conduction orbital and the Fermi level of the electrode. This exhaustive statistical approach was employed to study single-molecule junctions of 1,4-benzenediamine (BDA), 1,4-butanediamine (C4DA), and 1,4-benzenedithiol (BDT). A single interfacial configuration was observed for both BDA and C4DA junctions, while three different interfacial arrangements were resolved for BDT. This multiplicity is due to different molecular adsorption sites on the Au surface namely on-top, hollow, and bridge. Furthermore, C4DA junctions present a fluctuating I-V curve arising from the greater conformational freedom of the saturated alkyl chain, in sharp contrast with the rigid aromatic backbone of both BDA and BDT.

The influence of polymeric membrane gas spargers on hydrodynamics and mass transfer in bubble column bioreactors.

PubMed

Tirunehe, Gossaye; Norddahl, B

2016-04-01

Gas sparging performances of a flat sheet and tubular polymeric membranes were investigated in 3.1 m bubble column bioreactor operated in a semi batch mode. Air-water and air-CMC (Carboxymethyl cellulose) solutions of 0.5, 0.75 and 1.0 % w/w were used as interacting gas-liquid mediums. CMC solutions were employed in the study to simulate rheological properties of bioreactor broth. Gas holdup, bubble size distribution, interfacial area and gas-liquid mass transfer were studied in the homogeneous bubbly flow hydrodynamic regime with superficial gas velocity (U(G)) range of 0.0004-0.0025 m/s. The study indicated that the tubular membrane sparger produced the highest gas holdup and densely populated fine bubbles with narrow size distribution. An increase in liquid viscosity promoted a shift in bubble size distribution to large stable bubbles and smaller specific interfacial area. The tubular membrane sparger achieved greater interfacial area and an enhanced overall mass transfer coefficient (K(L)a) by a factor of 1.2-1.9 compared to the flat sheet membrane.

Aqueous Solution-Deposited Molybdenum Oxide Films as an Anode Interfacial Layer for Organic Solar Cells.

PubMed

Yi, Qinghua; Zhai, Pengfei; Sun, Yinghui; Lou, Yanhui; Zhao, Jie; Sun, Baoquan; Patterson, Brian; Luo, Hongmei; Zhang, Wenrui; Jiao, Liang; Wang, Haiyan; Zou, Guifu

2015-08-26

In this study, we report the growth of molybdenum oxide (MoOx) film by polymer-assisted deposition (PAD), an environmentally friendly strategy in an aqueous system. The MoOx film has good crystal quality and is dense and smooth. The transparency of the film is >95% in the wavelength range of 300-900 nm. The device based on P3HT:PCBM absorber material was fabricated. The solar cell with PAD-MoOx as an anode interfacial layer exhibits great performance, even better than that of a solar cell with PSS or evaporated MoOx as an anode interfacial layer. More importantly, the solar cells based on the growth of MoOx have a longer term stability than that of solar cells based on PSS. These results demonstrate the aqueous PAD technology provides an alternative strategy not only for the thin films' growth of applied materials but also for the solution processing for the low-cost fabrication of future materials to be applied in the field of solar cells.

Fabrication of CA/TPU Helical Nanofibers and its Mechanism Analysis

NASA Astrophysics Data System (ADS)

Wu, Huihui; Zhao, Shihang; Han, Lei

2018-04-01

To explore the mechanism of cellulose acetate (CA)/thermoplastic polyurethane (TPU) on the fabrication of helical nanofibers, a series of experiments were conducted to find the optimum spinning conditions. The experimental results show that the CA (14 wt%, DMAc/acetone, 1/2 volume ratio)/TPU2 (18 wt%, DMAc/acetone, 3/1 volume ratio) system can fabricate helical nanofibers effectively via co-electrospinning. We focus on the interfacial interaction between the polymer components induced by the polymer structure and intrinsic properties, including solution properties, hydrogen bonding, and miscibility behavior of the two solutions. Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) are employed to investigate the interfacial interaction between the two phases of the polymer system. The analysis results provide the explanation of the experimental results that the CA/TPU system has the potential for producing helical nanofibers effectively. This study based on the interfacial interaction between polymer components provides an insight into the mechanism of CA/TPU helical fiber formation and introduces a richer choice of materials for the application of helical fibers.

Spatially-resolved magnetic resonance study of the dissolution interface between soaps and water

NASA Astrophysics Data System (ADS)

Ciampi, E.; Goerke, U.; McDonald, P. J.; Chambers, J. G.; Newling, B.

2002-06-01

The developing interfacial region between a soap bar and water has been studied using a suite of spatially resolved NMR techniques. Stray field imaging (STRAFI) allowed the dynamics of water ingress into a shop-bought, commercial soap to be followed. A simplistic analysis of the data shows the ingress to be a Fickian process (∝t1/2) in the first 4 h. The T2 contrast employed in the STRAFI method is not sufficient to resolve detail of the mesophase formation at the interface. However, double quantum filtered 2H spectroscopy at different positions in the interfacial region allowed water concentration (and mesophase distribution) to be mapped over the first 120 h of dissolution. A simple model shows good agreement with the water concentration data. In the isotropic soap solution above the interfacial region, J-cyclic cross polarization was used to selectively interrogate the CH2 1H of the soap alkyl chains and, in combination with a pulsed field gradient measurement of self-diffusion, suggests a micellar solution in which the hydrodynamic radius of the micelles is ~5nm.

Ice-surface adsorption enhanced colligative effect of antifreeze proteins in ice growth inhibition

NASA Astrophysics Data System (ADS)

Mao, Yougang; Ba, Yong

2006-09-01

This Communication describes a mechanism to explain antifreeze protein's function to inhibit the growth of ice crystals. We propose that the adsorption of antifreeze protein (AFP) molecules on an ice surface induces a dense AFP-water layer, which can significantly decrease the mole fraction of the interfacial water and, thus, lower the temperature for a seed ice crystal to grow in a super-cooled AFP solution. This mechanism can also explain the nearly unchanged melting point for the ice crystal due to the AFP's ice-surface adsorption. A mathematical model combining the Langmuir theory of adsorption and the colligative effect of thermodynamics has been proposed to find the equilibrium constants of the ice-surface adsorptions, and the interfacial concentrations of AFPs through fitting the theoretical curves to the experimental thermal hysteresis data. This model has been demonstrated by using the experimental data of serial size-mutated beetle Tenebrio molitor (Tm) AFPs. It was found that the AFP's ice-surface adsorptions could increase the interfacial AFP's concentrations by 3 to 4 orders compared with those in the bulk AFP solutions.

Aggregation of concentrated monoclonal antibody solutions studied by rheology and neutron scattering

NASA Astrophysics Data System (ADS)

Castellanos, Maria Monica; Pathak, Jai; Colby, Ralph

2013-03-01

Protein solutions are studied using rheology and scattering techniques to investigate aggregation. Here we present a monoclonal antibody (mAb) that aggregates after incubation at 40 °C (below its unfolding temperature), with a decrease in monomer purity of 6% in 10 days. The mAb solution contains surfactant and behaves as a Newtonian fluid when reconstituted into solution from the lyophilized form (before incubation at 40 °C). In contrast, mAb solutions incubated at 40 °C for 1 month exhibit shear yielding in torsional bulk rheometers. Interfacial rheology reveals that interfacial properties are controlled by the surfactant, producing a negligible surface contribution to the bulk yield stress. These results provide evidence that protein aggregates formed in the bulk are responsible for the yield stress. Small-angle neutron scattering (SANS) measurements show an increase in intensity at low wavevectors (q < 4*10-2 nm-1) that we attribute to protein aggregation, and is not observed in solutions stored at 4 °C for 3 days before the measurement. This work suggests a correlation between the aggregated state of the protein (stability) and the yield stress from rheology. Research funded by MedImmune

Interfacial wave theory for dendritic structure of a growing needle crystal. I - Local instability mechanism. II - Wave-emission mechanism at the turning point

NASA Technical Reports Server (NTRS)

Xu, Jian-Jun

1989-01-01

The complicated dendritic structure of a growing needle crystal is studied on the basis of global interfacial wave theory. The local dispersion relation for normal modes is derived in a paraboloidal coordinate system using the multiple-variable-expansion method. It is shown that the global solution in a dendrite growth process incorporates the morphological instability factor and the traveling wave factor.

Effects of a type I antifreeze protein (AFP) on the melting of frozen AFP and AFP+solute aqueous solutions studied by NMR microimaging experiment.

PubMed

Ba, Yong; Mao, Yougang; Galdino, Luiz; Günsen, Zorigoo

2013-01-01

The effects of a type I AFP on the bulk melting of frozen AFP solutions and frozen AFP+solute solutions were studied through an NMR microimaging experiment. The solutes studied include sodium chloride and glucose and the amino acids alanine, threonine, arginine, and aspartic acid. We found that the AFP is able to induce the bulk melting of the frozen AFP solutions at temperatures lower than 0 °C and can also keep the ice melted at higher temperatures in the AFP+solute solutions than those in the corresponding solute solutions. The latter shows that the ice phases were in super-heated states in the frozen AFP+solute solutions. We have tried to understand the first experimental phenomenon via the recent theoretical prediction that type I AFP can induce the local melting of ice upon adsorption to ice surfaces. The latter experimental phenomenon was explained with the hypothesis that the adsorption of AFP to ice surfaces introduces a less hydrophilic water-AFP-ice interfacial region, which repels the ionic/hydrophilic solutes. Thus, this interfacial region formed an intermediate chemical potential layer between the water phase and the ice phase, which prevented the transfer of water from the ice phase to the water phase. We have also attempted to understand the significance of the observed melting phenomena to the survival of organisms that express AFPs over cold winters.

Liquid-Vapor Interfacial Properties of Aqueous Solutions of Guanidinium and Methyl Guanidinium Chloride: Influence of Molecular Orientation on Interface Fluctuations

PubMed Central

Ou, Shuching; Cui, Di; Patel, Sandeep

2014-01-01

The guanidinium cation (C(NH2)3+) is a highly stable cation in aqueous solution due to its efficient solvation by water molecules and resonance stabilization of the charge. Its salts increase the solubility of nonpolar molecules (”salting-in”) and decrease the ordering of water. It is one of the strongest denaturants used in biophysical studies of protein folding. We investigate the behavior of guanidinium and its derivative, methyl guanidinium (an amino acid analogue) at the air-water surface, using atomistic molecular dynamics (MD) simulations and calculation of potentials of mean force. Methyl guanidinium cation is less excluded from the air-water surface than guanidinium cation, but both cations show orientational dependence of surface affinity. Parallel orientations of the guanidinium ring (relative to the Gibbs dividing surface) show pronounced free energy minima in the interfacial region, while ring orientations perpendicular to the GDS exhibit no discernible surface stability. Calculations of surface fluctuations demonstrate that near the air-water surface, the parallel-oriented cations generate significantly greater interfacial fluctuations compared to other orientations, which induces more long-ranged perturbations and solvent density redistribution. Our results suggest a strong correlation with induced interfacial fluctuations and ion surface stability. These results have implications for interpreting molecular-level, mechanistic action of this osmolyte’s interaction with hydrophobic interfaces as they impact protein denaturation (solubilization). PMID:23937431

Oxygen deficiency induced deterioration in microstructure and magnetic properties at Y{sub 3}Fe{sub 5}O{sub 12}/Pt interface

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

Song, Dongsheng; Zhu, Jing, E-mail: jzhu@mail.tsinghua.edu.cn; Ma, Li

2015-07-27

Transport efficiency of pure spin current across the ferromagnetic films adjacent with a nonmagnetic metal is strongly dependent on the spin mixing conductance, which is very sensitive to atomic-level interface conditions. Here, by the means of advanced electron microscopy techniques, atomic structure, electronic structure, and magnetic properties at Y{sub 3}Fe{sub 5}O{sub 12} (YIG)/Pt interface are detailed characterized to correlate the microstructure and magnetic properties with interfacial transport properties. It is found that the order-disorder structure transformation at the interface is accompanied with oxygen deficiency, thus the reduced iron valence and the break of magnetic atom-O-magnetic atom bridges, which is responsiblemore » for superexchange interaction and magnetic order. It is also found that the magnetic moment of interfacial iron ions is decreased. The disorder interfacial layer with suppressed magnetism finally contributes to the declined spin transport efficiency. Our results provide the knowledge to control and manipulate the interfacial structure and properties in order to obtain higher spin transport efficiency.« less

High On/Off Ratio Memristive Switching of Manganite/Cuprate Bilayer by Interfacial Magnetoelectricity

DOE PAGES

Shen, Xiao; Pennycook, Timothy J.; Hernandez-Martin, David; ...

2016-05-27

Memristive switching serves as the basis for a new generation of electronic devices. Conventional memristors are two-terminal devices in which the current is turned on and off by redistributing point defects, e.g., vacancies. Memristors based on alternative mechanisms have been explored, but achieving both high on/off ratio and low switching energy, as needed in applications, remains a challenge. This paper reports memristive switching in La 0.7Ca 0.3MnO 3/PrBa 2Cu 3O 7 bilayers with an on/off ratio greater than 103 and results of density functional theory calculations in terms of which it is concluded that the phenomenon is likely the resultmore » of a new type of interfacial magnetoelectricity. More specifically, this study shows that an external electric field induces subtle displacements of the interfacial Mn ions, which switches on/off an interfacial magnetic “dead layer”, resulting in memristive behavior for spin-polarized electron transport across the bilayer. The interfacial nature of the switching entails low energy cost, about of a tenth of atto Joule for writing/erasing a “bit”. To conclude, the results indicate new opportunities for manganite/cuprate systems and other transition metal oxide junctions in memristive applications.« less

Schottky barrier and band edge engineering via the interfacial structure and strain for the Pt/TiO2 heterostructure.

PubMed

Ma, Xiangchao; Wu, Xin; Wang, Yucheng; Dai, Ying

2017-07-19

Charge transfer across the Pt/TiO 2 interface, which is mainly determined by the interface Schottky barrier height (SBH), is an important process in the (photo)catalytic and electronic applications of the Pt/TiO 2 composite. Therefore, systematic investigation of the factors that affect the interface SBH is indispensable for understanding and optimizing its performance. In this work, a systematic study of the effects of the interfacial structure and strain on the SBH of the Pt/TiO 2 (001) interface has been carried out based on the first-principles calculations. The results of interface adhesion energy show that two different interfacial structures for the Pt/TiO 2 (001) heterointerface may exist experimentally, namely, O-Pt bonding and Ti-Pt bonding. Moreover, the interfacial structures result in not only different values for the SBH, but also different dependences of the SBH on strain. Detailed investigations show that these versatile modulations of the SBH with the structure and strain are mainly attributed to the strong dependence of the band edges of TiO 2 and the interfacial potential alignments on the strain and structure, suggesting that these results are general and may be applicable to other metal/TiO 2 heterostructures.

Highly improved Uv resistance and composite interfacial properties of aramid fiber via iron (III) coordination

NASA Astrophysics Data System (ADS)

Cheng, Zheng; Hong, Dawei; Dai, Yu; Jiang, Chan; Meng, Chenbo; Luo, Longbo; Liu, Xiangyang

2018-03-01

The poor Uv stability and weak interfacial adhesion are considered as the bottleneck problems for further application of aramid fiber. Herein, a new strategy, Fe3+ coordination, was reported for aramid fiber to simultaneous improve its Uv resistance and composite interfacial shear strength. Fe3+ was introduced onto aramid fiber by coordinating with benzimidazole unit of fiber structure. It can reach a doping capacity of as high as 1516ug/g fiber, and the fiber surface is saturatedly covered with Fe3+. The chemical structure of Fe3+-benzimidazole brings about strong metal-enhanced fluorescence emission effect, which, in turn, greatly raises its Uv stability. Owing to the Fe3+ coordination, the tensile strength of Fe-coordinated fiber could preserve as high as 96% after Uv irradiation, compared with 73% of untreated fiber. Meanwhile, the introduction of Fe3+ improves the surface polarity of aramid fiber and consequently leads to the increase of the composite interfacial shear strength by 39%. It is believed that the Fe-coordinated fiber integrates the advantages of easy production, cost-effective and increased Uv stability, as well as high composite interfacial adhesion, and can be used as promising enhancement for the advanced composite material in harsh environment.

Impact of Interfacial Layers in Perovskite Solar Cells.

PubMed

Cho, An-Na; Park, Nam-Gyu

2017-10-09

Perovskite solar cells (PCSs) are composed of organic-inorganic lead halide perovskite as the light harvester. Since the first report on a long-term-durable, 9.7 % efficient, solid-state perovskite solar cell, organic-inorganic halide perovskites have received considerable attention because of their excellent optoelectronic properties. As a result, a power conversion efficiency (PCE) exceeding 22 % was certified. Controlling the grain size, grain boundary, morphology, and defects of the perovskite layer is important for achieving high efficiency. In addition, interfacial engineering is equally or more important to further improve the PCE through better charge collection and a reduction in charge recombination. In this Review, the type of interfacial layers and their impact on photovoltaic performance are investigated for both the normal and the inverted cell architectures. Four different interfaces of fluorine-doped tin oxide (FTO)/electron-transport layer (ETL), ETL/perovskite, perovskite/hole-transport layer (HTL), and HTL/metal are classified, and their roles are investigated. The effects of interfacial engineering with organic or inorganic materials on photovoltaic performance are described in detail. Grain-boundary engineering is also included because it is related to interfacial engineering and the grain boundary in the perovskite layer plays an important role in charge conduction, recombination, and chargecarrier life time. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An analytical/numerical correlation study of the multiple concentric cylinder model for the thermoplastic response of metal matrix composites

NASA Technical Reports Server (NTRS)

Pindera, Marek-Jerzy; Salzar, Robert S.; Williams, Todd O.

1993-01-01

The utility of a recently developed analytical micromechanics model for the response of metal matrix composites under thermal loading is illustrated by comparison with the results generated using the finite-element approach. The model is based on the concentric cylinder assemblage consisting of an arbitrary number of elastic or elastoplastic sublayers with isotropic or orthotropic, temperature-dependent properties. The elastoplastic boundary-value problem of an arbitrarily layered concentric cylinder is solved using the local/global stiffness matrix formulation (originally developed for elastic layered media) and Mendelson's iterative technique of successive elastic solutions. These features of the model facilitate efficient investigation of the effects of various microstructural details, such as functionally graded architectures of interfacial layers, on the evolution of residual stresses during cool down. The available closed-form expressions for the field variables can readily be incorporated into an optimization algorithm in order to efficiently identify optimal configurations of graded interfaces for given applications. Comparison of residual stress distributions after cool down generated using finite-element analysis and the present micromechanics model for four composite systems with substantially different temperature-dependent elastic, plastic, and thermal properties illustrates the efficacy of the developed analytical scheme.

Efficient Dual-Site Carbon Monoxide Electro-Catalysts via Interfacial Nano-Engineering

PubMed Central

Liu, Zhen; Huang, Zhongyuan; Cheng, Feifei; Guo, Zhanhu; Wang, Guangdi; Chen, Xu; Wang, Zhe

2016-01-01

Durable, highly efficient, and economic sound electrocatalysts for CO electrooxidation (COE) are the emerging key for wide variety of energy solutions, especially fuel cells and rechargeable metal−air batteries. Herein, we report the novel system of nickel−aluminum double layered hydroxide (NiAl-LDH) nanoplates on carbon nanotubes (CNTs) network. The formulation of such complexes system was to be induced through the assistance of gold nanoparticles in order to form dual-metal active sites so as to create a extended Au/NiO two phase zone. Bis (trifluoromethylsulfonyl)imide (NTf2) anion of ionic liquid electrolyte was selected to enhance the CO/O2 adsorption and to facilitate electro-catalyzed oxidation of Ni (OH)2 to NiOOH by increasing the electrophilicity of catalytic interface. The resulting neutral catalytic system exhibited ultra-high electrocatalytic activity and stability for CO electrooxidation than commercial and other reported precious metal catalysts. The turnover frequency (TOF) of the LDH-Au/CNTs COE catalyst was much higher than the previous reported other similar electrocatalysts, even close to the activity of solid-gas chemical catalysts at high temperature. Moreover, in the long-term durability testing, the negligible variation of current density remains exsisting after 1000 electrochemistry cycles. PMID:27650532

Impact of oxygen plasma postoxidation process on Al2O3/n-In0.53Ga0.47As metal-oxide-semiconductor capacitors

NASA Astrophysics Data System (ADS)

Lechaux, Y.; Fadjie-Djomkam, A. B.; Bollaert, S.; Wichmann, N.

2016-09-01

Capacitance-voltage (C-V) measurements and x-ray photoelectron spectroscopy (XPS) analysis were performed in order to investigate the effect of a oxygen (O2) plasma after oxide deposition on the Al2O3/n-In0.53Ga0.47As metal-oxide-semiconductor structure passivated with ammonia NH4OH solution. From C-V measurements, an improvement of charge control is observed using the O2 plasma postoxidation process on In0.53Ga0.47As, while the minimum of interface trap density remains at a good value lower than 1 × 1012 cm-2 eV-1. From XPS measurements, we found that NH4OH passivation removes drastically the Ga and As native oxides on the In0.53Ga0.47As surface and the O2 plasma postoxidation process enables the reduction of interface re-oxidation after post deposition annealing (PDA) of the oxide. The advanced hypothesis is the formation of interfacial barrier between Al2O3 and In0.53Ga0.47As which prevents the diffusion of oxygen species into the semiconductor surface during PDA.

A Workshop on 3-5 Semiconductor: Metal Interfacial Chemistry and Its Effect on Electrical Properties, November 3-5, 1986,

DTIC Science & Technology

1986-11-05

band bending condition eliminated after metal deposition onto Ga203 * up to "𔃺.7 eY shift in EF occurs with sequential oxide and metal surface...and the tables of band- lineups to estimate the sign and magnitude of the effect. *Supported, in part, by ONR Contract No. N00014-85-C-0i35 ** Permanent...V1a,3. c SL. c93 1 Ill-V Interfaces: Schottky Barriers vs. Heterojunctions Giorgio Margaritondo University of Wisconsin HETE-ROJUNCTION BAND LINEUPS VS

Volumetric Interpretation of Protein Adsorption: Interfacial Packing of Protein Adsorbed to Hydrophobic Surfaces from Surface-Saturating Solution Concentrations

PubMed Central

Kao, Ping; Parhi, Purnendu; Krishnan, Anandi; Noh, Hyeran; Haider, Waseem; Tadigadapa, Srinivas; Allara, David L.; Vogler, Erwin A.

2010-01-01

The maximum capacity of a hydrophobic adsorbent is interpreted in terms of square or hexagonal (cubic and face-centered-cubic, FCC) interfacial packing models of adsorbed blood proteins in a way that accommodates experimental measurements by the solution-depletion method and quartz-crystal-microbalance (QCM) for the human proteins serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa). A simple analysis shows that adsorbent capacity is capped by a fixed mass/volume (e.g. mg/mL) surface-region (interphase) concentration and not molar concentration. Nearly analytical agreement between the packing models and experiment suggests that, at surface saturation, above-mentioned proteins assemble within the interphase in a manner that approximates a well-ordered array. HSA saturates a hydrophobic adsorbent with the equivalent of a single square-or-hexagonally-packed layer of hydrated molecules whereas the larger proteins occupy two-or-more layers, depending on the specific protein under consideration and analytical method used to measure adsorbate mass (solution depletion or QCM). Square-or-hexagonal (cubic and FCC) packing models cannot be clearly distinguished by comparison to experimental data. QCM measurement of adsorbent capacity is shown to be significantly different than that measured by solution depletion for similar hydrophobic adsorbents. The underlying reason is traced to the fact that QCM measures contribution of both core protein, water of hydration, and interphase water whereas solution depletion measures only the contribution of core protein. It is further shown that thickness of the interphase directly measured by QCM systematically exceeds that inferred from solution-depletion measurements, presumably because the static model used to interpret solution depletion does not accurately capture the complexities of the viscoelastic interfacial environment probed by QCM. PMID:21035180

Volumetric interpretation of protein adsorption: interfacial packing of protein adsorbed to hydrophobic surfaces from surface-saturating solution concentrations.

PubMed

Kao, Ping; Parhi, Purnendu; Krishnan, Anandi; Noh, Hyeran; Haider, Waseem; Tadigadapa, Srinivas; Allara, David L; Vogler, Erwin A

2011-02-01

The maximum capacity of a hydrophobic adsorbent is interpreted in terms of square or hexagonal (cubic and face-centered-cubic, FCC) interfacial packing models of adsorbed blood proteins in a way that accommodates experimental measurements by the solution-depletion method and quartz-crystal-microbalance (QCM) for the human proteins serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa). A simple analysis shows that adsorbent capacity is capped by a fixed mass/volume (e.g. mg/mL) surface-region (interphase) concentration and not molar concentration. Nearly analytical agreement between the packing models and experiment suggests that, at surface saturation, above-mentioned proteins assemble within the interphase in a manner that approximates a well-ordered array. HSA saturates a hydrophobic adsorbent with the equivalent of a single square or hexagonally-packed layer of hydrated molecules whereas the larger proteins occupy two-or-more layers, depending on the specific protein under consideration and analytical method used to measure adsorbate mass (solution depletion or QCM). Square or hexagonal (cubic and FCC) packing models cannot be clearly distinguished by comparison to experimental data. QCM measurement of adsorbent capacity is shown to be significantly different than that measured by solution depletion for similar hydrophobic adsorbents. The underlying reason is traced to the fact that QCM measures contribution of both core protein, water of hydration, and interphase water whereas solution depletion measures only the contribution of core protein. It is further shown that thickness of the interphase directly measured by QCM systematically exceeds that inferred from solution-depletion measurements, presumably because the static model used to interpret solution depletion does not accurately capture the complexities of the viscoelastic interfacial environment probed by QCM. Copyright © 2010 Elsevier Ltd. All rights reserved.

Roles of interfacial reaction on mechanical properties of solder interfaces

NASA Astrophysics Data System (ADS)

Liu, Pilin

This study investigated roles of interfacial reaction in fracture and fatigue of solder interconnects. The interfacial reaction phases in the as-reflowed and after aging were examined by cross-sectional transmission electron microscopy (TEM) while interfacial mechanical properties were determined from a flexural peel fracture mechanics technique. Because of their widespread uses in microelectronic packaging, SnPb solder interfaces, and Bi-containing Pb-free solder interfaces were chosen as the subjects of this study. In the interfacial reaction study, we observed a complicated micro structural evolution during solid-state aging of electroless-Ni(P)/SnPb solder interconnects. In as-reflowed condition, the interfacial reaction produced Ni3Sn 4 and P-rich layers. Following overaging, the interfacial microstructure degenerated into a complex multilayer structure consisting of multiple layers of Ni-Sn compounds and transformed Ni-P phases. In SnPb solder interfacial system, fatigue study showed that the overaging of the high P electroless Ni-P/SnPb interconnects resulted in a sharp reduction in the fatigue resistance of the interface in the high crack growth rate regime. Fracture mechanism analysis indicated that the sharp drop in fatigue resistance was triggered by the brittle fracture of the Ni3Sn2 intermetallic phase developed at the overaged interface. The fatigue behavior was strongly dependent on P concentration in electroless Ni. Kirkendall voids were found in the interfacial region after aging, but they did not cause premature fracture of the solder interfaces. In Bi-containing solder interfacial system, we found that Bi segregated to the Cu-intermetallic interface during aging in SnBi/Cu interconnect. This caused serious embrittlement of Sn-Bi/Cu interface. Further aging induced numerous voids along the Cu3Sn/Cu interface. These interfacial voids were different from Kirkendall voids. Their formation was explained on basis of vacancy condensation at the interface as the Bi segregants reduced the number of effective Cu vacancy sink sites and enhanced void nucleation at the interface. The Bi segregation was avoided by replacing the Cu metallization with Ni. It was found that Bi developed a concentration gradient in the Ni 3Sn4 during interfacial reaction, with the Bi concentration falling off to zero as the Ni/IMC interface was approached. Therefore, the inhibition of Bi segregation by Ni was due to the inability of Bi to reach Ni/IMC interface.

Relating the variation of secondary structure of gelatin at fish oil-water interface to adsorption kinetics, dynamic interfacial tension and emulsion stability.

PubMed

Liu, Huihua; Wang, Bo; Barrow, Colin J; Adhikari, Benu

2014-01-15

The objectives of this study were to quantify the relationship between secondary structure of gelatin and its adsorption at the fish-oil/water interface and to quantify the implication of the adsorption on the dynamic interfacial tension (DST) and emulsion stability. The surface hydrophobicity of the gelatin solutions decreased when the pH increased from 4.0 to 6.0, while opposite tend was observed in the viscosity of the solution. The DST values decreased as the pH increased from 4.0 to 6.0, indicating that higher positive charges (measured trough zeta potential) in the gelatin solution tended to result in higher DST values. The adsorption kinetics of the gelatin solution was examined through the calculated diffusion coefficients (Deff). The addition of acid promoted the random coil and β-turn structures at the expense of α-helical structure. The addition of NaOH decreased the β-turn and increased the α-helix and random coil. The decrease in the random coil and triple helix structures in the gelatin solution resulted into increased Deff values. The highest diffusion coefficients, the highest emulsion stability and the lowest amount of random coil and triple helix structures were observed at pH=4.8. The lowest amount of random coil and triple helix structures in the interfacial protein layer correlated with the highest stability of the emulsion (highest ESI value). The lower amount of random coil and triple helix structures allowed higher coverage of the oil-water interface by relatively highly ordered secondary structure of gelatin. Copyright © 2013 Elsevier Ltd. All rights reserved.

FEM Modeling of In-Plane Stress Distribution in Thick Brittle Coatings/Films on Ductile Substrates Subjected to Tensile Stress to Determine Interfacial Strength.

PubMed

Wang, Kaishi; Zhang, Fangzhou; Bordia, Rajendra K

2018-03-27

The ceramic-metal interface is present in various material structures and devices that are vulnerable to failures, like cracking, which are typically due to their incompatible properties, e.g., thermal expansion mismatch. In failure of these multilayer systems, interfacial shear strength is a good measure of the robustness of interfaces, especially for planar films. There is a widely-used shear lag model and method by Agrawal and Raj to analyse and measure the interfacial shear strength of thin brittle film on ductile substrates. The use of this classical model for a type of polymer derived ceramic coatings (thickness ~18 μm) on steel substrate leads to high values of interfacial shear strength. Here, we present finite element simulations for such a coating system when it is subjected to in-plane tension. Results show that the in-plane stresses in the coating are non-uniform, i.e., varying across the thickness of the film. Therefore, they do not meet one of the basic assumptions of the classical model: uniform in-plane stress. Furthermore, effects of three significant parameters, film thickness, crack spacing, and Young's modulus, on the in-plane stress distribution have also been investigated. 'Thickness-averaged In-plane Stress' (TIS), a new failure criterion, is proposed for estimating the interfacial shear strength, which leads to a more realistic estimation of the tensile strength and interfacial shear strength of thick brittle films/coatings on ductile substrates.

FEM Modeling of In-Plane Stress Distribution in Thick Brittle Coatings/Films on Ductile Substrates Subjected to Tensile Stress to Determine Interfacial Strength

PubMed Central

Zhang, Fangzhou; Bordia, Rajendra K.

2018-01-01

The ceramic-metal interface is present in various material structures and devices that are vulnerable to failures, like cracking, which are typically due to their incompatible properties, e.g., thermal expansion mismatch. In failure of these multilayer systems, interfacial shear strength is a good measure of the robustness of interfaces, especially for planar films. There is a widely-used shear lag model and method by Agrawal and Raj to analyse and measure the interfacial shear strength of thin brittle film on ductile substrates. The use of this classical model for a type of polymer derived ceramic coatings (thickness ~18 μm) on steel substrate leads to high values of interfacial shear strength. Here, we present finite element simulations for such a coating system when it is subjected to in-plane tension. Results show that the in-plane stresses in the coating are non-uniform, i.e., varying across the thickness of the film. Therefore, they do not meet one of the basic assumptions of the classical model: uniform in-plane stress. Furthermore, effects of three significant parameters, film thickness, crack spacing, and Young’s modulus, on the in-plane stress distribution have also been investigated. ‘Thickness-averaged In-plane Stress’ (TIS), a new failure criterion, is proposed for estimating the interfacial shear strength, which leads to a more realistic estimation of the tensile strength and interfacial shear strength of thick brittle films/coatings on ductile substrates. PMID:29584647

Silver nanoparticles-incorporated Nb2O5 surface passivation layer for efficiency enhancement in dye-sensitized solar cells.

PubMed

Suresh, S; Unni, Gautam E; Satyanarayana, M; Sreekumaran Nair, A; Mahadevan Pillai, V P

2018-08-15

Guiding and capturing photons at the nanoscale by means of metal nanoparticles and interfacial engineering for preventing back-electron transfer are well documented techniques for performance enhancement in excitonic solar cells. Drifting from the conventional route, we propose a simple one-step process to integrate both metal nanoparticles and surface passivation layer in the porous photoanode matrix of a dye-sensitized solar cell. Silver nanoparticles and Nb 2 O 5 surface passivation layer are simultaneously deposited on the surface of a highly porous nanocrystalline TiO 2 photoanode, facilitating an absorption enhancement in the 465 nm and 570 nm wavelength region and a reduction in back-electron transfer in the fabricated dye-sensitized solar cells together. The TiO 2 photoanodes were prepared by spray pyrolysis deposition method from a colloidal solution of TiO 2 nanoparticles. An impressive 43% enhancement in device performance was accomplished in photoanodes having an Ag-incorporated Nb 2 O 5 passivation layer as against a cell without Ag nanoparticles. By introducing this idea, we were able to record two benefits - the metal nanoparticles function as the absorption enhancement agent, and the Nb 2 O 5 layer as surface passivation for TiO 2 nanoparticles and as an energy barrier layer for preventing back-electron transfer - in a single step. Copyright © 2018 Elsevier Inc. All rights reserved.

Numerical Simulation of Delamination Growth in Composite Materials

NASA Technical Reports Server (NTRS)

Camanho, P. P.; Davila, C. G.; Ambur, D. R.

2001-01-01

The use of decohesion elements for the simulation of delamination in composite materials is reviewed. The test methods available to measure the interfacial fracture toughness used in the formulation of decohesion elements are described initially. After a brief presentation of the virtual crack closure technique, the technique most widely used to simulate delamination growth, the formulation of interfacial decohesion elements is described. Problems related with decohesion element constitutive equations, mixed-mode crack growth, element numerical integration and solution procedures are discussed. Based on these investigations, it is concluded that the use of interfacial decohesion elements is a promising technique that avoids the need for a pre-existing crack and pre-defined crack paths, and that these elements can be used to simulate both delamination onset and growth.

DIFFUSED SOLUTE-SOLVENT INTERFACE WITH POISSON-BOLTZMANN ELECTROSTATICS: FREE-ENERGY VARIATION AND SHARP-INTERFACE LIMIT.

PubMed

Li, B O; Liu, Yuan

A phase-field free-energy functional for the solvation of charged molecules (e.g., proteins) in aqueous solvent (i.e., water or salted water) is constructed. The functional consists of the solute volumetric and solute-solvent interfacial energies, the solute-solvent van der Waals interaction energy, and the continuum electrostatic free energy described by the Poisson-Boltzmann theory. All these are expressed in terms of phase fields that, for low free-energy conformations, are close to one value in the solute phase and another in the solvent phase. A key property of the model is that the phase-field interpolation of dielectric coefficient has the vanishing derivative at both solute and solvent phases. The first variation of such an effective free-energy functional is derived. Matched asymptotic analysis is carried out for the resulting relaxation dynamics of the diffused solute-solvent interface. It is shown that the sharp-interface limit is exactly the variational implicit-solvent model that has successfully captured capillary evaporation in hydrophobic confinement and corresponding multiple equilibrium states of underlying biomolecular systems as found in experiment and molecular dynamics simulations. Our phase-field approach and analysis can be used to possibly couple the description of interfacial fluctuations for efficient numerical computations of biomolecular interactions.

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

Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.

All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte – electrode interfaces will be critical to improve performance. In this paper, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grewmore » in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. Finally, the stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.« less

A discontinuous Poisson-Boltzmann equation with interfacial jump: homogenisation and residual error estimate.

PubMed

Fellner, Klemens; Kovtunenko, Victor A

2016-01-01

A nonlinear Poisson-Boltzmann equation with inhomogeneous Robin type boundary conditions at the interface between two materials is investigated. The model describes the electrostatic potential generated by a vector of ion concentrations in a periodic multiphase medium with dilute solid particles. The key issue stems from interfacial jumps, which necessitate discontinuous solutions to the problem. Based on variational techniques, we derive the homogenisation of the discontinuous problem and establish a rigorous residual error estimate up to the first-order correction.

Computational simulation of subatomic-resolution AFM and STM images for graphene/hexagonal boron nitride heterostructures with intercalated defects

NASA Astrophysics Data System (ADS)

Lee, Junsu; Kim, Minjung; Chelikowsky, James R.; Kim, Gunn

2016-07-01

Using ab initio density functional calculations, we predict subatomic-resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) images of vertical heterostructures of graphene/hexagonal boron nitride (h-BN) with an intercalated metal atom (Li, K, Cr, Mn, Co, or Cu), and study the effects of the extrinsic metal defect on the interfacial coupling. We find that the structural deformation of the graphene/h-BN layer caused by the metal defect strongly affects the AFM images, whereas orbital hybridization between the metal defect and the graphene/h-BN layer characterizes the STM images.

Investigation of Heat Transfer at the Mold/Metal Interface in Permanent Mold Casting of Light Alloys

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

Robert D. Pehlke; John T. Berry

2005-12-16

Accurate modeling of the metal casting process prior to creating a mold design demands reliable knowledge of the interfacial heat transfer coefficient at the mold metal interface as a function of both time and location. The phenomena concerned with the gap forming between the mold and the solidifying metal are complex but need to be understood before any modeling is attempted. The presence of mold coatings further complicates the situation. A commercial casting was chosen and studied in a gravity permanent mold casting process. The metal/mold interfacial heat transfer coefficient (IHTC) was the focus of the research. A simple, directmore » method has been used to evaluate the IHTC. Both the simulation and experiments have shown that a reasonably good estimate of the heat transfer coefficient could be made in the case studied. It has been found that there is a good agreement between experiments and simulations in the temperature profiles during the solidification process, given that the primary mechanism of heat transfer across the gap in permanent mold casting of light alloys is by conduction across the gap. The procedure utilized to determine the interfacial heat transfer coefficient can be applied to other casting processes. A recently completed project involving The University of Michigan and Mississippi State University, together with several industrial partners, which was supported by the USDOE through the Cast Metals Coalition, examined a number of cases of thermal contact. In an investigation which gave special consideration to the techniques of measurement, several mold coatings were employed and results presented as a function of time. Realistic conditions of coating thickness and type together with an appropriate combination of mold preheat and metal pouring temperature were strictly maintained throughout the investigation. Temperature sensors, in particular thermocouples, play an important part in validating the predictions of solidification models. Cooling curve information, as well as temperature gradient history both in the solidifying metal and within the mold are invariably required to be validated. This validation depends upon the response of the sensor concerned, but also on its own effect upon the thermal environment. A joint university/industry team has completed an investigation of the invasive effects of thermocouples upon temperature history in permanent molds determining the degree of uncertainty associated with placement and indicating how the time-temperature history may be recovered. In addition to its relevance to the all important study of thermal contact of the casting with metallic molds, the observations also impact the determination of heat flux and interfacial heat transfer coefficients. In these respects the study represents the first of its kind that has tackled the problem in depth for permanent mold castings. An important ramification of this investigation has been the errors likely to be encountered in mold temperature measurement with thin section aluminum castings, especially with respect to the plans for thermocouple placement. A comparison between the degree of uncertainty experienced in sand molds compared with that found in permanent molds reveals that the associated problems have a lesser impact. These conclusions and the related recommendations have been disseminated to industry and the technical community through project reports and publications.« less

Perpendicular magnetic anisotropy at transition metal/oxide interfaces and applications

NASA Astrophysics Data System (ADS)

Dieny, B.; Chshiev, M.

2017-04-01

Spin electronics is a rapidly expanding field stimulated by a strong synergy between breakthrough basic research discoveries and industrial applications in the fields of magnetic recording, magnetic field sensors, nonvolatile memories [magnetic random access memories (MRAM) and especially spin-transfer-torque MRAM (STT-MRAM)]. In addition to the discovery of several physical phenomena (giant magnetoresistance, tunnel magnetoresistance, spin-transfer torque, spin-orbit torque, spin Hall effect, spin Seebeck effect, etc.), outstanding progress has been made on the growth and nanopatterning of magnetic multilayered films and nanostructures in which these phenomena are observed. Magnetic anisotropy is usually observed in materials that have large spin-orbit interactions. However, in 2002 perpendicular magnetic anisotropy (PMA) was discovered to exist at magnetic metal/oxide interfaces [for instance Co (Fe )/alumina ]. Surprisingly, this PMA is observed in systems where spin-orbit interactions are quite weak, but its amplitude is remarkably large—comparable to that measured at Co /Pt interfaces, a reference for large interfacial anisotropy (anisotropy˜1.4 erg /cm2=1.4 mJ /m2 ). Actually, this PMA was found to be very common at magnetic metal/oxide interfaces since it has been observed with a large variety of amorphous or crystalline oxides, including AlOx, MgO, TaOx, HfOx, etc. This PMA is thought to be the result of electronic hybridization between the oxygen and the magnetic transition metal orbit across the interface, a hypothesis supported by ab initio calculations. Interest in this phenomenon was sparked in 2010 when it was demonstrated that the PMA at magnetic transition metal/oxide interfaces could be used to build out-of-plane magnetized magnetic tunnel junctions for STT-MRAM cells. In these systems, the PMA at the CoFeB /MgO interface can be used to simultaneously obtain good memory retention, thanks to the large PMA amplitude, and a low write current, thanks to a relatively weak Gilbert damping. These two requirements for memories tend to be difficult to reconcile since they rely on the same spin-orbit coupling. PMA-based approaches have now become ubiquitous in the designs for perpendicular STT-MRAM, and major microelectronics companies are actively working on their development with the first goal of addressing embedded FLASH and static random access memory-type of applications. Scalability of STT-MRAM devices based on this interfacial PMA is expected to soon exceed the 20-nm nodes. Several very active new fields of research also rely on interfacial PMA at magnetic metal/oxide interfaces, including spin-orbit torques associated with Rashba or spin Hall effects, record high speed domain wall propagation in buffer/magnetic metal/oxide-based magnetic wires, and voltage-based control of anisotropy. This review deals with PMA at magnetic metal/oxide interfaces from its discovery, by examining the diversity of systems in which it has been observed and the physicochemical methods through which the key roles played by the electronic hybridization at the metal/oxide interface were elucidated. The physical origins of the phenomenon are also covered and how these are supported by ab initio calculations is dealt with. Finally, some examples of applications of this interfacial PMA in STT-MRAM are listed along with the various emerging research topics taking advantage of this PMA.

Statistical analysis of interfacial gap in a cementless stem FE model.

PubMed

Park, Youngbae; Choi, Donok; Hwang, Deuk Soo; Yoon, Yong-San

2009-02-01

In cementless total hip arthroplasty, a fair amount of interfacial gap exists between the femoral stem and the bone. However, the effect of these gaps on the mechanical stability of the stem is poorly understood. In this paper, a finite element model with various interfacial gap definitions is used to quantify the effect of interfacial gaps on the primary stability of a Versys Fiber Metal Taper stem under stair climbing loads. In the first part, 500 random interfacial gap definitions were simulated. The resulting micromotion was approximately inversely proportional to the contact ratio, and the variance of the micromotion was greater with a lower contact ratio. Moreover, when the magnitude of the micromotion was compared between the gap definitions that had contact at a specific site and those that had no contact at that site, it was found that gaps located in the proximal-medial region of the stem surface had the most important effect on the micromotion. In a second trial, 17 gap definitions mimicking a gap pattern that has been observed experimentally were simulated. For a given contact ratio, the micromotion observed in the second trial was lower than the average result of those in the first, where the gaps were placed randomly. In either trial, when the contact ratio was higher than 40%, the micromotion showed no significant difference (first trial) or a gentle slope (-0.24 mum% in the second trial) in relation to the contact ratio. Considering the reported contact ratios for properly implanted stems, variations in the amount of interfacial gap would not likely cause a drastic difference in micromotion, and this effect could be easily overshadowed by other clinical factors. In conclusion, differences in interfacial gaps are not expected to have a noticeable effect on the clinical micromotion of this cementless stem.

Polymer-Silica Nanocomposites: A Versatile Platform for Multifunctional Materials

NASA Astrophysics Data System (ADS)

Chiu, Chi-Kai

Solution sol-gel synthesis is a versatile approach to create polymer-silica nanocomposite materials. The solution-to-solid transformation results in a solid consisting of interconnected nanoporous structure in 3D space, making it the ideal material for filtration, encapsulation, optics, electronics, drug release, and biomaterials, etc. Although the pore between nano and meso size may be tunable using different reaction conditions, the intrinsic properties such as limited diffusion within pore structure, complicated interfacial interactions at the pore surfaces, shrinkage and stress-induced cracking and brittleness have limited the applications of this material. To overcome these problems, diffusion, pore size, shrinkage and stress-induced defects need further investigation. Thus, the presented thesis will address these important questions such as whether these limitations can be utilized as the novel method to create new materials and lead to new applications. First, the behaviors of polymers such as poly(ethylene glycol) inside the silica pores are examined by studying the nucleation and growth of AgCl at the surface of the porous matrix. The pore structure and the pressure induced by the shrinkage affect have been found to induce the growth of AgCl nanocrystals. When the same process is carried out at 160 °C, silver metallization is possible. Due to the shrinkage-induced stresses, the polymer tends to move into open crack spaces and exterior surfaces, forming interconnected silver structure. This interconnected silver structure is very unique because its density is not related to the size scale of nanopore structures. These findings suggest that it is possible to utilize defect surface of silica material as the template to create interconnected silver structure. When the scale is small, polymer may no longer be needed if the diffusion length of Ag is more than the size of silica particles. To validate our assumption, monoliths of sol-gel sample containing AgNO3 was ground into two different sizes of powder followed by powder pressing, heat-treating and etching. A new robust porous silver foam was then successfully made. By combining the results from room temperature and high temperature processes, we further study the patterned silver nanoparticles arrays in order to examine how mobility of silver can be controlled on a quantifiable scale. Furthermore, we have identified a thiolcontaining sol-gel precursor to control the affinity between silver and silica matrix. Lastly, the effects of interfacial interactions between sol-gel silica and other nanocomposite components and the effect of thickness of the sol-gel layer on mechanical properties were investigated. These studies were applied to the biomimetic hydroxyapatite-gelatin system. We have found that by limiting the thickness while maintaining interfacial interactions of the sol-gel layer, a unique moldable property and short hardening time from these nanocomposites can be achieved without compromising its biocompatibility. Their biocompatibility has been proven based on the in vitro and in vivo testing of these materials. In conclusion, the present study has demonstrated that polymer-silica nanocomposite is a versatile platform to carry out applications in nanocrystal growth, nanoporous metals, metal-ceramic composites, nano-imprint thin film, and bone grafts. These important findings not only provide new insights into nanocomposites but also give new meanings to the previously functional-limited sol-gel materials.

High performance light-colored nitrile-butadiene rubber nanocomposites.

PubMed

Lei, Yanda; Guo, Baochun; Chen, Feng; Zhu, Lixin; Zhou, Wenyou; Jia, Demin

2011-12-01

High mechanical performance nitrile-butadiene rubber (NBR) with light color was fabricated by the method of in situ formation of zinc disorbate (ZDS) or magnesium disorbate (MDS). The in situ formed ZDS and its polymerization via internal mixing was confirmed by X-ray diffaraction. The mechanical properties, ageing resistance, morphology and the dynamic mechanical analysis were fully studied. It was found that with increasing loading of metallic disorbate both the curing rate and the ionic crosslink density was largely increased. The modulus, tensile strength and tear strength were largely increased. With a comparison between internal mixing and opening mixing, the mechanical performance for the former one was obviously better than the latter one. The high performance was ascribed to the finely dispersion nano domains with irregular shape and obscure interfacial structures. Except for the NBR vulcanizate with a high loading of MDS, the others' ageing resistance with incorporation of these two metallic disorbate was found to be good. Dynamic mechanical analysis (DMA) showed that, with increasing loading of metallic disorbate, the highly increased storage modulus above -20 degrees C, the up-shifted glass transition temperature (Tg) and the reduced mechanical loss were ascribed to strengthened interfacial interactions.

High-Potential Porphyrins Supported on SnO 2 and TiO 2 Surfaces for Photoelectrochemical Applications

DOE PAGES

Jiang, Jianbing; Swierk, John R.; Materna, Kelly L.; ...

2016-12-03

Here, we report CF 3-substituted porphyrins and evaluate their use as photosensitizers in water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) by characterizing interfacial electron transfer on metal oxide surfaces. Furthermore, by using (CF 3) 2C 6H 3 instead of C 6F 5 substituents at the meso positions, we obtain the desired high potentials while avoiding the sensitivity of C 6F 5 substituents to nucleophilic substitution, a process that limits the types of synthetic reactions that can be used. Both the number of CF 3 groups and the central metal tune the ground and excited-state potentials. A pair of porphyrins bearing carboxylic acidsmore » as anchoring groups were deposited on SnO 2 and TiO 2 surfaces and the interfacial charge-injection and charge-recombination kinetics were characterized by using a combination of computational modeling, terahertz measurements, and transient absorption spectroscopy. We also found that both free-base and metallated porphyrins inject into SnO 2, and that recombination is slower for the latter case. Our findings demonstrate that (CF 3) 2C 6H 3-substituted porphyrins are promising photosensitizers for use in WS-DSPECs.« less

Perpendicular Magnetic Anisotropy in Heusler Alloy Films and Their Magnetoresistive Junctions

PubMed Central

Frost, William; Samiepour, Marjan

2018-01-01

For the sustainable development of spintronic devices, a half-metallic ferromagnetic film needs to be developed as a spin source with exhibiting 100% spin polarisation at its Fermi level at room temperature. One of the most promising candidates for such a film is a Heusler-alloy film, which has already been proven to achieve the half-metallicity in the bulk region of the film. The Heusler alloys have predominantly cubic crystalline structures with small magnetocrystalline anisotropy. In order to use these alloys in perpendicularly magnetised devices, which are advantageous over in-plane devices due to their scalability, lattice distortion is required by introducing atomic substitution and interfacial lattice mismatch. In this review, recent development in perpendicularly-magnetised Heusler-alloy films is overviewed and their magnetoresistive junctions are discussed. Especially, focus is given to binary Heusler alloys by replacing the second element in the ternary Heusler alloys with the third one, e.g., MnGa and MnGe, and to interfacially-induced anisotropy by attaching oxides and metals with different lattice constants to the Heusler alloys. These alloys can improve the performance of spintronic devices with higher recording capacity. PMID:29324709

A theoretical study on the mechanism of hydrogen evolution on non-precious partially oxidized nickel-based heterostructures for fuel cells.

PubMed

Pan, Xinju; Zhou, Gang

2018-03-28

It is desirable, yet challenging, to utilize non-precious metals instead of noble-metals as efficient catalysts in the renewable energy manufacturing industry. Using first principles calculations, we study the structural characteristics of partially oxidized nickel-based nanoheterostructures (NiO/Ni NHSs), and the interfacial effects on hydrogen evolution. The origin of the enhanced hydrogen evolution performance is discussed at the microscopic level. This study identifies two types of active sites of the exposed Ni surface available for the hydrogen evolution reaction (HER). One is the hcp-hollow sites near the perimeter boundary that exhibit a more excellent HER performance than platinum (Pt), and the other the second nearest neighbor fcc-hollow sites away from the boundary that exhibit a similar performance to Pt. The interfacial effects result from the competitive charge transfer between NiO and Ni surfaces in NHSs, and enhance the reactivity of NiO/Ni NHSs by shifting the d-states of surface atoms down in energy. The illumination of the mechanism would be helpful for the design of more efficient and cheap transition metal-based catalysts.

A novel broadband impedance method for detection of cell-derived microparticles.

PubMed

Lvovich, Vadim; Srikanthan, Sowmya; Silverstein, Roy L

2010-10-15

A novel label-free method is presented to detect and quantify cell-derived microparticles (MPs) by the electrochemical potential-modulated electrochemical impedance spectroscopy (EIS). MPs are present in elevated concentrations during pathological conditions and play a major role in the establishment and pathogenesis of many diseases. Considering this, accurate detection and quantification of MPs is very important in clinical diagnostics and therapeutics. A combination of bulk solution electrokinetic sorting and interfacial impedance responses allows achieving detection limits as low as several MPs per μL. By fitting resulting EIS spectra with an equivalent electrical circuit, the bulk solution electrokinetic and interfacial impedance responses were characterized. In the bulk solution two major relaxations were prominent-β-relaxation in low MHz region due to the MP capacitive membrane bridging, and α-relaxation at ∼10 kHz due to counter ions diffusion. At low frequencies (10-0.1 Hz) at electrochemical potentials exceeding -100 mV, a facile interfacial Faradaic process of oxidation in MPs coupled with diffusion and non-Faradaic double layer charging dominate, probably due to oxidation of phospholipids and/or proteins on the MP surface and MP lysis. Buffer influence on the MP detection demonstrated that a relatively low conductivity Tyrode's buffer background solution is preferential for the MP electrokinetic separation and characterization. This study also demonstrated that standard laboratory methods such as flow cytometry underestimate MP concentrations, especially those with smaller average sizes, by as much as a factor of 2-40. Copyright © 2010 Elsevier B.V. All rights reserved.

Recovering oil by injecting aqueous alkali, cosurfactant and gas

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

Reisberg, J.; Bielmowicz, L. J.; Thigpen, D. R.

1985-01-15

A process of recovering oil from a subterranean reservoir in which the oil is acidic but forms monovalent cation soaps of only relatively low interfacial activity when reacted with aqueous alkaline solutions, comprises displacing the oil toward a production location with a mixture of gas and cosurfactant-containing aqueous alkaline solution.

The Role of Interfaces in Polyethylene/Metal-Oxide Nanocomposites for Ultrahigh-Voltage Insulating Materials.

PubMed

Pourrahimi, Amir Masoud; Olsson, Richard T; Hedenqvist, Mikael S

2018-01-01

Recent progress in the development of polyethylene/metal-oxide nanocomposites for extruded high-voltage direct-current (HVDC) cables with ultrahigh electric insulation properties is presented. This is a promising technology with the potential of raising the upper voltage limit in today's underground/submarine cables, based on pristine polyethylene, to levels where the loss of energy during electric power transmission becomes low enough to ensure intercontinental electric power transmission. The development of HVDC insulating materials together with the impact of the interface between the particles and the polymer on the nanocomposites electric properties are shown. Important parameters from the atomic to the microlevel, such as interfacial chemistry, interfacial area, and degree of particle dispersion/aggregation, are discussed. This work is placed in perspective with important work by others, and suggested mechanisms for improved insulation using nanoparticles, such as increased charge trap density, adsorption of impurities/ions, and induced particle dipole moments are considered. The effects of the nanoparticles and of their interfacial structures on the mechanical properties and the implications of cavitation on the electric properties are also discussed. Although the main interest in improving the properties of insulating polymers has been on the use of nanoparticles, leading to nanodielectrics, it is pointed out here that larger microscopic hierarchical metal-oxide particles with high surface porosity also impart good insulation properties. The impact of the type of particle and its inherent properties (purity and conductivity) on the nanocomposite dielectric and insulating properties are also discussed based on data obtained by a newly developed technique to directly observe the charge distribution on a nanometer scale in the nanocomposite. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-healing gold mirrors and filters at liquid-liquid interfaces

NASA Astrophysics Data System (ADS)

Smirnov, Evgeny; Peljo, Pekka; Scanlon, Micheál D.; Gumy, Frederic; Girault, Hubert H.

2016-03-01

The optical and morphological properties of lustrous metal self-healing liquid-like nanofilms were systematically studied for different applications (e.g., optical mirrors or filters). These nanofilms were formed by a one-step self-assembly methodology of gold nanoparticles (AuNPs) at immiscible water-oil interfaces, previously reported by our group. We investigated a host of experimental variables and herein report their influence on the optical properties of nanofilms: AuNP mean diameter, interfacial AuNP surface coverage, nature of the organic solvent, and nature of the lipophilic organic molecule that caps the AuNPs in the interfacial nanofilm. To probe the interfacial gold nanofilms we used in situ (UV-vis-NIR spectroscopy and optical microscopy) as well as ex situ (SEM and TEM of interfacial gold nanofilms transferred to silicon substrates) techniques. The interfacial AuNP surface coverage strongly influenced the morphology of the interfacial nanofilms, and in turn their maximum reflectance and absorbance. We observed three distinct morphological regimes; (i) smooth 2D monolayers of ``floating islands'' of AuNPs at low surface coverages, (ii) a mixed 2D/3D regime with the beginnings of 3D nanostructures consisting of small piles of adsorbed AuNPs even under sub-full-monolayer conditions and, finally, (iii) a 3D regime characterised by the 2D full-monolayer being covered in significant piles of adsorbed AuNPs. A maximal value of reflectance reached 58% in comparison with a solid gold mirror, when 38 nm mean diameter AuNPs were used at a water-nitrobenzene interface. Meanwhile, interfacial gold nanofilms prepared with 12 nm mean diameter AuNPs exhibited the highest extinction intensities at ca. 690 nm and absorbance around 90% of the incident light, making them an attractive candidate for filtering applications. Furthermore, the interparticle spacing, and resulting interparticle plasmon coupling derived optical properties, varied significantly on replacing tetrathiafulvalene with neocuproine as the AuNP capping ligand in the nanofilm. These interfacial nanofilms formed with neocuproine and 38 nm mean diameter AuNPs, at monolayer surface coverages and above, were black due to aggregation and broadband absorbance.The optical and morphological properties of lustrous metal self-healing liquid-like nanofilms were systematically studied for different applications (e.g., optical mirrors or filters). These nanofilms were formed by a one-step self-assembly methodology of gold nanoparticles (AuNPs) at immiscible water-oil interfaces, previously reported by our group. We investigated a host of experimental variables and herein report their influence on the optical properties of nanofilms: AuNP mean diameter, interfacial AuNP surface coverage, nature of the organic solvent, and nature of the lipophilic organic molecule that caps the AuNPs in the interfacial nanofilm. To probe the interfacial gold nanofilms we used in situ (UV-vis-NIR spectroscopy and optical microscopy) as well as ex situ (SEM and TEM of interfacial gold nanofilms transferred to silicon substrates) techniques. The interfacial AuNP surface coverage strongly influenced the morphology of the interfacial nanofilms, and in turn their maximum reflectance and absorbance. We observed three distinct morphological regimes; (i) smooth 2D monolayers of ``floating islands'' of AuNPs at low surface coverages, (ii) a mixed 2D/3D regime with the beginnings of 3D nanostructures consisting of small piles of adsorbed AuNPs even under sub-full-monolayer conditions and, finally, (iii) a 3D regime characterised by the 2D full-monolayer being covered in significant piles of adsorbed AuNPs. A maximal value of reflectance reached 58% in comparison with a solid gold mirror, when 38 nm mean diameter AuNPs were used at a water-nitrobenzene interface. Meanwhile, interfacial gold nanofilms prepared with 12 nm mean diameter AuNPs exhibited the highest extinction intensities at ca. 690 nm and absorbance around 90% of the incident light, making them an attractive candidate for filtering applications. Furthermore, the interparticle spacing, and resulting interparticle plasmon coupling derived optical properties, varied significantly on replacing tetrathiafulvalene with neocuproine as the AuNP capping ligand in the nanofilm. These interfacial nanofilms formed with neocuproine and 38 nm mean diameter AuNPs, at monolayer surface coverages and above, were black due to aggregation and broadband absorbance. Electronic supplementary information (ESI) available: Interfacial tension measurements for various water-organic solvent systems, step-by-step optical microscopy and SEM characterization of the obtained film, optical photographs of all tested solvents and molecules, and influence of the interfacial tension on optical responses of AuNPs assemblies. See DOI: 10.1039/c6nr00371k

Determination of induction period and crystal growth mechanism of dexamethasone sodium phosphate in methanol-acetone system

NASA Astrophysics Data System (ADS)

Hao, Hongxun; Wang, Jingkang; Wang, Yongli

2005-02-01

The induction period of dexamethasone sodium phosphate at different supersaturation was experimentally determined in a methanol-acetone system. The laser monitoring observation technique was used to determine the appearance of the first nucleus in solution. The effect of solution composition on induction period was discussed. Based on classical homogeneous nucleation theory, the solid-liquid interfacial tension and surface entropy factor were calculated from the induction period data. The experimentally determined values of interfacial tension are in agreement with the theoretical values predicted by the Mersmann equation. It was found that the nucleus of dexamethasone sodium phosphate grows continuously in pure methanol and turns from continuous growth to birth and spread growth with increasing acetone content in a methanol-acetone mixture.

Elucidating the influence of polymorph-dependent interfacial solvent structuring at chitin surfaces.

PubMed

Brown, Aaron H; Walsh, Tiffany R

2016-10-20

Interfacial solvent structuring is thought to be influential in mediating the adsorption of biomolecules at aqueous materials interfaces. However, despite the enormous potential for exploitation of aqueous chitin interfaces in industrial, medical and drug-delivery applications, little is known at the molecular-level about such interfacial solvent structuring for chitin. Here we use molecular simulation to predict the structure of the [100] and [010] interfaces of α-chitin and β-chitin dihydrate in contact with liquid water and saline solution. We find the α-chitin [100] interface supports lateral high-density regions in the first water layer at the interface, which are also present, but not as pronounced, for β-chitin. The lateral structuring of interfacial ions at the saline/chitin interface is also more pronounced for α-chitin compared with β-chitin. Our findings provide a foundation for the systematic design of biomolecules with selective binding affinity for different chitin polymorphs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Computer modelling of the surface tension of the gas-liquid and liquid-liquid interface.

PubMed

Ghoufi, Aziz; Malfreyt, Patrice; Tildesley, Dominic J

2016-03-07

This review presents the state of the art in molecular simulations of interfacial systems and of the calculation of the surface tension from the underlying intermolecular potential. We provide a short account of different methodological factors (size-effects, truncation procedures, long-range corrections and potential models) that can affect the results of the simulations. Accurate calculations are presented for the calculation of the surface tension as a function of the temperature, pressure and composition by considering the planar gas-liquid interface of a range of molecular fluids. In particular, we consider the challenging problems of reproducing the interfacial tension of salt solutions as a function of the salt molality; the simulations of spherical interfaces including the calculation of the sign and size of the Tolman length for a spherical droplet; the use of coarse-grained models in the calculation of the interfacial tension of liquid-liquid surfaces and the mesoscopic simulations of oil-water-surfactant interfacial systems.

Effect of chemical treatment of Kevlar fibers on mechanical interfacial properties of composites.

PubMed

Park, Soo-Jin; Seo, Min-Kang; Ma, Tae-Jun; Lee, Douk-Rae

2002-08-01

In this work, the effects of chemical treatment on Kevlar 29 fibers have been studied in a composite system. The surface characteristics of Kevlar 29 fibers were characterized by pH, acid-base value, X-ray photoelectron spectroscopy (XPS), and FT-IR. The mechanical interfacial properties of the final composites were studied by interlaminar shear strength (ILSS), critical stress intensity factor (K(IC)), and specific fracture energy (G(IC)). Also, impact properties of the composites were investigated in the context of differentiating between initiation and propagation energies and ductile index (DI) along with maximum force and total energy. As a result, it was found that chemical treatment with phosphoric acid solution significantly affected the degree of adhesion at interfaces between fibers and resin matrix, resulting in improved mechanical interfacial strength in the composites. This was probably due to the presence of chemical polar groups on Kevlar surfaces, leading to an increment of interfacial binding force between fibers and matrix in a composite system.

Surface and interfacial chemistry of high-k dielectric and interconnect materials on silicon

NASA Astrophysics Data System (ADS)

Kirsch, Paul Daniel

Surfaces and interfaces play a critical role in the manufacture and function of silicon based integrated circuits. It is therefore reasonable to study the chemistries at these surfaces and interfaces to improve existing processes and to develop new ones. Model barium strontium titanate high-k dielectric systems have been deposited on ultrathin silicon oxynitride in ultrahigh vacuum. The resulting nanostructures are characterized with secondary ion mass spectroscopy (SIMS) and X-ray photoelectron spectroscopy (XPS). An interfacial reaction between Ba and Sr atoms and SiOxNy was found to create silicates, BaSixOy or SrSi xOy. Inclusion of N in the interfacial oxide decreased silicate formation in both Ba and Sr systems. Furthermore, inclusion of N in the interfacial oxide decreased the penetration of Ba and Sr containing species, such as silicides and silicates. Sputter deposited HfO2 was studied on nitrided and unnitrided Si(100) surfaces. XPS and SIMS were used to verify the presence of interfacial HfSixOy and estimate its relative amount on both nitrided and unnitrided samples. More HfSixOy formed without the SiNx interfacial layer. These interfacial chemistry results are then used to explain the electrical measurements obtained from metal oxide semiconductor (MOS) capacitors. MOS capacitors with interfacial SiNx exhibit reduced leakage current and increased capacitance. Lastly, surface science techniques were used to develop a processing technique for reducing thin films of copper (II) and copper (I) oxide to copper. Deuterium atoms (D*) and methyl radicals (CH3*) were shown to reduce Cu 2+ and/or Cu1+ to Cu0 within 30 min at a surface temperature of 400 K under a flux of 1 x 1015 atoms/cm2s. Temperature programmed desorption experiments suggest that oxygen leaves the surface as D2O and CO2 for the D* and CH3* treated surfaces, respectively.

Effect of ionization on the oxidation kinetics of aluminum nanoparticles

NASA Astrophysics Data System (ADS)

Zheng, Yao-Ting; He, Min; Cheng, Guang-xu; Zhang, Zaoxiao; Xuan, Fu-Zhen; Wang, Zhengdong

2018-03-01

Molecular dynamics simulation (MD) of the observed stepwise oxidation of core-shell structured Al/Al2O3 nanoparticles is presented. Different from the metal ion hopping process in the Cabrera-Mott model, which is assumed to occur only at a certain distance from the oxide layer, the MD simulation shows that Al atoms jump over various interfacial gaps directly under the thermal driving force. The energy barrier for Al ionization is found to be increased along with the enlargement of interfacial gap. A mechanism of competition between thermal driving force and ionization potential barrier is proposed in the interpretation of stepwise oxidation behavior.

Electrical Control of Magnetic Dynamics in Hybrid Metal-Semiconductor Systems

DTIC Science & Technology

2014-07-25

abandoning perfection for quantum technologies”, Munich Center for NanoScience Workshop on Nanosciences: Great Adventures on Small Scales, Venice ...International University, Venice , Italy, September 16-20, 2013. 20. R. A. Buhrman, “Spin Hall effects, spin torque and interfacial spin-orbit phenomena in

Nonreciprocal Surface Acoustic Waves in Multilayers with Magnetoelastic and Interfacial Dzyaloshinskii-Moriya Interactions

NASA Astrophysics Data System (ADS)

Verba, Roman; Lisenkov, Ivan; Krivorotov, Ilya; Tiberkevich, Vasil; Slavin, Andrei

2018-06-01

Surface acoustic waves (SAWs) propagating in a piezoelectric substrate covered with a thin ferromagnetic-heavy-metal bilayer are found to exhibit a substantial degree of nonreciprocity, i.e., the frequencies of these waves are nondegenerate with respect to the inversion of the SAW propagation direction. The simultaneous action of the magnetoelastic interaction in the ferromagnetic layer and the interfacial Dzyaloshinskii-Moriya interaction in the ferromagnetic-heavy-metal interface results in the openings of magnetoelastic band gaps in the SAW spectrum, and the frequency position of these band gaps is different for opposite SAW propagation directions. The band-gap widths and the frequency separation between them can be controlled by a proper selection of the magnetization angle and the thickness of the ferromagnetic layer. Using numerical simulations, we demonstrate that the isolation between SAWs propagating in opposite directions in such a system can exceed the direct SAW propagation losses by more than 1 order of magnitude.

Induced Ferromagnetism at BiFeO 3/YBa 2Cu 3O 7 Interfaces

DOE PAGES

Zhu, Jian-Xin; Wen, Xiao-Dong; Haraldsen, J. T.; ...

2014-06-20

We report that transition metal oxides (TMOs) exhibit many emergent phenomena ranging from high-temperature superconductivity and giant magnetoresistance to magnetism and ferroelectricity. In addition, when TMOs are interfaced with each other, new functionalities can arise, which are absent in individual components. Here, we report results from first-principles calculations on the magnetism at the BiFeO 3/YBa 2Cu 3O 7 interfaces. By comparing the total energy for various magnetic spin configurations inside BiFeO 3, we are able to show that a metallic ferromagnetism is induced near the interface. We further develop an interface exchange-coupling model and place the extracted exchange coupling interactionmore » strengths, from the first-principles calculations, into a resultant generic phase diagram. Our conclusion of interfacial ferromagnetism is confirmed by the presence of a hysteresis loop in field-dependent magnetization data. Lastly, the emergence of interfacial ferromagnetism should have implications to electronic and transport properties.« less

The electrical and interfacial properties of metal-high-k oxide-semiconductor field effect transistors with CeO2/HfO2 laminated gate dielectrics

NASA Astrophysics Data System (ADS)

Chang, Ingram Yin-ku; Chen, Chun-Heng; Chiu, Fu-Chien; Lee, Joseph Ya-min

2007-11-01

Metal-oxide-semiconductor field-effect transistors with CeO2/HfO2 laminated gate dielectrics were fabricated. The transistors have a subthreshold slope of 74.9mV/decade. The interfacial properties were measured using gated diodes. The surface state density Dit was 9.78×1011cm-2eV-1. The surface-recombination velocity (s0) and the minority carrier lifetime in the field-induced depletion region (τ0,FIJ) measured from the gated diode were about 6.11×103cm /s and 1.8×10-8s, respectively. The effective capture cross section of surface state (σs) extracted using the subthreshold-swing measurement and the gated diode was about 7.69×10-15cm2. The effective electron mobility of CeO2/HfO2 laminated gated transistors was determined to be 212cm2/Vs.

Surface and interfacial engineering of iron oxide nanoplates for highly efficient magnetic resonance angiography.

PubMed

Zhou, Zijian; Wu, Changqiang; Liu, Hanyu; Zhu, Xianglong; Zhao, Zhenghuan; Wang, Lirong; Xu, Ye; Ai, Hua; Gao, Jinhao

2015-03-24

Magnetic resonance angiography using gadolinium-based molecular contrast agents suffers from short diagnostic window, relatively low resolution and risk of toxicity. Taking into account the chemical exchange between metal centers and surrounding protons, magnetic nanoparticles with suitable surface and interfacial features may serve as alternative T1 contrast agents. Herein, we report the engineering on surface structure of iron oxide nanoplates to boost T1 contrast ability through synergistic effects between exposed metal-rich Fe3O4(100) facets and embedded Gd2O3 clusters. The nanoplates show prominent T1 contrast in a wide range of magnetic fields with an ultrahigh r1 value up to 61.5 mM(-1) s(-1). Moreover, engineering on nanobio interface through zwitterionic molecules adjusts the in vivo behaviors of nanoplates for highly efficient magnetic resonance angiography with steady-state acquisition window, superhigh resolution in vascular details, and low toxicity. This study provides a powerful tool for sophisticated design of MRI contrast agents for diverse use in bioimaging applications.

Extrinsic and Intrinsic Frequency Dispersion of High-k Materials in Capacitance-Voltage Measurements

PubMed Central

Tao, J.; Zhao, C.Z.; Zhao, C.; Taechakumput, P.; Werner, M.; Taylor, S.; Chalker, P. R.

2012-01-01

In capacitance-voltage (C-V) measurements, frequency dispersion in high-k dielectrics is often observed. The frequency dependence of the dielectric constant (k-value), that is the intrinsic frequency dispersion, could not be assessed before suppressing the effects of extrinsic frequency dispersion, such as the effects of the lossy interfacial layer (between the high-k thin film and silicon substrate) and the parasitic effects. The effect of the lossy interfacial layer on frequency dispersion was investigated and modeled based on a dual frequency technique. The significance of parasitic effects (including series resistance and the back metal contact of the metal-oxide-semiconductor (MOS) capacitor) on frequency dispersion was also studied. The effect of surface roughness on frequency dispersion is also discussed. After taking extrinsic frequency dispersion into account, the relaxation behavior can be modeled using the Curie-von Schweidler (CS) law, the Kohlrausch-Williams-Watts (KWW) relationship and the Havriliak-Negami (HN) relationship. Dielectric relaxation mechanisms are also discussed. PMID:28817021

Effects of Transition Metals on the Grain Boundary Cohesion in Tungsten

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

Setyawan, Wahyu; Kurtz, Richard J.

2012-04-01

We report on the effects of alloying transition metals on the interfacial cohesion of W {Sigma}27<110>{l_brace}525{r_brace} symmetrical tilt grain boundary (GB). Density-functional-theory calculations show that the effects are related to the sensitivity of the d-orbital's occupation with respect to the atomic environments at the GB. Systematic trends of cleavage energy as a function of the electronic valence of the impurities were observed across different interfacial positions. Segregation formation energies were calculated to study the stability of the substitutional sites. All of the energetically preferred sites also correspond to the positions at which the alloying elements increase the GB cleavage energy.more » For each element, the more stable the configuration, the higher the cleavage energy. This finding is crucial in designing polycrystalline W-alloys with improved fracture toughness. Considering the solubility limit, the results suggest that Ta, Nb, Re, Ru, and Os are potential additives against intergranular fracture.« less

Interfacial Dzyaloshinskii-Moriya Interaction: Effect of 5 d Band Filling and Correlation with Spin Mixing Conductance

NASA Astrophysics Data System (ADS)

Ma, Xin; Yu, Guoqiang; Tang, Chi; Li, Xiang; He, Congli; Shi, Jing; Wang, Kang L.; Li, Xiaoqin

2018-04-01

The Dzyaloshinskii-Moriya interaction (DMI) at the heavy metal (HM) and ferromagnetic metal (FM) interface has been recognized as a key ingredient in spintronic applications. Here we investigate the chemical trend of DMI on the 5 d band filling (5 d3- 5 d10 ) of the HM element in HM/FM (FM =CoFeB ,Co )/MgO multilayer thin films. DMI is quantitatively evaluated by measuring asymmetric spin wave dispersion using Brillouin light scattering. Sign reversal and 20 times modification of the DMI coefficient D have been measured as the 5 d HM element is varied. The chemical trend can be qualitatively understood by considering the 5 d and 3 d bands alignment at the HM/FM interface and the subsequent orbital hybridization around the Fermi level. Furthermore, a correlation is observed between DMI and effective spin mixing conductance at the HM/FM interfaces. Our results provide new insights into the interfacial DMI for designing future spintronic devices.

Unravelling surface and interfacial structures of a metal-organic framework by transmission electron microscopy.

PubMed

Zhu, Yihan; Ciston, Jim; Zheng, Bin; Miao, Xiaohe; Czarnik, Cory; Pan, Yichang; Sougrat, Rachid; Lai, Zhiping; Hsiung, Chia-En; Yao, Kexin; Pinnau, Ingo; Pan, Ming; Han, Yu

2017-05-01

Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

Unravelling surface and interfacial structures of a metal-organic framework by transmission electron microscopy

NASA Astrophysics Data System (ADS)

Zhu, Yihan; Ciston, Jim; Zheng, Bin; Miao, Xiaohe; Czarnik, Cory; Pan, Yichang; Sougrat, Rachid; Lai, Zhiping; Hsiung, Chia-En; Yao, Kexin; Pinnau, Ingo; Pan, Ming; Han, Yu

2017-05-01

Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules.

Modulate Organic-Metal Oxide Heterojunction via [1,6] Azafulleroid for Highly Efficient Organic Solar Cells.

PubMed

Li, Chang-Zhi; Huang, Jiang; Ju, Huanxin; Zang, Yue; Zhang, Jianyuan; Zhu, Junfa; Chen, Hongzheng; Jen, Alex K-Y

2016-09-01

By creating an effective π-orbital hybridization between the fullerene cage and the aromatic anchor (addend), the azafulleroid interfacial modifiers exhibit enhanced electronic coupling to the underneath metal oxides. High power conversion efficiency of 10.3% can be achieved in organic solar cells using open-cage phenyl C61 butyric acid methyl ester (PCBM)-modified zinc oxide layer. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rupture dynamics along bimaterial interfaces: a parametric study of the coupling between interfacial sliding and normal traction perturbation

NASA Astrophysics Data System (ADS)

Scala, Antonio; Festa, Gaetano; Vilotte, Jean-Pierre

2017-04-01

Earthquake ruptures often develop along faults separating materials with dissimilar elastic properties. Due to the broken symmetry, the propagation of the rupture along the bimaterial interface is driven by the coupling between interfacial sliding and normal traction perturbations. We numerically investigate in-plane rupture growth along a planar interface, under slip weakening friction, separating two dissimilar isotropic linearly elastic half-spaces. We perform a parametric study of the classical Prakash-Clifton regularisation for different material contrasts. In particular mesh-dependence and regularisation-dependence of the numerical solutions are analysed in this parameter space. When regularisation involves a slip-rate dependent relaxation time, a characteristic sliding distance is identified below which numerical solutions no longer depend on the regularisation parameter, i.e. they are consistent solutions of the same physical problem. Such regularisation provides an adaptive high-frequency filter of the slip-induced normal traction perturbations, following the dynamic shrinking of the dissipation zone during the acceleration phase. In contrast, regularisation involving a constant relaxation time leads to numerical solutions that always depend on the regularisation parameter since it fails adapting to the shrinking of the process zone. Dynamic regularisation is further investigated using a non-local regularisation based on a relaxation time that depends on the dynamic length of the dissipation zone. Such reformulation is shown to provide similar results as the dynamic time scale regularisation proposed by Prakash-Clifton when slip rate is replaced by the maximum slip rate along the sliding interface. This leads to the identification of a dissipative length scale associated with the coupling between interfacial sliding and normal traction perturbations, together with a scaling law between the maximum slip rate and the dynamic size of the process zone during the rupture propagation. Dynamic time scale regularisation is show to provide mesh-independent and physically well-posed numerical solutions during the acceleration phase toward an asymptotic speed. When generalised Rayleigh wave does not exist, numerical solutions are shown to tend toward an asymptotic velocity higher than the slowest shear wave speed. When generalised Rayleigh wave speed exists, as numerical solutions tend toward this velocity, increasing spurious oscillations develop and solutions become unstable. In this regime regularisation dependent and unstable finite-size pulses may be generated. This instability is associated with the singular behaviour of the slip-induced normal traction perturbations, and of the slip rate at the rupture front, in relation with complete shrinking of the dissipation zone. This phase requires to be modelled either by more complex interface constitutive laws involving velocity-strengthening effects that may stabilize short wavelength interfacial propagating modes or by considering non-ideal interfaces that introduce a new length scale in the problem that may promote selection and stabilization of the slip pulses.

Orientation-dependent hydration structures at yttria-stabilized cubic zirconia surfaces

DOE PAGES

Hou, Binyang; Kim, Seunghyun; Kim, Taeho; ...

2016-11-30

Water interaction with surfaces is very important and plays key roles in many natural and technological processes. Because the experimental challenges that arise when studying the interaction water with specific crystalline surfaces, most studies on metal oxides have focused on powder samples, which averaged the interaction over different crystalline surfaces. As a result, studies on the crystal orientation-dependent interaction of water with metal oxides are rarely available in the literature. In this work, water adsorption at 8 mol % yttria-stabilized cubic single crystal zirconia (100) and (111) surfaces was studied in terms of interfacial hydration structures using high resolution X-raymore » reflectivity measurements. The interfacial electron density profiles derived from the structure factor analysis of the measured data show the existence of multiple layers of adsorbed water with additional peculiar metal adsorption near the oxide surfaces.Surface relaxation, depletion, and interaction between the adsorbed layers and bulk water are found to vary greatly between the two surfaces and are also different when compared to the previously studied (110) surface. The fractional ratio between chemisorbed and physisorbed water species were also quantitatively estimated, which turned out to vary dramatically from surface to surface. Finally, the result gives us a unique opportunity to reconsider the simplified 2:1 relation between chemisorption and physisorption, originally proposed by Morimoto et al. based on the adsorption isotherms of water on powder metal oxide samples.« less

Understanding the adsorption of CuPc and ZnPc on noble metal surfaces by combining quantum-mechanical modelling and photoelectron spectroscopy.

PubMed

Huang, Yu Li; Wruss, Elisabeth; Egger, David A; Kera, Satoshi; Ueno, Nobuo; Saidi, Wissam A; Bucko, Tomas; Wee, Andrew T S; Zojer, Egbert

2014-03-07

Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc) and Zn-phthalocyanine (ZnPc) on Au(111) and Ag(111) surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW) interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111) are exclusively due to Pauli pushback. On Ag(111), we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS) experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states.

Development of bubble microstructure in ErT2 films during aging

NASA Astrophysics Data System (ADS)

Bond, Gillian M.; Browning, James F.; Snow, Clark S.

2010-04-01

Helium bubbles form in metal tritide films as tritium decays into H3e, influencing mechanical properties and long-term film stability. The bubble nucleation and growth mechanisms comprise an active research area, but there has been only one previous systematic experimental study of helium bubble growth in metal tritides, on zirconium tritides. There have been no such studies on tritides such as ErT2 that form platelike bubbles and lack a secondary bubble population on a network of line dislocations, and yet such a study is needed to inform the modeling of helium bubble microstructure development in a broader range of metal tritides. Transmission electron microscopy has been used to study the growth and evolution of helium bubbles in ErT2 films over a four-year period. The results have been used to test the present models of helium bubble nucleation and growth in metal tritides, particularly those forming platelike bubbles. The results support the models of Trinkaus and Cowgill. The observations of nonuniform bubble thicknesses and the pattern of grain-boundary bubble formation, however, indicate that these models could be strengthened by closer attention to details of interfacial energy. It is strongly recommended that efforts be made (either experimentally or by calculation) to determine anisotropy of tritide/helium interfacial energy, both for clean, stoichiometric interfaces, and also allowing for such factors as nonstoichiometry and segregation.

X-ray photoelectron spectroscopy and friction studies of nickel-zinc and manganese-zinc ferrites in contact with metals

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

X-ray photoelectron spectroscopy analysis and sliding friction experiments were conducted with hot-pressed, polycrystalline Ni-Zn and Mn-Zn ferrites in sliding contact with various transition metals at room temperature in a vacuum of 30 nPa. The results indicate that the coefficients of friction for Ni-Zn and Mn-Zn ferrites in contact with metals are related to the relative chemical activity in these metals: the more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites correlate with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite surfaces increases the coefficients of friction for the Ni-Zn and Mn-Zn ferrite-metal interfaces.

Effect of demulsifiers on interfacial properties governing crude oil demulsification

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

Mukherjee, S.; Kushnick, A.P.

1988-05-01

Crude oil is almost always produced as persistent water-in-oil emulsions which must be resolved into two separate phases before the crude can be accepted for pipelining. The water droplets are sterically stabilized by the asphaltene and resin fractions of the crude oil. These are condensed aromatic rings containing saturated carbon chains and napthenic rings as substituents, along with a distribution of heteroatoms and metals. They are capable of crosslinking at the water drop-oil interface. Chemical demulsifiers are most commonly used to separate the emulsions into water and oil phases. The demulsifiers are moderate (2,000-50,000) molecular weight polydisperse mostly nonionic blockmore » copolymers with hydrophilic and hydrophobic segments. An example (Figure 1) of the most commonly used demulsifier is the oxyalkylated alkyl phenol formaldehyde resin. The alkyl group can be butyl, amyl, or nonyl and the interfacial activity is controlled by the relative amounts of ethylene oxide (EO) and propylene oxide (PO) attached to the polar end. The purpose of this paper is to illustrate how various parameters such as interfacial tension, interfacial shear viscosity, dynamic interfacial tension gradient, dilational elasticity and demulsifier clustering affect the demulsification effectiveness. To this end, the authors have studied both crude oil as well as asphaltene stabilized ''model' water-in-oil emulsions. In this paper, some of the results of the authors' study are presented.« less