Bonded ultrasonic transducer and method for making

DOEpatents

Dixon, R.D.; Roe, L.H.; Migliori, A.

1995-11-14

An ultrasonic transducer is formed as a diffusion bonded assembly of piezoelectric crystal, backing material, and, optionally, a ceramic wear surface. The mating surfaces of each component are silver films that are diffusion bonded together under the application of pressure and heat. Each mating surface may also be coated with a reactive metal, such as hafnium, to increase the adhesion of the silver films to the component surfaces. Only thin silver films are deposited, e.g., a thickness of about 0.00635 mm, to form a substantially non-compliant bond between surfaces. The resulting transducer assembly is substantially free of self-resonances over normal operating ranges for taking resonant ultrasound measurements. 12 figs.

Cleanliness evaluation of rough surfaces with diffuse IR reflectance

NASA Technical Reports Server (NTRS)

Pearson, L. H.

1995-01-01

Contamination on bonding surfaces has been determined to be a primary cause for degraded bond strength in certain solid rocket motor bondlines. Hydrocarbon and silicone based organic contaminants that are airborne or directly introduced to a surface are a significant source of contamination. Diffuse infrared (IR) reflectance has historically been used as an effective technique for detection of organic contaminants, however, common laboratory methods involving the use of a Fourier transform IR spectrometer (FTIR) are impractical for inspecting the large bonding surface areas found on solid rocket motors. Optical methods involving the use of acousto-optic tunable filters and fixed bandpass optical filters are recommended for increased data acquisition speed. Testing and signal analysis methods are presented which provide for simultaneous measurement of contamination concentration and roughness level on rough metal surfaces contaminated with hydrocarbons.

Joining of Silicon Carbide Through the Diffusion Bonding Approach

NASA Technical Reports Server (NTRS)

Halbig, Michael .; Singh, Mrityunjay

2009-01-01

In order for ceramics to be fully utilized as components for high-temperature and structural applications, joining and integration methods are needed. Such methods will allow for the fabrication the complex shapes and also allow for insertion of the ceramic component into a system that may have different adjacent materials. Monolithic silicon carbide (SiC) is a ceramic material of focus due to its high temperature strength and stability. Titanium foils were used as an interlayer to form diffusion bonds between chemical vapor deposited (CVD) SiC ceramics with the aid of hot pressing. The influence of such variables as interlayer thickness and processing time were investigated to see which conditions contributed to bonds that were well adhered and crack free. Optical microscopy, scanning electron microscopy, and electron microprobe analysis were used to characterize the bonds and to identify the reaction formed phases.

Random walks on cubic lattices with bond disorder

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

Ernst, M.H.; van Velthoven, P.F.J.

1986-12-01

The authors consider diffusive systems with static disorder, such as Lorentz gases, lattice percolation, ants in a labyrinth, termite problems, random resistor networks, etc. In the case of diluted randomness the authors can apply the methods of kinetic theory to obtain systematic expansions of dc and ac transport properties in powers of the impurity concentration c. The method is applied to a hopping model on a d-dimensional cubic lattice having two types of bonds with conductivity sigma and sigma/sub 0/ = 1, with concentrations c and 1-c, respectively. For the square lattice the authors explicitly calculate the diffusion coefficient D(c,sigma)more » as a function of c, to O(c/sup 2/) terms included for different ratios of the bond conductivity sigma. The probability of return at long times is given by P/sub 0/(t) approx. (4..pi..D(c,sigma)t)/sup -d/2/, which is determined by the diffusion coefficient of the disordered system.« less

Joining of materials using laser heating

DOEpatents

Cockeram, Brian V.; Hicks, Trevor G.; Schmid, Glenn C.

2003-07-01

A method for diffusion bonding ceramic layers such as boron carbide, zirconium carbide, or silicon carbide uses a defocused laser beam to heat and to join ceramics with the use of a thin metal foil insert. The metal foil preferably is rhenium, molybdenum or titanium. The rapid, intense heating of the ceramic/metal/ceramic sandwiches using the defocused laser beam results in diffusive conversion of the refractory metal foil into the ceramic and in turn creates a strong bond therein.

Molecular dynamics investigation of dynamical properties of phosphatidylethanolamine lipid bilayers

NASA Astrophysics Data System (ADS)

Pitman, Michael C.; Suits, Frank; Gawrisch, Klaus; Feller, Scott E.

2005-06-01

We describe the dynamic behavior of a 1-stearoyl-2-oleoyl-phosphatidylethanolamine (SOPE) bilayer from a 20ns molecular dynamics simulation. The dynamics of individual molecules are characterized in terms of H2 spin-lattice relaxation rates, nuclear overhauser enhancement spectroscopy (NOESY) cross-relaxation rates, and lateral diffusion coefficients. Additionally, we describe the dynamics of hydrogen bonding through an analysis of hydrogen bond lifetimes and the time evolution of clusters of hydrogen bonded lipids. The simulated trajectory is shown to be consistent with experimental measures of internal, intermolecular, and diffusive motion. Consistent with our analysis of SOPE structure in the companion paper, we see hydrogen bonding dominating the dynamics of the interface region. Comparison of H2 T1 relaxation rates for chain methylene segments in phosphatidylcholine and phosphatidylethanolamine bilayers indicates that slower motion resulting from hydrogen bonding extends at least three carbons into the hydrophobic core. NOESY cross-relaxation rates compare well with experimental values, indicating the observed hydrogen bonding dynamics are realistic. Calculated lateral diffusion rates (4±1×10-8cm2/s) are comparable, though somewhat lower than, those determined by pulsed field gradient NMR methods.

Irradiation resistance of silicon carbide joint at light water reactor–relevant temperature

DOE PAGES

Koyanagi, T.; Katoh, Y.; Kiggans, J. O.; ...

2017-03-10

We fabricated and irradiated monolithic silicon carbide (SiC) to SiC plate joints with neutrons at 270–310 °C to 8.7 dpa for SiC. The joining methods included solid state diffusion bonding using titanium and molybdenum interlayers, SiC nanopowder sintering, reaction sintering with a Ti-Si-C system, and hybrid processing of polymer pyrolysis and chemical vapor infiltration (CVI). All the irradiated joints exhibited apparent shear strength of more than 84 MPa on average. Significant irradiation-induced cracking was found in the bonding layers of the Ti and Mo diffusion bonds and Ti-Si-C reaction sintered bond. Furthermore, the SiC-based bonding layers of the SiC nanopowdermore » sintered and hybrid polymer pyrolysis and CVI joints all showed stable microstructure following the irradiation.« less

Preparation and Testing of Corrosion and Spallation-Resistant Coatings

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

Hurley, John

2015-11-01

This Energy & Environmental Research Center (EERC) project is designed to determine if plating APMT®, a specific highly oxidation-resistant oxide dispersion-strengthened FeCrAl alloy made by Kanthal, onto nickel-based superalloy turbine parts is a viable method for substantially improving the lifetimes and maximum use temperatures of the parts. The method for joining the APMT plate to the superalloys is called evaporative metal bonding and involves placing a thin foil of zinc between the plate and the superalloy, clamping them together, and heating in an atmosphere-controlled furnace. Upon heating, the zinc melts and dissolves the oxide skins of the alloys at themore » bond line, allowing the two alloys to diffuse into each other. The zinc then diffuses through the alloys and evaporates from their surfaces. During this annual reporting period, the finite element model was completed and used to design clamping jigs to hold the APMT plate to the larger blocks of superalloys during the bonding process. The clamping system was machined from titanium–zirconium–molybdenum and used to bond the APMT plate to the superalloy blocks. The bond between the APMT plate was weak for one of each of the superalloy blocks. We believe that this occurred because enough oxidation had occurred on the surface of the parts as a result of a 1-month time period between sandblasting to prepare the parts and the actual bonding process. The other blocks were, therefore, bonded within 1 day of preparing the parts for bonding, and their joints appear strong. Scanning electron microscopy analyses of representative joints showed that no zinc remained in the alloys after bonding. Also, phases rich in hafnium and tantalum had precipitated near the bond line in the APMT. Iron from the APMT had diffused into the superalloys during bonding, more extensively in the CM247LC than in the Rene 80. Nickel from the superalloys had diffused into the APMT, again more extensively in the joint with the CM247LC than with the Rene 80. One-inch-diameter buttons were machined from each of the bonded blocks and sent to Siemens for standard oxidation, spallation, and corrosion testing, which should be complete in the spring of 2016.« less

Diffusion bonding

DOEpatents

Anderson, Robert C.

1976-06-22

1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

Ceramic-to-metal bonding for pressure transducers

NASA Technical Reports Server (NTRS)

Mackenzie, J. D.

1984-01-01

A solid-state diffusion technique involving the placement of a gold foil between INCONEL X-750 and a machinable glass-ceramic "MACOR" was shown to be successful in bonding these two materials. This technique was selected after an exhaustive literature search on ceramic-metal bonding methods. Small expansion mismatch between the Inconel and the MACOR resulted in fracture of the MACOR when the bonded body was subjected to tensile stress of 535 psi. The bonded parts were submitted to a cyclic loading test in an air atmosphere at 1 Hz from 0 to 60 KPa. Failure was observed after 700,000 cycles at 650 C. Ceramic-Inconel bonding was not achieved with this method for boron nitride and silica glass.

Bond-selective photoacoustic imaging by converting molecular vibration into acoustic waves

PubMed Central

Hui, Jie; Li, Rui; Phillips, Evan H.; Goergen, Craig J.; Sturek, Michael; Cheng, Ji-Xin

2016-01-01

The quantized vibration of chemical bonds provides a way of detecting specific molecules in a complex tissue environment. Unlike pure optical methods, for which imaging depth is limited to a few hundred micrometers by significant optical scattering, photoacoustic detection of vibrational absorption breaks through the optical diffusion limit by taking advantage of diffused photons and weak acoustic scattering. Key features of this method include both high scalability of imaging depth from a few millimeters to a few centimeters and chemical bond selectivity as a novel contrast mechanism for photoacoustic imaging. Its biomedical applications spans detection of white matter loss and regeneration, assessment of breast tumor margins, and diagnosis of vulnerable atherosclerotic plaques. This review provides an overview of the recent advances made in vibration-based photoacoustic imaging and various biomedical applications enabled by this new technology. PMID:27069873

[A study on the bond interface between low-fusing dental porcelain and pure titanium].

PubMed

Mo, A; Cen, Y; Liao, Y; Wang, J; Shi, X

2001-09-01

To evaluate the bond interface between low fusing dental porcelain and pure titanium by observing the topography and detecting the ionic diffusion in the interface area. The low fusing-porcelain La-porcelain produced by the authors or Vita Titankeramik porcelain was fused to the surfaces of pure titanium. The topography of the interface between pure titanium and porcelain, and the structure of experimental materials were observed with SEM. The state of ionic diffusion in the interface area was investigated with EPMA. Excellent permeation and diffusion of La-porcelain were observed on the surfaces of pure titanium. The diffusion of ions of stannum and silicon was discovered in the interface area. The microstructure of La-porcelain to pure titanium bond interface was finer than that of Vita Titankeramik porcelain. Excellent bond can be produced in the interface between La-porcelain and pure titanium. The bonding mechanism may involve mechanical bond and chemical bond. The ionic diffusion of stannum plays an important role in the bonding of porcelain to pure titanium.

Interface bonding of SA508-3 steel under deformation and high temperature diffusion

NASA Astrophysics Data System (ADS)

Xu, Bin; Shao, Chunjuan; Sun, Mingyue

2018-05-01

There are mainly two parameters affecting high temperature interface bonding: deformation and diffusion. To study these two parameters, interface bonding of SA508-3 bainitic steel at 1100°C are simulated by gleeble3500 thermal simulator. The results show that interface of SA508-3 steel can be bonded under deformation and high temperature. For a specimen pressed at 1100°C without further high temperature diffusion, a reduction ratio of 30% can make the interface begun to bond, but the interface is still part of the grain boundary and small grains exist near the interface. When reduction ratio reaches 50%, the interface can be completely bonded and the microstructure near the interface is the same as that of the base material. When deformation is small, long time diffusion can also help the interface bonding. The results show that when the diffusion time is long enough, the interface under small deformation can also be bonded. For a specimen holding for 24h at 1100°C, only 13% reduction ratio is enough for interface bonding.

Diffusional interaction behavior of NSAIDs in lipid bilayer membrane using molecular dynamics (MD) simulation: Aspirin and Ibuprofen.

PubMed

Sodeifian, Gholamhossein; Razmimanesh, Fariba

2018-05-10

In this research, for the first time, molecular dynamics (MD) method was used to simulate aspirin and ibuprofen at various concentrations and in neutral and charged states. Effects of the concentration (dosage), charge state, and existence of an integral protein in the membrane on the diffusion rate of drug molecules into lipid bilayer membrane were investigated on 11 systems, for which the parameters indicating diffusion rate and those affecting the rate were evaluated. Considering the diffusion rate, a suitable score was assigned to each system, based on which, analysis of variance (ANOVA) was performed. By calculating the effect size of the indicative parameters and total scores, an optimum system with the highest diffusion rate was determined. Consequently, diffusion rate controlling parameters were obtained: the drug-water hydrogen bond in protein-free systems and protein-drug hydrogen bond in the systems containing protein.

Dynamics behavior of lithium in graphite lattice: MD calculation approach

NASA Astrophysics Data System (ADS)

Shimizu, A.; Tachikawa, H.

2000-12-01

In order to investigate the diffusion process of Li atom in graphite, molecular dynamics simulation was achieved on the basis of molecular mechanics 2 (MM2) method using four layers cluster model one of which is composed of C150H30 with terminating hydrogen atoms. According to the simulations at 500 K, Li atom stabilizes initially around the center of mass, gets out of the graphite layers after 3.0 ps through diffusion, which is different from the movement of Li+ ion captured by the dangling bonds of the edge carbon atoms. The diffusion process of Li atom is found to be composed of following four steps in series: (1) vibration around the stabilization point; (2) bulk diffusion; (3) vibration under influence of the dangling bonds of edge carbon atoms; and (4) escape from the graphite layers. The diffusivity for step (3) is smaller than that for step (2).

Targets for the production of radioisotopes and method of assembly

DOEpatents

Quinby, Thomas C.

1976-01-01

A target for preparation of radioisotopes by nuclear bombardment, and a method for its assembly are provided. A metallic sample to be bombarded is enclosed within a metallic support structure and the resulting target subjected to heat and pressure to effect diffusion bonds therebetween. The bonded target is capable of withstanding prolonged exposure to nuclear bombardment without thermal damage to the sample.

CVD aluminiding process for producing a modified platinum aluminide bond coat for improved high temperature performance

NASA Technical Reports Server (NTRS)

Nagaraj, Bangalore A. (Inventor); Williams, Jeffrey L. (Inventor)

2003-01-01

A method of depositing by chemical vapor deposition a modified platinum aluminide diffusion coating onto a superalloy substrate comprising the steps of applying a layer of a platinum group metal to the superalloy substrate; passing an externally generated aluminum halide gas through an internal gas generator which is integral with a retort, the internal gas generator generating a modified halide gas; and co-depositing aluminum and modifier onto the superalloy substrate. In one form, the modified halide gas is hafnium chloride and the modifier is hafnium with the modified platinum aluminum bond coat comprising a single phase additive layer of platinum aluminide with at least about 0.5 percent hafnium by weight percent and about 1 to about 15 weight percent of hafnium in the boundary between a diffusion layer and the additive layer. The bond coat produced by this method is also claimed.

Method of manufacturing lightweight thermo-barrier material

NASA Technical Reports Server (NTRS)

Blair, Winford (Inventor)

1987-01-01

A method of manufacturing thermal barrier structures comprising at least three dimpled cores separated by flat plate material with the outer surface of the flat plate material joined together by diffusion bonding.

Compact cladding-pumped planar waveguide amplifier and fabrication method

DOEpatents

Bayramian, Andy J.; Beach, Raymond J.; Honea, Eric; Murray, James E.; Payne, Stephen A.

2003-10-28

A low-cost, high performance cladding-pumped planar waveguide amplifier and fabrication method, for deployment in metro and access networks. The waveguide amplifier has a compact monolithic slab architecture preferably formed by first sandwich bonding an erbium-doped core glass slab between two cladding glass slabs to form a multi-layer planar construction, and then slicing the construction into multiple unit constructions. Using lithographic techniques, a silver stripe is deposited and formed at a top or bottom surface of each unit construction and over a cross section of the bonds. By heating the unit construction in an oven and applying an electric field, the silver stripe is then ion diffused to increase the refractive indices of the core and cladding regions, with the diffusion region of the core forming a single mode waveguide, and the silver diffusion cladding region forming a second larger waveguide amenable to cladding pumping with broad area diodes.

Diffusion Bonding of Silicon Carbide for MEMS-LDI Applications

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay; Shpargel, Tarah P.; Kiser, J. Douglas

2007-01-01

A robust joining approach is critically needed for a Micro-Electro-Mechanical Systems-Lean Direct Injector (MEMS-LDI) application which requires leak free joints with high temperature mechanical capability. Diffusion bonding is well suited for the MEMS-LDI application. Diffusion bonds were fabricated using titanium interlayers between silicon carbide substrates during hot pressing. The interlayers consisted of either alloyed titanium foil or physically vapor deposited (PVD) titanium coatings. Microscopy shows that well adhered, crack free diffusion bonds are formed under optimal conditions. Under less than optimal conditions, microcracks are present in the bond layer due to the formation of intermetallic phases. Electron microprobe analysis was used to identify the reaction formed phases in the diffusion bond. Various compatibility issues among the phases in the interlayer and substrate are discussed. Also, the effects of temperature, pressure, time, silicon carbide substrate type, and type of titanium interlayer and thickness on the microstructure and composition of joints are discussed.

Effect of the Microstructure on Diffusion Bonded AA5083, AA6082 and AA7075 Aluminium Alloys

NASA Astrophysics Data System (ADS)

Venugopal, S.; Mahendran, G.

2018-05-01

Rolled plates of aluminium alloys AA5083, AA6082 and AA7075 of 5 mm thickness are joined by diffusion bonding at varied parameters. The microstructure evolution of AA5083, AA6082 and AA7075 aluminium alloys is characterized by Transmission Electron Microscopy (TEM). Metallurgical investigations and mechanical tests are also performed to correlate the results of the TEM investigations with the mechanical properties of the produced diffusion bonded joints. It is observed that the bonding and shear strength of the alloys increase with the increase in bonding temperature, due to the diffusion of micro-constituents in the interface. High temperature enhances the uniform distribution of secondary phase particles and reduces pore formation/defects in the bonded joints.

TEM Analysis of Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

NASA Technical Reports Server (NTRS)

Ozaki, T.; Tsuda, H.; Halbig, M. C.; Singh, M.; Hasegawa, Y; Mori, S.; Asthana, R.

2017-01-01

Silicon Carbide (SiC) is a promising material for thermostructural applications due to its excellent high-temperature mechanical properties, oxidation resistance, and thermal stability. However, joining and integration technologies are indispensable for this material in order to fabricate large size and complex shape components with desired functionalities. Although diffusion bonding techniques using metallic interlayers have been commonly utilized to bond various SiC ceramics, detailed microstructural observation by Transmission Electron Microscopy (TEM) of the bonded area has not been carried out due to difficulty in preparing TEM samples. In this study, we tried to prepare TEM samples from joints of diffusion bonded SiC ceramics by Focused Ion Beam (FIB) system and carefully investigated the interfacial microstructure by TEM analysis. The samples used in this study were SiC fiber bonded ceramics (SA-Tyrannohex: SA-THX) diffusion bonded with metallic interlayers such as Ti, TiMo, Mo-B and TiCu. In this presentation, we report the microstructure of diffusion bonded SA-THX mainly with TiCu interlayers obtained by TEM observations, and the influence of metallic interlayers on the joint microstructure and microhardness will be discussed.

Welding and Joining of Titanium Aluminides

PubMed Central

Cao, Jian; Qi, Junlei; Song, Xiaoguo; Feng, Jicai

2014-01-01

Welding and joining of titanium aluminides is the key to making them more attractive in industrial fields. The purpose of this review is to provide a comprehensive overview of recent progress in welding and joining of titanium aluminides, as well as to introduce current research and application. The possible methods available for titanium aluminides involve brazing, diffusion bonding, fusion welding, friction welding and reactive joining. Of the numerous methods, solid-state diffusion bonding and vacuum brazing have been most heavily investigated for producing reliable joints. The current state of understanding and development of every welding and joining method for titanium aluminides is addressed respectively. The focus is on the fundamental understanding of microstructure characteristics and processing–microstructure–property relationships in the welding and joining of titanium aluminides to themselves and to other materials. PMID:28788113

Diffusion Bonding of Silicon Carbide Ceramics using Titanium Interlayers

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay; Shpargel, Tarah P.; Kiser, James D.

2006-01-01

Robust joining approaches for silicon carbide ceramics are critically needed to fabricate leak free joints with high temperature mechanical capability. In this study, titanium foils and physical vapor deposited (PVD) titanium coatings were used to form diffusion bonds between SiC ceramics using hot pressing. Silicon carbide substrate materials used for bonding include sintered SiC and two types of CVD SiC. Microscopy results show the formation of well adhered diffusion bonds. The bond strengths as determined from pull tests are on the order of several ksi, which is much higher than required for a proposed application. Microprobe results show the distribution of silicon, carbon, titanium, and other minor elements across the diffusion bond. Compositions of several phases formed in the joint region were identified. Potential issues of material compatibility and optimal bond formation will also be discussed.

Reliable aluminum contact formation by electrostatic bonding

NASA Astrophysics Data System (ADS)

Kárpáti, T.; Pap, A. E.; Radnóczi, Gy; Beke, B.; Bársony, I.; Fürjes, P.

2015-07-01

The paper presents a detailed study of a reliable method developed for aluminum fusion wafer bonding assisted by the electrostatic force evolving during the anodic bonding process. The IC-compatible procedure described allows the parallel formation of electrical and mechanical contacts, facilitating a reliable packaging of electromechanical systems with backside electrical contacts. This fusion bonding method supports the fabrication of complex microelectromechanical systems (MEMS) and micro-opto-electromechanical systems (MOEMS) structures with enhanced temperature stability, which is crucial in mechanical sensor applications such as pressure or force sensors. Due to the applied electrical potential of  -1000 V the Al metal layers are compressed by electrostatic force, and at the bonding temperature of 450 °C intermetallic diffusion causes aluminum ions to migrate between metal layers.

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

Samavatian, Majid, E-mail: m.samavatian@srbiau.ac.ir; Halvaee, Ayoub; Amadeh, Ahmad Ali

Joining mechanism of Ti/Al dissimilar alloys was studied during liquid state diffusion bonding process using Cu/Sn/Cu interlayer at 510 °C under vacuum of 7.5 × 10{sup −5} Torr for various bonding times. The microstructure and compositional changes in the joint zone were analyzed by scanning electron microscopy equipped with energy dispersive spectroscopy and X-ray diffraction. Microhardness and shear strength tests were also applied to study the mechanical properties of the joints. It was found that with an increase in bonding time, the elements of interlayer diffused into the parent metals and formed various intermetallic compounds at the interface. Diffusion processmore » led to the isothermal solidification and the bonding evolution in the joint zone. The results from mechanical tests showed that microhardness and shear strength values have a straight relation with bonding time so that the maximum shear strength of joint was obtained for a bond made with 60 min bonding time. - Highlights: • Liquid state diffusion bonding of Al2024 to Ti–6Al–4V was performed successfully. • Diffusion of the elements caused the formation of various intermetallics at the interface. • Microhardness and shear strength values have a straight relation with bonding time. • The maximum shear strength reached to 36 MPa in 60 min bonding time.« less

Fixed-Node Diffusion Quantum Monte Carlo Method on Dissociation Energies and Their Trends for R-X Bonds (R = Me, Et, i-Pr, t-Bu).

PubMed

Hou, Aiqiang; Zhou, Xiaojun; Wang, Ting; Wang, Fan

2018-05-15

Achieving both bond dissociation energies (BDEs) and their trends for the R-X bonds with R = Me, Et, i-Pr, and t-Bu reliably is nontrivial. Density functional theory (DFT) methods with traditional exchange-correlation functionals usually have large error on both the BDEs and their trends. The M06-2X functional gives rise to reliable BDEs, but the relative BDEs are determined not as accurately. More demanding approaches such as some double-hybrid functionals, for example, G4 and CCSD(T), are generally required to achieve the BDEs and their trends reliably. The fixed-node diffusion quantum Monte Carlo method (FN-DMC) is employed to calculated BDEs of these R-X bonds with X = H, CH 3 , OCH 3 , OH, and F in this work. The single Slater-Jastrow wave function is adopted as trial wave function, and pseudopotentials (PPs) developed for quantum Monte Carlo calculations are chosen. Error of these PPs is modest in wave function methods, while it is more pronounced in DFT calculations. Our results show that accuracy of BDEs with FN-DMC is similar to that of M06-2X and G4, and trends in BDEs are calculated more reliably than M06-2X. Both BDEs and trends in BDEs of these bonds are reproduced reasonably with FN-DMC. FN-DMC using PPs can thus be applied to BDEs and their trends of similar chemical bonds in larger molecules reliably and provide valuable information on properties of these molecules.

Investigation on the diffusion bonding of tungsten and EUROFER97

NASA Astrophysics Data System (ADS)

Basuki, Widodo Widjaja; Aktaa, Jarir

2011-10-01

Due to its advantages, tungsten is selected as armor and structural material for use in future fusion power plants. To apply tungsten as structural material, a joint to EUROFER97 is foreseen in current divertor design for which the diffusion bonding is considered in this work. The joining must have acceptable strength and ductility without significant change in microstructures. So far, numerous diffusion bonding experiments without and with post bonding heat treatment (PBHT) are performed at 1050 °C for various bonding duration. For the bonding processes without PBHT, the bonding seams obtained are defect free and have a very high tensile strength. However they are brittle due to a thin layer of FeW intermetallic phase and metal carbides. For the bonding processes with PBHT, the bonding specimens fail at the bonding seam.

Transition joints between Zircaloy-2 and stainless steel by diffusion bonding

NASA Astrophysics Data System (ADS)

Bhanumurthy, K.; Krishnan, J.; Kale, G. B.; Banerjee, S.

1994-11-01

The diffusion bonding between Zircaloy-2 and stainless steel (AISI 304L) using niobium, nickel and copper as intermediate layers has been investigated in the temperature range of 750 to 900°C. Bonding was carried out in a vacuum hot press, under compressive loading. Electron probe microanalysis and metallographic analysis showed a good metallurgical compatibility and also indicated the absence of discontunities, micropores and intermetallic compounds at various interfaces. The bond strength of the diffusion bonded assembly was found to be about 400 MPa for the couples bonded at 870°C for 2 h. The dimple structure on the fractured surface is indicative of the ductile mode of failure of the bonded assembly.

Diffusion bonding of IN 718 to VM 350 grade maraging steel

NASA Technical Reports Server (NTRS)

Crosby, S. R.; Biederman, R. R.; Reynolds, C. C.

1972-01-01

Diffusion bonding studies have been conducted on IN 718, VM 350 and the dissimilar alloy couple, IN 718 to maraging steel. The experimental processing parameters critical to obtaining consistently good diffusion bonds between IN 718 and VM 350 were determined. Interrelationships between temperature, pressure and surface preparation were explored for short bending intervals under vacuum conditions. Successful joining was achieved for a range of bonding cycle temperatures, pressures and surface preparations. The strength of the weaker parent material was used as a criterion for a successful tensile test of the heat treated bond. Studies of VM-350/VM-350 couples in the as-bonded condition showed a greater yielding and failure outside the bond region.

Understanding micro-diffusion bonding from the fabrication of B4C/Ni composites

NASA Astrophysics Data System (ADS)

Wang, Miao; Wang, Wen-xian; Chen, Hong-sheng; Li, Yu-li

2018-03-01

A Ni-B4C macroscopic diffusion welding couple and a Ni-15wt%B4C composite fabricated by spark plasma sintering (SPS) were used to understand the micro-scale diffusion bonding between metals and ceramics. In the Ni-B4C macroscopic diffusion welding couple a perfect diffusion welding joint was achieved. In the Ni-15wt%B4C sample, microstructure analyses demonstrated that loose structures occurred around the B4C particles. Energy dispersive X-ray spectroscopy analyses revealed that during the SPS process, the process of diffusion bonding between Ni and B4C particles can be divided into three stages. By employing a nano-indentation test, the room-temperature fracture toughness of the Ni matrix was found to be higher than that of the interface. The micro-diffusion bonding between Ni and B4C particles is quite different from the Ni-B4C reaction couple.

Modeling and experimental evaluation of the diffusion bonding of the oxide dispersion strengthened steel PM2000

NASA Astrophysics Data System (ADS)

Sittel, Wiebke; Basuki, Widodo W.; Aktaa, Jarir

2015-10-01

A modeling based optimization process of the solid state diffusion bonding is presented for joining ferritic oxide dispersion strengthened steels PM2000. An optimization study employing varying bonding temperatures and pressures results in almost the same strength and toughness of the bonded compared to the as received material. TEM investigations of diffusion bonded samples show a homogeneous distribution of oxide particles at the bonding seam similar to that in the bulk. Hence, no loss in strength or creep resistance due to oxide particle agglomeration is found, as verified by the mechanical properties observed for the joint.

TEM Analysis of Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

NASA Technical Reports Server (NTRS)

Ozaki, T.; Hasegawa, Y.; Tsuda, H.; Mori, S.; Halbig, M. C.; Asthana, R.; Singh, M.

2017-01-01

SiC fiber-bonded ceramics (SA-Tyrannohex: SA-THX) diffusion-bonded with TiCu metallic interlayers were investigated. Thin samples of the ceramics were prepared with a focused ion beam (FIB) and the interfacial microstructure of the prepared samples was studied by transmission electron microscopy (TEM) and scanning TEM (STEM). In addition to conventional microstructure observation, for detailed analysis of reaction compounds in diffusion-bonded area, we performed STEM-EDS measurements and selected area electron diffraction (SAD) experiments. The TEM and STEM experiments revealed the diffusion-bonded area was composed of only one reaction layer, which was characterized by TiC precipitates in Cu-Si compound matrix. This reaction layer was in good contact with the SA-THX substrates, and it is concluded that the joint structure led to the excellent bonding strength.

Metallic Thin-Film Bonding and Alloy Generation

NASA Technical Reports Server (NTRS)

Peotter, Brian S. (Inventor); Fryer, Jack Merrill (Inventor); Campbell, Geoff (Inventor); Droppers, Lloyd (Inventor)

2016-01-01

Diffusion bonding a stack of aluminum thin films is particularly challenging due to a stable aluminum oxide coating that rapidly forms on the aluminum thin films when they are exposed to atmosphere and the relatively low meting temperature of aluminum. By plating the individual aluminum thin films with a metal that does not rapidly form a stable oxide coating, the individual aluminum thin films may be readily diffusion bonded together using heat and pressure. The resulting diffusion bonded structure can be an alloy of choice through the use of a carefully selected base and plating metals. The aluminum thin films may also be etched with distinct patterns that form a microfluidic fluid flow path through the stack of aluminum thin films when diffusion bonded together.

Superplastic Forming/Diffusion Bonding Without Interlayer of 5A90 Al-Li Alloy Hollow Double-Layer Structure

NASA Astrophysics Data System (ADS)

Jiang, Shaosong; Jia, Yong; Lu, Zhen; Shi, Chengcheng; Zhang, Kaifeng

2017-09-01

The hollow double-layer structure of 5A90 Al-Li alloy was fabricated by SPF/DB process in this study. The characteristics and mechanism of 5A90 Al-Li alloy with respect to superplasticity and diffusion bonding were investigated. Tensile tests showed that the optimal elongation of tensile specimens was 243.97% at the temperature of 400 °C and the strain rate of 0.001 s-1. Effect of the surface roughness, bonding temperature and bonding time to determine the microstructure and mechanical properties of diffusion bonding joints was investigated, and the optimum bonding parameters were 540 °C/2.5 h/Ra18. Through the finite element simulation, it could be found that the SPF/DB process of hollow double-layer structure was feasible. The hollow double-layer structure of 5A90 Al-Li alloy was manufactured, showing that the thickness distribution of the bonding area was uniform and the thinnest part was the round corner. The SEM images of diffusion bonding joints showed that sound bonding interfaces were obtained in which no discontinuity existed.

Energy efficient engine shroudless, hollow fan blade technology report

NASA Technical Reports Server (NTRS)

Michael, C. J.

1981-01-01

The Shroudless, Hollow Fan Blade Technology program was structured to support the design, fabrication, and subsequent evaluation of advanced hollow and shroudless blades for the Energy Efficient Engine fan component. Rockwell International was initially selected to produce hollow airfoil specimens employing the superplastic forming/diffusion bonding (SPF/DB) fabrication technique. Rockwell demonstrated that a titanium hollow structure could be fabricated utilizing SPF/DB manufacturing methods. However, some problems such as sharp internal cavity radii and unsatisfactory secondary bonding of the edge and root details prevented production of the required quantity of fatigue test specimens. Subsequently, TRW was selected to (1) produce hollow airfoil test specimens utilizing a laminate-core/hot isostatic press/diffusion bond approach, and (2) manufacture full-size hollow prototype fan blades utilizing the technology that evolved from the specimen fabrication effort. TRW established elements of blade design and defined laminate-core/hot isostatic press/diffusion bonding fabrication techniques to produce test specimens. This fabrication technology was utilized to produce full size hollow fan blades in which the HIP'ed parts were cambered/twisted/isothermally forged, finish machined, and delivered to Pratt & Whitney Aircraft and NASA for further evaluation.

Analytic method for calculating properties of random walks on networks

NASA Technical Reports Server (NTRS)

Goldhirsch, I.; Gefen, Y.

1986-01-01

A method for calculating the properties of discrete random walks on networks is presented. The method divides complex networks into simpler units whose contribution to the mean first-passage time is calculated. The simplified network is then further iterated. The method is demonstrated by calculating mean first-passage times on a segment, a segment with a single dangling bond, a segment with many dangling bonds, and a looplike structure. The results are analyzed and related to the applicability of the Einstein relation between conductance and diffusion.

Hydrogen bonds and heat diffusion in α-helices: a computational study.

PubMed

Miño, German; Barriga, Raul; Gutierrez, Gonzalo

2014-08-28

Recent evidence has shown a correlation between the heat diffusion pathways and the known allosteric communication pathways in proteins. Allosteric communication in proteins is a central, yet unsolved, problem in biochemistry, and the study and characterization of the structural determinants that mediate energy transfer among different parts of proteins is of major importance. In this work, we characterized the role of hydrogen bonds in diffusivity of thermal energy for two sets of α-helices with different abilities to form hydrogen bonds. These hydrogen bonds can be a constitutive part of the α-helices or can arise from the lateral chains. In our in vacuo simulations, it was observed that α-helices with a higher possibility of forming hydrogen bonds also had higher rates of thermalization. Our simulations also revealed that heat readily flowed through atoms involved in hydrogen bonds. As a general conclusion, according to our simulations, hydrogen bonds fulfilled an important role in heat diffusion in structural patters of proteins.

A Novel Fabrication Method of Bi₂Te₃-Based Thermoelectric Modules by Indium Electroplating and Thermocompression Bonding.

PubMed

Yoon, Jongchan; Bae, Sung Hwa; Sohn, Ho-Sang; Son, Injoon; Kim, Kyung Tae; Ju, Young-Wan

2018-09-01

In this study, we devised a method to bond thermoelectric elements directly to copper electrodes by plating indium with a relatively low melting point. A coating of indium, ~30 μm in thickness, was fabricated by electroplating the surface of a Bi2Te3-based thermoelectric element with a nickel diffusion barrier layer. They were then subjected to direct thermocompression bonding at 453 K on a hotplate for 10 min at a pressure of 1.1 kPa. Scanning electron microscopy images confirmed that a uniform bond was formed at the copper electrode/thermoelectric element interface, and the melted/solidified indium layer was defect free. Thus, the proposed novel method of fabricating a thermoelectric module by electroplating indium on the surface of the thermoelectric element and directly bonding with the copper electrode can be used to obtain a uniformly bonded interface even at a relatively low temperature without the use of solder pastes.

Evaluation of laminated aluminum plate for shuttle applications

NASA Technical Reports Server (NTRS)

Martin, M. J.

1973-01-01

Flaw growth behavior in roll diffusion bonded and adhesive bonded 2219-T87 aluminum alloy was compared to that in monolothic 2219-T87. Based on tests at 40 KSI cyclic stress, for equivalent cyclic life, a .004 interlayer laminate can tolerate a surface flaw twice as wide as in monolithic material, or provide an 8% weight saving by operating at higher stress for the same initial flaw. Roll diffusion bonded material with three structural plies of 2219-T87 and two interlayers of 1100 aluminum was prepared with interlayer thicknesses of .004, .007 and .010 in. Total laminate thickness was .130 in. The .004 interlayer laminate was most effective and gave better results than monolithic material at 40 and 48 ksi. Adhesive bonded specimens were fabricated of three sheets of 2219-T87 aluminum alloy bonded with METLBOND 329 adhesive. Adhesive bonded specimens gave longer lives to failure than diffusion bonded specimens at 40 ksi the diffusion bonded material was superior. Flaws initiated in one ply of the laminate grew to the edges of the specimen in that ply but did not propagate into adjacent plies.

Chemical insight from density functional modeling of molecular adsorption: Tracking the bonding and diffusion of anthracene derivatives on Cu(111) with molecular orbitals

NASA Astrophysics Data System (ADS)

Wyrick, Jonathan; Einstein, T. L.; Bartels, Ludwig

2015-03-01

We present a method of analyzing the results of density functional modeling of molecular adsorption in terms of an analogue of molecular orbitals. This approach permits intuitive chemical insight into the adsorption process. Applied to a set of anthracene derivates (anthracene, 9,10-anthraquinone, 9,10-dithioanthracene, and 9,10-diselenonanthracene), we follow the electronic states of the molecules that are involved in the bonding process and correlate them to both the molecular adsorption geometry and the species' diffusive behavior. We additionally provide computational code to easily repeat this analysis on any system.

Method For Improving The Oxidation Resistance Of Metal Substrates Coated With Thermal Barrier Coatings

DOEpatents

Thompson, Anthony Mark; Gray, Dennis Michael; Jackson, Melvin Robert

2003-05-13

A method for providing a protective coating on a metal-based substrate is disclosed. The method involves the application of an aluminum-rich mixture to the substrate to form a discontinuous layer of aluminum-rich particles, followed by the application of a second coating over the discontinuous layer of aluminum-rich particles. Aluminum diffuses from the aluminum-rich layer into the substrate, and into any bond coat layer which is subsequently applied. Related articles are also described. A method for providing a protective coating on a metal-based substrate is disclosed. The method involves the application of an aluminum-rich mixture to the substrate to form a discontinuous layer of aluminum-rich particles, followed by the application of a second coating over the discontinuous layer of aluminum-rich particles. Aluminum diffuses from the aluminum-rich layer into the substrate, and into any bond coat layer which is subsequently applied. Related articles are also described.

Thermal analysis of a diffusion bonded Er3+,Yb3+:glass/Co2+: MgAl2O4 microchip lasers

NASA Astrophysics Data System (ADS)

Belghachem, Nabil; Mlynczak, Jaroslaw; Kopczynski, krzysztof; Mierczyk, Zygmunt; Gawron, Michal

2016-10-01

The analysis of thermal effects in a diffusion bonded Er3+,Yb3+:glass/Co2+:MgAl2O4 microchip laser is presented. The analysis is performed for both wavelengths at 940 nm and at 975 nm as well as for two different sides of pumping, glass side and saturable absorber side. The heat sink effect of Co2+:MgAl2O4, as well as the impact of the thermal expansion and induced stress on the diffusion bonding are emphasised. The best configurations for reducing the temperature peaks, the Von Mises stresses on the diffusion bonding, and the thermal lensing are determined.

Preparation and Bond Properties of Thermal Barrier Coatings on Mg Alloy with Sprayed Al or Diffused Mg-Al Intermetallic Interlayer

NASA Astrophysics Data System (ADS)

Fan, Xizhi; Wang, Ying; Zou, Binglin; Gu, Lijian; Huang, Wenzhi; Cao, Xueqiang

2014-02-01

Sprayed Al or diffused Mg-Al layer was designed as interlayer between the thermal barrier coatings (TBCs) and Mg alloy substrate. The effects of the interlayer on the bond properties of the coats were investigated. Al layers were prepared by arc spraying and atmospheric plasma spraying (APS), respectively. Mg-Al diffused layer was obtained after the heat treatment of the sprayed sample (Mg alloy with APS Al coat) at 400 °C. The results show that sprayed Al interlayer does not improve the bond stability of TBCs. The failure of the TBCs on Mg alloy with Al interlayer occurs mainly due to the low strength of Al layer. Mg-Al diffused layer improves corrosion resistance of substrate and the bond interface. The TBCs on Mg alloy with Mg-Al diffused interlayer shows better bond stability than the sample of which the TBCs is directly sprayed on Mg alloy substrate by APS.

Manufacturing Complicated Shells And Liners

NASA Technical Reports Server (NTRS)

Sobol, Paul J.; Faucher, Joseph E.

1993-01-01

Explosive forming, wax filling, and any one of welding, diffusion bonding, or brazing used in method of manufacturing large, complicated shell-and-liner vessels or structures. Method conceived for manufacture of film-cooled rocket nozzles but applicable to joining large coaxial shells and liners in general.

The latent fingerprint in mass transport of polycrystalline materials

NASA Astrophysics Data System (ADS)

Thirunavukarasu, Gopinath; Kundu, Sukumar; Chatterjee, Subrata

2016-02-01

Herein, a systematic investigation was carried out to reach a rational understanding and to provide information concerning the possible causes for a significant influence of pressure variation in the underlying processes of mass transport in polycrystalline materials. The authors focused their research in solid-state diffusion, a part of the subject "Mass Transport in Solids". Theories on diffusion are the subject by itself which exists as a latent fingerprint in every text of higher learning in interdisciplinary science. In this research, authors prepared sandwich samples of titanium alloy and stainless steel using nickel as an intermediate metal. The samples were processed at three different levels of bonding pressure (3, 4 and 5 MPa) while bonding temperature and bonding time was maintained at 750 °C and 1 h, respectively, throughout the experiments. It was observed that the net flux of atomic diffusion of nickel atoms into Ti-alloy at TiA/Ni interface increased by ~63 % with the rise in the bonding pressure from 3 to 4 MPa, but decreased by ~40 % with the rise in the bonding pressure from 4 to 5 MPa. At the same time, the net flux of atomic diffusion of nickel atoms into stainless steel at Ni/SS interface increased by ~19 % with the rise in the bonding pressure from 3 to 4 MPa, but increased by ~17 % with the rise in the bonding pressure from 4 to 5 MPa. Here authors showed that the pressure variations have different effects at the TiA/Ni interface and Ni/SS interface, and tried to explain the explicit mechanisms operating behind them. In general for sandwich samples processed irrespective of bonding pressure chosen, the net flux of Ni-atoms diffused into SS is greater than that of the net flux of Ni-atoms diffused in Ti-alloy matrix by four orders of magnitude. The calculated diffusivity of Ni-atoms into Ti-alloy reaches its highest value of ~5.083 × 10-19 m2/s for the sandwich sample processed using 4-MPa bonding-pressure, whereas the diffusivity of Ni-atoms into SS reaches its peak value of ~1.615 × 10-14 m2/s for the sample bonded using 5-MPa bonding-pressure.

Diffusion Bonding Technology of Tungsten and SiC/SiC Composites for Nuclear Applications

NASA Astrophysics Data System (ADS)

Kishimoto, Hirotatsu; Shibayama, Tamaki; Abe, Takahiro; Shimoda, Kazuya; Kawamura, Satoshi; Kohyama, Akira

2011-10-01

Silicon carbide (SiC) is a candidate for the structural material in the next generation nuclear plants. Use of SiC/SiC composites is expected to increase the operation temperature of system over 1000 °C. For the high temperature system, refractory metals are planned to be used for several components. Tungsten is a candidate of armor on the divertor component in fusion, and is planned to be used for an upper-end plug of SiC/SiC fuel pin in a Gas cooled Fast Reactor (GFR). Joining technique of the SiC/SiC composites and tungsten is an important issue for nuclear systems in future. Nano-Infiltration and Transient Eutectoid (NITE) method is able to provide dense stable and high strength SiC/SiC composites having high resistance against pressure at elevated temperature, a diffusion bonding technique is usable to join the materials. Present research produces a NITE-SiC/SiC composite and tungsten as the similar dimension as a projected cladding tube of fuel pin for GFR using diffusion bonding, and investigated microstructure and mechanical properties.

A high level Ab initio study of the anionic hydrogen-bonded complexes FH-CN-, FH-NC-, H2O-CN- and H2O-NC-

NASA Technical Reports Server (NTRS)

Lee, Timothy J.

1989-01-01

HF, H2O, CN- and their hydrogen-bonded complexes were studied using state-of-the-art ab initio quantum mechanical methods. A large Gaussian one particle basis set consisting of triple zeta plus double polarization plus diffuse s and p functions (TZ2P + diffuse) was used. The theoretical methods employed include self consistent field, second order Moller-Plesset perturbation theory, singles and doubles configuration interaction theory and the singles and doubles coupled cluster approach. The FH-CN- and FH-NC- and H2O-CN-, H2O-NC- pairs of complexes are found to be essentially isoenergetic. The first pair of complexes are predicted to be bound by approx. 24 kcal/mole and the latter pair bound by approximately 15 kcal/mole. The ab initio binding energies are in good agreement with the experimental values. The two being shorter than the analogous C-N hydrogen bond. The infrared (IR) spectra of the two pairs of complexes are also very similar, though a severe perturbation of the potential energy surface by proton exchange means that the accurate prediction of the band center of the most intense IR mode requires a high level of electronic structure theory as well as a complete treatment of anharmonic effects. The bonding of anionic hydrogen-bonded complexes is discussed and contrasted with that of neutral hydrogen-bonded complexes.

TEM Analysis of Interfaces in Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

NASA Technical Reports Server (NTRS)

Ozaki, T.; Tsuda, H.; Halbig, M. C.; Singh, M.; Hasegawa, Y.; Mori, S.; Asthana R.

2016-01-01

Silicon Carbide (SiC) is a promising material for thermo-structural applications due to its excellent high-temperature mechanical properties, oxidation resistance, and thermal stability. However, joining and integration technologies are indispensable for this material in order to fabricate large size and complex shape components with desired functionalities. Although diffusion bonding techniques using metallic interlayers have been commonly utilized to bond various SiC ceramics, detailed microstructural observation by Transmission Electron Microscopy (TEM) of the bonded area has not been carried out due to difficulty in preparing TEM samples. In this study, we tried to prepare TEM samples from joints of diffusion bonded SiC ceramics by Focused Ion Beam (FIB) system and carefully investigated the interfacial microstructure by TEM analysis. The samples used in this study were SiC fiber bonded ceramics (SA-Tyrannohex: SA-THX) diffusion bonded with metallic interlayers such as Ti, TiMo, and Mo-B. In this presentation, the result of microstructural analysis obtained by TEM observations and the influence of metallic interlayers and fiber orientation of SA-THX on the joint microstructure will be discussed.

Solid state diffusion bonded damascus steel and its role within custom knifemaking

NASA Astrophysics Data System (ADS)

Horne, Grace

This thesis describes practice-based research that applied new technology to an ancient process of laminating metals for blades and explored the application of the new possibilities to a craft context. This research built on work by Ferguson on solid-state diffusion bonded Mokume Gane by moving from metal combinations suitable for vessel-making to metal combinations suitable for knife-making. Solid-state diffusion bonding1 is well established within industry. This research applied the industrial process to a craft based setting, and explored the bonding of metals with very dissimilar properties; ferrous and non-ferrous metals, hard and soft, high and low melting points. The materials included in this study were stainless and carbon steel, iron, nickel, vanadium and silver. The characteristics of the carbon steel and silver laminates were explored further by knifemakers, including heat-treating, forging, machining, flex and pattern creation. Analysis of the knifemakers feedback showed that the steel/silver metal was of interest to makers who machined or ground their blades rather than relying on forging.The study used a multi-method approach. The two broad researchquestions were; Is it possible to make a damascus steel using solid-state diffusion bonding that would be impossible using traditional techniques? And would the results be worth the work? Although carried out mainly within a craft setting the investigation is highly metallurgical in subject matter. The methodology was developed to reflect this crossing of subject areas and answer the research questions outlined above. The results are communicated through this thesis and a documentation of an exhibition of the work produced by the researcher and other selected knifemakers.The research produced a coherent composite of steel and pure silver and successfully produced a number of knives using the material.

Process optimization for diffusion bonding of tungsten with EUROFER97 using a vanadium interlayer

NASA Astrophysics Data System (ADS)

Basuki, Widodo Widjaja; Aktaa, Jarir

2015-04-01

Solid-state diffusion bonding is a selected joining technology to bond divertor components consisting of tungsten and EUROFER97 for application in fusion power plants. Due to the large mismatch in their coefficient of thermal expansions, which leads to serious thermally induced residual stresses after bonding, a thin vanadium plate is introduced as an interlayer. However, the diffusion of carbon originated from EUROFER97 in the vanadium interlayer during the bonding process can form a vanadium carbide layer, which has detrimental influences on the mechanical properties of the joint. For optimal bonding results, the thickness of this layer and the residual stresses has to be decreased sufficiently without a significant reduction of material transport especially at the vanadium/tungsten interface, which can be achieved by varying the diffusion bonding temperature and duration. The investigation results show that at a sufficiently low bonding temperature of 700 °C and a bonding duration of 4 h, the joint reaches a reasonable high ductility and toughness especially at elevated test temperature of 550 °C with elongation to fracture of 20% and mean absorbed Charpy impact energy of 2 J (using miniaturized Charpy impact specimens). The strength of the bonded materials is about 332 MPa at RT and 291 MPa at 550 °C. Furthermore, a low bonding temperature of 700 °C can also help to avoid the grain coarsening and the alteration of the grain structure especially of the EUROFER97 close to the bond interface.

Thermal Skin fabrication technology

NASA Technical Reports Server (NTRS)

Milam, T. B.

1972-01-01

Advanced fabrication techniques applicable to Thermal Skin structures were investigated, including: (1) chemical machining; (2) braze bonding; (3) diffusion bonding; and (4) electron beam welding. Materials investigated were nickel and nickel alloys. Sample Thermal Skin panels were manufactured using the advanced fabrication techniques studied and were structurally tested. Results of the program included: (1) development of improved chemical machining processes for nickel and several nickel alloys; (2) identification of design geometry limits; (3) identification of diffusion bonding requirements; (4) development of a unique diffusion bonding tool; (5) identification of electron beam welding limits; and (6) identification of structural properties of Thermal Skin material.

In vitro antibacterial activity of adhesive systems on Streptococcus mutans.

PubMed

Paradella, Thaís Cachuté; Koga-Ito, Cristiane Yumi; Jorge, Antonio Olavo Cardoso

2009-04-01

To evaluate the antibacterial activity of three adhesive systems -- Prime & Bond 2.1 (PB), Clearfil SE Bond (CS) and One Up Bond F (OU) -- on Streptococcus mutans in vitro. Adherence and agar disk-diffusion tests were performed. For the adherence testing, 40 human enamel specimens (4 mm2) were sterilized and the adhesive sytems were applied (n = 10). The control group did not receive the application of any adhesive system. Specimens were immersed in brain heart infusion broth (BHI) inoculated with S. mutans standardized suspension (10(6) cells/ml) for 48 h at 37 degrees C and 5% CO2. The number of S. mutans cells adhered to each specimen was evaluated by the plating method on BHI agar. For agar disk-diffusion testing, adhesive disks and disks soaked in distilled water (negative control) or 0.2% chlorexidine (positive control) were incubated with S. mutans for 48 h. The diameters of the zones of bacterial inhibition were measured. Adherence data were transformed in logarithms of base 10 (log10). Data were submitted to Kruskal-Wallis and Student-Neuman-Keuls tests at the 5% level of significance. The results of the adherence test showed that One Up Bond F (OU) and Clearfil SE Bond (CS) did not differ significantly from one another, but allowed significantly less adherence than Prime & Bond 2.1 (PB) and control [mean log10 (standard deviation) values: PB 6.10 (0.19); CS primer 4.55 (0.98); OU 4.65 (0.54); control group 6.34 (0.27)]. The disk-diffusion test showed no significant difference between OU (diameter in mm: 3.02 +/- 0.13) and CS (3.0 +/- 0.12), but both were significantly more effective in inhibiting bacterial growth than PB (1.0 +/- 0.10). The self-etching systems Clearfil SE Bond and One Up Bond F presented a greater inhibitory effect against S. mutans, also in terms of adherence, than did the conventional system, Prime & Bond 2.1.

Diffusion doping in quantum dots: bond strength and diffusivity.

PubMed

Saha, Avijit; Makkar, Mahima; Shetty, Amitha; Gahlot, Kushagra; A R, Pavan; Viswanatha, Ranjani

2017-02-23

Semiconducting materials uniformly doped with optical or magnetic impurities have been useful in a number of potential applications. However, clustering or phase separation during synthesis has made this job challenging. Recently the "inside out" diffusion doping was proposed to be successful in obtaining large sized quantum dots (QDs) uniformly doped with a dilute percentage of dopant atoms. Herein, we demonstrate the use of basic physical chemistry of diffusion to control the size and concentration of the dopants within the QDs for a given transition metal ion. We have studied three parameters; the bond strength of the core molecules and the diffusion coefficient of the diffusing metal ion are found to be important while the ease of cation exchange was not highly influential in the control of size and concentration of the single domain dilute magnetic semiconductor quantum dots (DMSQDs) with diverse dopant ions M 2+ (Fe 2+ , Ni 2+ , Co 2+ , Mn 2+ ). Steady state optical emission spectra reveal that the dopants are incorporated inside the semiconducting CdS and the emission can be tuned during shell growth. We have shown that this method enables control over doping percentage and the QDs show a superior ferromagnetic response at room temperature as compared to previously reported systems.

Influence of anatomical, physical, and mechanical properties of diffuse-porous hardwoods on moisture durability of bonded assemblies

Treesearch

Daniel J. Yelle; Ashley M. Stirgus

2016-01-01

Studying wood adhesive bond durability is challenging because wood is highly variable and heterogeneous at all length scales. In this study, three North American diffuse-porous hardwoods (hard maple, soft maple, and basswood) and their adhesively bonded as-semblies were exposed to wet and dry cyclic tests. Then, their den-sity differences were related to bond...

METHOD OF MAKING METAL BONDED CARBON BODIES

DOEpatents

Goeddel, W.V.; Simnad, M.T.

1961-09-26

A method of producing carbon bodies having high structural strength and low permeability is described. The method comprises mixing less than 10 wt.% of a diffusional bonding material selected from the group consisting of zirconium, niobium, molybdenum, titanium, nickel, chromium, silicon, and decomposable compounds thereof with finely divided particles of carbon or graphite. While being maintained at a mechanical pressure over 3,000 psi, the mixture is then heated uniformly to a temperature of 1500 deg C or higher, usually for less than one hour. The resulting carbon bodies have a low diffusion constant, high dimensional stability, and high mechanical strength.

Study of Diffusion Bonding of 45 Steel through the Compacted Nickel Powder Layer

NASA Astrophysics Data System (ADS)

Zeer, G. M.; Zelenkova, E. G.; Temnykh, V. I.; Tokmin, A. M.; Shubin, A. A.; Koroleva, Yu. P.; Mikheev, A. A.

2018-02-01

The microstructure of the transition zone and powder spacer, the concentration distribution of chemical elements over the width of the diffusion-bonded joint, and microhardness of 45 steel-compacted Ni powder spacer-45 steel layered composites formed by diffusion bonding have been investigated. It has been shown that the relative spacer thickness χ < 0.06 is optimal for obtaining a high-quality joint has been formed under a compacting pressure of 500 MPa. The solid-state diffusion bonding is accompanied by sintering the nickel powder spacer and the formation of the transition zone between the spacer and steel. The transition zone consists of solid solution of nickel in the α-Fe phase and ordered solid solution of iron in nickel (FeNi3).

The Structure and Properties of Diffusion Assisted Bonded Joints in 17-4 PH, Type 347, 15-5 PH and Nitronic 40 Stainless Steels

NASA Technical Reports Server (NTRS)

Wigley, D. A.

1981-01-01

Diffusion assisted bonds are formed in 17-4 PH, 15-5 PH, type 347 and Nitronic 40 stainless steels using electrodeposited copper as the bonding agent. The bonds are analyzed by conventional metallographic, electron microprobe analysis, and scanning electron microscopic techniques as well as Charpy V-notch impact tests at temperatures of 77 and 300 K. Results are discussed in terms of a postulated model for the bonding process.

Fineblanking, Diffusion Bonding, and Testing of Fluidic Laminates.

DTIC Science & Technology

1980-07-01

AD-AU69 347 TRITEC INC COLUMBIA ND F/$ 13/7 FINEBLANKING, DIFFUSION BONDING, AND TESTING OF FLUIDIC LAMINAT --ETCIU) JUL 80 L K PECAN OAAK21-79-C-0074...amplifier assembly. The effects of die roll and burrs can be minimized by secondary operations *such as abrasive machining , but this adds to the expense...clad material. Experience has shown that a clad thickness of 0.038 + 0.008 mm is required for the semi-solid diffusion bonding process. The composition

Communication: Surface-to-bulk diffusion of isolated versus interacting C atoms in Ni(111) and Cu(111) substrates: A first principle investigation.

PubMed

Harpale, Abhilash; Panesi, Marco; Chew, Huck Beng

2015-02-14

Using first principle calculations, we study the surface-to-bulk diffusion of C atoms in Ni(111) and Cu(111) substrates, and compare the barrier energies associated with the diffusion of an isolated C atom versus multiple interacting C atoms. We find that the preferential Ni-C bonding over C-C bonding induces a repulsive interaction between C atoms located at diagonal octahedral voids in Ni substrates. This C-C interaction accelerates C atom diffusion in Ni with a reduced barrier energy of ∼1 eV, compared to ∼1.4-1.6 eV for the diffusion of isolated C atoms. The diffusion barrier energy of isolated C atoms in Cu is lower than in Ni. However, bulk diffusion of interacting C atoms in Cu is not possible due to the preferential C-C bonding over C-Cu bonding, which results in C-C dimer pair formation near the surface. The dramatically different C-C interaction effects within the different substrates explain the contrasting growth mechanisms of graphene on Ni(111) and Cu(111) during chemical vapor deposition.

Hydration dynamics of a lipid membrane: Hydrogen bond networks and lipid-lipid associations

NASA Astrophysics Data System (ADS)

Srivastava, Abhinav; Debnath, Ananya

2018-03-01

Dynamics of hydration layers of a dimyristoylphosphatidylcholine (DMPC) bilayer are investigated using an all atom molecular dynamics simulation. Based upon the geometric criteria, continuously residing interface water molecules which form hydrogen bonds solely among themselves and then concertedly hydrogen bonded to carbonyl, phosphate, and glycerol head groups of DMPC are identified. The interface water hydrogen bonded to lipids shows slower relaxation rates for translational and rotational dynamics compared to that of the bulk water and is found to follow sub-diffusive and non-diffusive behaviors, respectively. The mean square displacements and the reorientational auto-correlation functions are slowest for the interfacial waters hydrogen bonded to the carbonyl oxygen since these are buried deep in the hydrophobic core among all interfacial water studied. The intermittent hydrogen bond auto-correlation functions are calculated, which allows breaking and reformations of the hydrogen bonds. The auto-correlation functions for interfacial hydrogen bonded networks develop humps during a transition from cage-like motion to eventual power law behavior of t-3/2. The asymptotic t-3/2 behavior indicates translational diffusion dictated dynamics during hydrogen bond breaking and formation irrespective of the nature of the chemical confinement. Employing reactive flux correlation analysis, the forward rate constant of hydrogen bond breaking and formation is calculated which is used to obtain Gibbs energy of activation of the hydrogen bond breaking. The relaxation rates of the networks buried in the hydrophobic core are slower than the networks near the lipid-water interface which is again slower than bulk due to the higher Gibbs energy of activation. Since hydrogen bond breakage follows a translational diffusion dictated mechanism, chemically confined hydrogen bond networks need an activation energy to diffuse through water depleted hydrophobic environments. Our calculations reveal that the slow relaxation rates of interfacial waters in the vicinity of lipids are originated from the chemical confinement of concerted hydrogen bond networks. The analysis suggests that the networks in the hydration layer of membranes dynamically facilitate the water mediated lipid-lipid associations which can provide insights on the thermodynamic stability of soft interfaces relevant to biological systems in the future.

Information diffusion, Facebook clusters, and the simplicial model of social aggregation: a computational simulation of simplicial diffusers for community health interventions.

PubMed

Kee, Kerk F; Sparks, Lisa; Struppa, Daniele C; Mannucci, Mirco A; Damiano, Alberto

2016-01-01

By integrating the simplicial model of social aggregation with existing research on opinion leadership and diffusion networks, this article introduces the constructs of simplicial diffusers (mathematically defined as nodes embedded in simplexes; a simplex is a socially bonded cluster) and simplicial diffusing sets (mathematically defined as minimal covers of a simplicial complex; a simplicial complex is a social aggregation in which socially bonded clusters are embedded) to propose a strategic approach for information diffusion of cancer screenings as a health intervention on Facebook for community cancer prevention and control. This approach is novel in its incorporation of interpersonally bonded clusters, culturally distinct subgroups, and different united social entities that coexist within a larger community into a computational simulation to select sets of simplicial diffusers with the highest degree of information diffusion for health intervention dissemination. The unique contributions of the article also include seven propositions and five algorithmic steps for computationally modeling the simplicial model with Facebook data.

Thermo-electric modular structure and method of making same

DOEpatents

Freedman, N.S.; Horsting, C.W.; Lawrence, W.F.; Carrona, J.J.

1974-01-29

A method is presented for making a thermoelectric module wtth the aid of an insulating wafer having opposite metallized surfaces, a pair of similar equalizing sheets of metal, a hot-junction strap of metal, a thermoelectric element having hot- and cold-junction surfaces, and a radiator sheet of metal. The method comprises the following steps: brazing said equalizer sheets to said opposite metallized surfaces, respectively, of said insulating wafer with pure copper in a non-oxidizing ambient; brazing one surface of said hot-junction strap to one of the surfaces of said equalizing sheet with a nickel-gold alloy in a non- oxidizing ambient; and diffusion bonding said hot-junction surface of said thermoelectric element to the other surface of said hot-junction strap and said radiator sheet to said cold-junction surface of said thermoelectric element, said diffusion bonding being carried out in a non-oxidizing ambient, under compressive loading, at a temperature of about 550 deg C., and for about one-half hour. (Official Gazette)

Thin-film diffusion brazing of titanium alloys

NASA Technical Reports Server (NTRS)

Mikus, E. B.

1972-01-01

A thin film diffusion brazing technique for joining titanium alloys by use of a Cu intermediate is described. The method has been characterized in terms of static and dynamic mechanical properties on Ti-6Al-4V alloy. These include tensile, fracture toughness, stress corrosion, shear, corrosion fatigue, mechanical fatigue and acoustic fatigue. Most of the properties of titanium joints formed by thin film diffusion brazing are equal or exceed base metal properties. The advantages of thin film diffusion brazing over solid state diffusion bonding and brazing with conventional braze alloys are discussed. The producibility advantages of this process over others provide the potential for producing high efficiency joints in structural components of titanium alloys for the minimum cost.

Interface bonding of NiCrAlY coating on laser modified H13 tool steel surface

NASA Astrophysics Data System (ADS)

Reza, M. S.; Aqida, S. N.; Ismail, I.

2016-06-01

Bonding strength of thermal spray coatings depends on the interfacial adhesion between bond coat and substrate material. In this paper, NiCrAlY (Ni-164/211 Ni22 %Cr10 %Al1.0 %Y) coatings were developed on laser modified H13 tool steel surface using atmospheric plasma spray (APS). Different laser peak power, P p, and duty cycle, DC, were investigated in order to improve the mechanical properties of H13 tool steel surface. The APS spraying parameters setting for coatings were set constant. The coating microstructure near the interface was analyzed using IM7000 inverted optical microscope. Interface bonding of NiCrAlY was investigated by interfacial indentation test (IIT) method using MMT-X7 Matsuzawa Hardness Tester Machine with Vickers indenter. Diffusion of atoms along NiCrAlY coating, laser modified and substrate layers was investigated by energy-dispersive X-ray spectroscopy (EDXS) using Hitachi Tabletop Microscope TM3030 Plus. Based on IIT method results, average interfacial toughness, K avg, for reference sample was 2.15 MPa m1/2 compared to sample L1 range of K avg from 6.02 to 6.96 MPa m1/2 and sample L2 range of K avg from 2.47 to 3.46 MPa m1/2. Hence, according to K avg, sample L1 has the highest interface bonding and is being laser modified at lower laser peak power, P p, and higher duty cycle, DC, prior to coating. The EDXS analysis indicated the presence of Fe in the NiCrAlY coating layer and increased Ni and Cr composition in the laser modified layer. Atomic diffusion occurred in both coating and laser modified layers involved in Fe, Ni and Cr elements. These findings introduce enhancement of coating system by substrate surface modification to allow atomic diffusion.

A novel method combining additive manufacturing and alloy infiltration for NdFeB bonded magnet fabrication

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

Li, Ling; Tirado, Angelica; Conner, Benjamin S.

In this paper, binder jetting additive manufacturing technique is employed to fabricate NdFeB isotropic bonded magnets, followed by an infiltration process with low-melting point eutectic alloys [i.e., Nd 3Cu 0.25Co 0.75 (NdCuCo) and Pr 3Cu 0.25Co 0.75 (PrCuCo)]. Densification and mechanical strength improvement are achieved for the as-printed porous part. Meanwhile, the intrinsic coercivity H ci is enhanced from 732 to 1345 kA/m and 1233 kA/m after diffusion of NdCuCo and PrCuCo, respectively. This study presents a novel method for fabricating complex-shaped bonded magnets with promising mechanical and magnetic properties.

A novel method combining additive manufacturing and alloy infiltration for NdFeB bonded magnet fabrication

DOE PAGES

Li, Ling; Tirado, Angelica; Conner, Benjamin S.; ...

2017-04-27

In this paper, binder jetting additive manufacturing technique is employed to fabricate NdFeB isotropic bonded magnets, followed by an infiltration process with low-melting point eutectic alloys [i.e., Nd 3Cu 0.25Co 0.75 (NdCuCo) and Pr 3Cu 0.25Co 0.75 (PrCuCo)]. Densification and mechanical strength improvement are achieved for the as-printed porous part. Meanwhile, the intrinsic coercivity H ci is enhanced from 732 to 1345 kA/m and 1233 kA/m after diffusion of NdCuCo and PrCuCo, respectively. This study presents a novel method for fabricating complex-shaped bonded magnets with promising mechanical and magnetic properties.

Influence of Hydrogen Bonding on the Surface Diffusion of Molecular Glasses: Comparison of Three Triazines

DOE PAGES

Chen, Yinshan; Zhu, Men; Laventure, Audrey; ...

2017-06-26

Surface grating decay measurements have been performed on three closely related molecular glasses to study the effect of intermolecular hydrogen bonds on surface diffusion. The three molecules are derivatives of bis(3,5-dimethyl-phenylamino)-1,3,5-triazine and differ only in the functional group R at the 2-position, with R being C 2H 5, OCH 3, and NHCH 3, and referred to as “Et”, “OMe”, and “NHMe”, respectively. Of the three molecules, NHMe forms more extensive intermolecular hydrogen bonds than Et and OMe and was found to have slower surface diffusion. For Et and OMe, surface diffusion is so fast that it replaces viscous flow asmore » the mechanism of surface grating decay as temperature is lowered. In contrast, no such transition was observed for NHMe under the same conditions, indicating significantly slower surface diffusion. This result is consistent with the previous finding that extensive intermolecular hydrogen bonds slow down surface diffusion in molecular glasses and is attributed to the persistence of hydrogen bonds even in the surface environment. Here, this result is also consistent with the lower stability of the vapor-deposited glass of NHMe relative to those of Et and OMe and supports the view that surface mobility controls the stability of vapor-deposited glasses.« less

The Effect of Limited Diffusion and Wet-Dry Cycling on Reversible Polymerization Reactions: Implications for Prebiotic Synthesis of Nucleic Acids.

PubMed

Higgs, Paul G

2016-06-08

A long-standing problem for the origins of life is that polymerization of many biopolymers, including nucleic acids and peptides, is thermodynamically unfavourable in aqueous solution. If bond making and breaking is reversible, monomers and very short oligomers predominate. Recent experiments have shown that wetting and drying cycles can overcome this problem and drive the formation of longer polymers. In the dry phase, bond formation is favourable, but diffusion is restricted, and bonds only form between monomers that are initially close together. In the wet phase, some of the bonds are hydrolyzed. However, repositioning of the molecules allows new bonds to form in the next dry phase, leading to an increase in mean polymer length. Here, we consider a simple theoretical model that explains the effect of cycling. There is an equilibrium length distribution with a high mean length that could be achieved if diffusion occurred freely in the dry phase. This equilibrium is inaccessible without diffusion. A single dry cycle without diffusion leads to mean lengths much shorter than this. Repeated cycling leads to a significant increase in polymerization relative to a single cycle. In the most favourable case, cycling leads to the same equilibrium length distribution as would be achieved if free diffusion were possible in the dry phase. These results support the RNA World scenario by explaining a potential route to synthesis of long RNAs; however, they also imply that cycling would be beneficial to the synthesis of other kinds of polymers, including peptides, where bond formation involves a condensation reaction.

The Effect of Limited Diffusion and Wet–Dry Cycling on Reversible Polymerization Reactions: Implications for Prebiotic Synthesis of Nucleic Acids

PubMed Central

Higgs, Paul G.

2016-01-01

A long-standing problem for the origins of life is that polymerization of many biopolymers, including nucleic acids and peptides, is thermodynamically unfavourable in aqueous solution. If bond making and breaking is reversible, monomers and very short oligomers predominate. Recent experiments have shown that wetting and drying cycles can overcome this problem and drive the formation of longer polymers. In the dry phase, bond formation is favourable, but diffusion is restricted, and bonds only form between monomers that are initially close together. In the wet phase, some of the bonds are hydrolyzed. However, repositioning of the molecules allows new bonds to form in the next dry phase, leading to an increase in mean polymer length. Here, we consider a simple theoretical model that explains the effect of cycling. There is an equilibrium length distribution with a high mean length that could be achieved if diffusion occurred freely in the dry phase. This equilibrium is inaccessible without diffusion. A single dry cycle without diffusion leads to mean lengths much shorter than this. Repeated cycling leads to a significant increase in polymerization relative to a single cycle. In the most favourable case, cycling leads to the same equilibrium length distribution as would be achieved if free diffusion were possible in the dry phase. These results support the RNA World scenario by explaining a potential route to synthesis of long RNAs; however, they also imply that cycling would be beneficial to the synthesis of other kinds of polymers, including peptides, where bond formation involves a condensation reaction. PMID:27338479

Technical Note: Preliminary investigations into the use of a functionalised polymer to reduce diffusion in Fricke gel dosimeters

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

Smith, S. T., E-mail: s164.smith@qut.edu.au; Masters, K.-S.; Hosokawa, K.

2015-12-15

Purpose: A modification of the existing PVA-FX hydrogel has been made to investigate the use of a functionalised polymer in a Fricke gel dosimetry system to decrease Fe{sup 3+} diffusion. Methods: The chelating agent, xylenol orange, was chemically bonded to the gelling agent, polyvinyl alcohol (PVA) to create xylenol orange functionalised PVA (XO-PVA). A gel was created from the XO-PVA (20% w/v) with ferrous sulfate (0.4 mM) and sulfuric acid (50 mM). Results: This resulted in an optical density dose sensitivity of 0.014 Gy{sup −1}, an auto-oxidation rate of 0.0005 h{sup −1}, and a diffusion rate of 0.129 mm{sup 2}more » h{sup −1}; an 8% reduction compared to the original PVA-FX gel, which in practical terms adds approximately 1 h to the time span between irradiation and accurate read-out. Conclusions: Because this initial method of chemically bonding xylenol orange to polyvinyl alcohol has inherently low conversion, the improvement on existing gel systems is minimal when compared to the drawbacks. More efficient methods of functionalising polyvinyl alcohol with xylenol orange must be developed for this system to gain clinical relevance.« less

New valve and bonding designs for microfluidic biochips containing proteins.

PubMed

Lu, Chunmeng; Xie, Yubing; Yang, Yong; Cheng, Mark M-C; Koh, Chee-Guan; Bai, Yunling; Lee, L James; Juang, Yi-Je

2007-02-01

Two major concerns in the design and fabrication of microfluidic biochips are protein binding on the channel surface and protein denaturing during device assembly. In this paper, we describe new methods to solve these problems. A "fishbone" microvalve design based on the concept of superhydrophobicity was developed to replace the capillary valve in applications where the chip surface requires protein blocking to prevent nonspecific binding. Our experimental results show that the valve functions well in a CD-like ELISA device. The packaging of biochips containing pre-loaded proteins is also a challenging task since conventional sealing methods often require the use of high temperatures, electric voltages, or organic solvents that are detrimental to the protein activity. Using CO2 gas to enhance the diffusion of polymer molecules near the device surface can result in good bonding at low temperatures and low pressure. This bonding method has little influence on the activity of the pre-loaded proteins after bonding.

Interplay between translational diffusion and large-amplitude angular jumps of water molecules

NASA Astrophysics Data System (ADS)

Liu, Chao; Zhang, Yangyang; Zhang, Jian; Wang, Jun; Li, Wenfei; Wang, Wei

2018-05-01

Understanding the microscopic mechanism of water molecular translational diffusion is a challenging topic in both physics and chemistry. Here, we report an investigation on the interplay between the translational diffusion and the large-amplitude angular jumps of water molecules in bulk water using molecular dynamics simulations. We found that large-amplitude angular jumps are tightly coupled to the translational diffusions. Particularly, we revealed that concurrent rotational jumps of spatially neighboring water molecules induce inter-basin translational jumps, which contributes to the fast component of the water translational diffusion. Consequently, the translational diffusion shows positional heterogeneity; i.e., the neighbors of the water molecules with inter-basin translational jumps have larger probability to diffuse by inter-basin translational jumps. Our control simulations showed that a model water molecule with moderate hydrogen bond strength can diffuse much faster than a simple Lennard-Jones particle in bulk water due to the capability of disturbing the hydrogen bond network of the surrounding water molecules. Our results added to the understanding of the microscopic picture of the water translational diffusion and demonstrated the unique features of water diffusion arising from their hydrogen bond network structure compared with those of the simple liquids.

Molecular Dynamic Simulation of Diffusion Coefficients for Alkanols in Supercritical CO2 1

NASA Astrophysics Data System (ADS)

Li, Zhiwei; Lai, Shuhui; Gao, Wei; Chen, Liuping

2018-07-01

The infinite dilution diffusion coefficients ( D 12) of methanol, ethanol, 1-propanol, 1-butanol and 1-pentanol in supercritical CO2 (scCO2) at 313.2 K and 10-16 MPa were simulated by molecular dynamics (MD) simulation. The microscopic structure was also analyzed by calculation of the radial distribution function, coordination number (CN) between the center mass of solute and solvent molecules, and the average number of hydrogen bonding of this system. In infinite dilute solution, the probability of forming hydrogen bond between alkanol molecules is greatly reduced relative to pure alkanol fluid, and the weak hydrogen bonds formed between alkanol and CO2 molecules. In general, this work provides a reliable simulation method for transfer properties of solutes in scCO2. The prediction data were provides for the design and development of chemical processing. The results are helpful for one to deeper understand the relationship between microscopic structures of fluid and its transfer properties.

Rhenium Rocket Manufacturing Technology

NASA Technical Reports Server (NTRS)

1997-01-01

The NASA Lewis Research Center's On-Board Propulsion Branch has a research and technology program to develop high-temperature (2200 C), iridium-coated rhenium rocket chamber materials for radiation-cooled rockets in satellite propulsion systems. Although successful material demonstrations have gained much industry interest, acceptance of the technology has been hindered by a lack of demonstrated joining technologies and a sparse materials property data base. To alleviate these concerns, we fabricated rhenium to C-103 alloy joints by three methods: explosive bonding, diffusion bonding, and brazing. The joints were tested by simulating their incorporation into a structure by welding and by simulating high-temperature operation. Test results show that the shear strength of the joints degrades with welding and elevated temperature operation but that it is adequate for the application. Rhenium is known to form brittle intermetallics with a number of elements, and this phenomena is suspected to cause the strength degradation. Further bonding tests with a tantalum diffusion barrier between the rhenium and C-103 is planned to prevent the formation of brittle intermetallics.

Diffusion Bonding of Silicon Carbide for a Micro-Electro-Mechanical Systems Lean Direct Injector

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay; Shpargel, Tarah P.; Kiser, James D.

2006-01-01

Robust approaches for joining silicon carbide (SiC) to silicon carbide sub-elements have been developed for a micro-electro-mechanical systems lean direct injector (MEMS LDI) application. The objective is to join SiC sub-elements to form a leak-free injector that has complex internal passages for the flow and mixing of fuel and air. Previous bonding technology relied upon silicate glass interlayers that were not uniform or leak free. In a newly developed joining approach, titanium foils and physically vapor deposited titanium coatings were used to form diffusion bonds between SiC materials during hot pressing. Microscopy results show the formation of well adhered diffusion bonds. Initial tests show that the bond strength is much higher than required for the component system. Benefits of the joining technology are fabrication of leak free joints with high temperature and mechanical capability.

Diffusion barriers in modified air brazes

DOEpatents

Weil, Kenneth Scott; Hardy, John S; Kim, Jin Yong; Choi, Jung-Pyung

2013-04-23

A method for joining two ceramic parts, or a ceramic part and a metal part, and the joint formed thereby. The method provides two or more parts, a braze consisting of a mixture of copper oxide and silver, a diffusion barrier, and then heats the braze for a time and at a temperature sufficient to form the braze into a bond holding the two or more parts together. The diffusion barrier is an oxidizable metal that forms either a homogeneous component of the braze, a heterogeneous component of the braze, a separate layer bordering the braze, or combinations thereof. The oxidizable metal is selected from the group Al, Mg, Cr, Si, Ni, Co, Mn, Ti, Zr, Hf, Pt, Pd, Au, lanthanides, and combinations thereof.

Diffusion barriers in modified air brazes

DOEpatents

Weil, Kenneth Scott [Richland, WA; Hardy, John S [Richland, WA; Kim, Jin Yong [Richland, WA; Choi, Jung-Pyung [Richland, WA

2010-04-06

A method for joining two ceramic parts, or a ceramic part and a metal part, and the joint formed thereby. The method provides two or more parts, a braze consisting of a mixture of copper oxide and silver, a diffusion barrier, and then heats the braze for a time and at a temperature sufficient to form the braze into a bond holding the two or more parts together. The diffusion barrier is an oxidizable metal that forms either a homogeneous component of the braze, a heterogeneous component of the braze, a separate layer bordering the braze, or combinations thereof. The oxidizable metal is selected from the group Al, Mg, Cr, Si, Ni, Co, Mn, Ti, Zr, Hf, Pt, Pd, Au, lanthanides, and combinations thereof.

Fabrication of Monolithic RERTR Fuels by Hot Isostatic Pressing

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

Jan-Fong Jue; Blair H. Park; Curtis R. Clark

2010-11-01

The RERTR (Reduced Enrichment for Research and Test Reactors) Program is developing advanced nuclear fuels for high-power test reactors. Monolithic fuel design provides higher uranium loading than that of the traditional dispersion fuel design. Hot isostatic pressing is a promising process for low-cost batch fabrication of monolithic RERTR fuel plates for these high-power reactors. Bonding U Mo fuel foil and 6061 Al cladding by hot isostatic press bonding was successfully developed at Idaho National Laboratory. Due to the relatively high processing temperature, the interaction between fuel meat and aluminum cladding is a concern. Two different methods were employed to mitigatemore » this effect: (1) a diffusion barrier and (2) a doping addition to the interface. Both types of fuel plates have been fabricated by hot isostatic press bonding. Preliminary results show that the direct fuel/cladding interaction during the bonding process was eliminated by introducing a thin zirconium diffusion barrier layer between the fuel and the cladding. Fuel plates were also produced and characterized with a silicon-rich interlayer between fuel and cladding. This paper reports the recent progress of this developmental effort and identifies the areas that need further attention.« less

Porous coatings from wire mesh for bone implants

DOEpatents

Sump, Kenneth R.

1986-01-01

A method of coating areas of bone implant elements and the resulting implant having a porous coating are described. Preselected surface areas are covered by a preform made from continuous woven lengths of wire. The preform is compressed and heated to assure that diffusion bonding occurs between the wire surfaces and between the surface boundaries of the implant element and the wire surfaces in contact with it. Porosity is achieved by control of the resulting voids between the bonded wire portions.

Microstructure and mechanical properties of diffusion bonded W/steel joint using V/Ni composite interlayer

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

Liu, W.S.; Cai, Q.S., E-mail: cai2009pm@163.com; Ma, Y.Z.

2013-12-15

Diffusion bonding between W and steel using V/Ni composite interlayer was carried out in vacuum at 1050 °C and 10 MPa for 1 h. The microstructural examination and mechanical property evaluation of the joints show that the bonding of W to steel was successful. No intermetallic compound was observed at the steel/Ni and V/W interfaces for the joints bonded. The electron probe microanalysis and X-ray diffraction analysis revealed that Ni{sub 3}V, Ni{sub 2}V, Ni{sub 2}V{sub 3} and NiV{sub 3} were formed at the Ni/V interface. The tensile strength of about 362 MPa was obtained for as-bonded W/steel joint and themore » failure occurred at W near the V/W interface. The nano-indentation test across the joining interfaces demonstrated the effect of solid solution strengthening and intermetallic compound formation in the diffusion zone. - Highlights: • Diffusion bonding of W to steel was realized using V/Ni composite interlayer. • The interfacial microstructure of the joint was clarified. • Several V–Ni intermetallic compounds were formed in the interface region. • The application of V/Ni composite interlayer improved the joining quality.« less

Method of bonding silver to glass and mirrors produced according to this method

DOEpatents

Pitts, J.R.; Thomas, T.M.; Czanderna, A.W.

1984-07-31

A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

Method of bonding silver to glass and mirrors produced according to this method

DOEpatents

Pitts, John R.; Thomas, Terence M.; Czanderna, Alvin W.

1985-01-01

A method for adhering silver to a glass substrate for producing mirrors includes attaining a silicon enriched substrate surface by reducing the oxygen therein in a vacuum and then vacuum depositing a silver layer onto the silicon enriched surface. The silicon enrichment can be attained by electron beam bombardment, ion beam bombardment, or neutral beam bombardment. It can also be attained by depositing a metal, such as aluminum, on the substrate surface, allowing the metal to oxidize by pulling oxygen from the substrate surface, thereby leaving a silicon enriched surface, and then etching or eroding the metal oxide layer away to expose the silicon enriched surface. Ultraviolet rays can be used to maintain dangling silicon bonds on the enriched surface until covalent bonding with the silver can occur. This disclosure also includes encapsulated mirrors with diffusion layers built therein. One of these mirrors is assembled on a polymer substrate.

Fluxless eutectic bonding of GaAs-on-Si by using Ag/Sn solder

NASA Astrophysics Data System (ADS)

Eo, Sung-Hwa; Kim, Dae-Seon; Jeong, Ho-Jung; Jang, Jae-Hyung

2013-11-01

Fluxless GaAs-on-Si wafer bonding using Ag/Sn solder was investigated to realize uniform and void-free heterogeneous material integration. The effects of the diffusion barrier, Ag/Sn thickness, and Ar plasma treatment were studied to achieve the optimal fluxless bonding process. Pt on a GaAs wafer and Mo on a Si wafer act as diffusion barriers by preventing the flow of Ag/Sn solder into both the wafers. The bonding strength is closely related to the Ag/Sn thickness and Ar plasma treatment. A shear strength test was carried out to investigate the bonding strength. Under identical bonding conditions, the Ag/Sn thickness was optimized to achieve higher bonding strength and to avoid the formation of voids due to thermal stress. An Ar plasma pretreatment process improved the bonding strength because the Ar plasma removed carbon contaminants and metal-oxide bonds from the metal surface.

Roll diffusion bonding of titanium alloy panels

NASA Technical Reports Server (NTRS)

Bennett, J.; De Witt, T. E.; Jones, A. G.; Koeller, F.; Muser, C.

1968-01-01

Roll diffusion bonding technique is used for fabricating T-stiffened panel assemblies from titanium alloy. The single unit fabrication exhibits excellent strength characteristics under tensile and compressive loads. This program is applied to structures in which weight/strength ratio and integral construction are important considerations.

Diffuse X-ray scattering from benzil, C(14)H(10)O(2): analysis via automatic refinement of a Monte Carlo model.

PubMed

Welberry, T R; Goossens, D J; Edwards, A J; David, W I

2001-01-01

A recently developed method for fitting a Monte Carlo computer-simulation model to observed single-crystal diffuse X-ray scattering has been used to study the diffuse scattering in benzil, diphenylethanedione, C(6)H(5)-CO-CO-C(6)H(5). A model involving 13 parameters consisting of 11 intermolecular force constants, a single intramolecular torsional force constant and a local Debye-Waller factor was refined to give an agreement factor, R = [summation operator omega(Delta I)(2)/summation operator omega I(obs)(2)](1/2), of 14.5% for 101,324 data points. The model was purely thermal in nature. The analysis has shown that the diffuse lines, which feature so prominently in the observed diffraction patterns, are due to strong longitudinal displacement correlations. These are transmitted from molecule to molecule via a network of contacts involving hydrogen bonding of an O atom on one molecule and the para H atom of the phenyl ring of a neighbouring molecule. The analysis also allowed the determination of a torsional force constant for rotations about the single bonds in the molecule. This is the first diffuse scattering study in which measurement of such internal molecular torsion forces has been attempted.

Theoretical and experimental studies of water interaction in acetate based ionic liquids.

PubMed

Shi, Wei; Damodaran, Krishnan; Nulwala, Hunaid B; Luebke, David R

2012-12-05

Water interactions in 1-ethyl-3-methylimidazolium acetate ([emim][CH(3)COO]) were studied utilizing classical and ab initio simulation methods. The self-diffusivities for water and the ionic liquid (IL) were studied experimentally using pulse field gradient NMR spectroscopy and correlated with computational results. Water forms hydrogen bonding networks with the ionic liquid, and depending on the concentration of water, there are profound effects on the self-diffusivities of the various species. Both simulation and experiments show that the self-diffusivities for species in the water-[emim][CH(3)COO] system exhibit minima at 40-50 mol% water. Water interaction with the [CH(3)COO](-) anion predominates over the water-water and water-cation interactions at most water concentrations. Simulations further indicate that decreasing water-[CH(3)COO](-) interaction will increase the IL and water self-diffusivities. Self-diffusivities in the water-IL systems are dependent upon the cation in a complex way. Water interactions with [P(4444)][CH(3)COO] are reduced compared to [emim][CH(3)COO]. The [P(4444)](+) cation is bulkier than the [emim](+) cation and has a smaller self-diffusivity, but when water was introduced to [P(4444)] [CH(3)COO], the water-[CH(3)COO](-) hydrogen bonding network in the [P(4444)][CH(3)COO] was much smaller than the one observed in [emim][CH(3)COO].

Kinetic Monte Carlo Simulations of Oxygen Diffusion in Environmental Barrier Coating Materials

NASA Technical Reports Server (NTRS)

Good, Brian S.

2017-01-01

Ceramic Matrix Composite (CMC) materials are of interest for use in next-generation turbine engine components, offering a number of significant advantages, including reduced weight and high operating temperatures. However, in the hot environment in which such components operate, the presence of water vapor can lead to corrosion and recession, limiting the useful life of the components. Such degradation can be reduced through the use of Environmental Barrier Coatings (EBCs) that limit the amount of oxygen and water vapor reaching the component. Candidate EBC materials include Yttrium and Ytterbium silicates. In this work we present results of kinetic Monte Carlo (kMC) simulations of oxygen diffusion, via the vacancy mechanism, in Yttrium and Ytterbium disilicates, along with a brief discussion of interstitial diffusion. An EBC system typically includes a bond coat located between the EBC and the component surface. Bond coat materials are generally chosen for properties other than low oxygen diffusivity, but low oxygen diffusivity is nevertheless a desirable characteristic, as the bond coat could provide some additional component protection, particularly in the case where cracks in the coating system provide a direct path from the environment to the bond coat interface. We have therefore performed similar kMC simulations of oxygen diffusion in this material.

Method of thermal strain hysteresis reduction in metal matrix composites

NASA Technical Reports Server (NTRS)

Dries, Gregory A. (Inventor); Tompkins, Stephen S. (Inventor)

1987-01-01

A method is disclosed for treating graphite reinforced metal matrix composites so as to eliminate thermal strain hysteresis and impart dimensional stability through a large thermal cycle. The method is applied to the composite post fabrication and is effective on metal matrix materials using graphite fibers manufactured by both the hot roll bonding and diffusion bonding techniques. The method consists of first heat treating the material in a solution anneal oven followed by a water quench and then subjecting the material to a cryogenic treatment in a cryogenic oven. This heat treatment and cryogenic stress reflief is effective in imparting a dimensional stability and reduced thermal strain hysteresis in the material over a -250.degree. F. to +250.degree. F. thermal cycle.

Self-Diffusion in Amorphous Silicon by Local Bond Rearrangements

NASA Astrophysics Data System (ADS)

Kirschbaum, J.; Teuber, T.; Donner, A.; Radek, M.; Bougeard, D.; Böttger, R.; Hansen, J. Lundsgaard; Larsen, A. Nylandsted; Posselt, M.; Bracht, H.

2018-06-01

Experiments on self-diffusion in amorphous silicon (Si) were performed at temperatures between 460 to 600 ° C . The amorphous structure was prepared by Si ion implantation of single crystalline Si isotope multilayers epitaxially grown on a silicon-on-insulator wafer. The Si isotope profiles before and after annealing were determined by means of secondary ion mass spectrometry. Isothermal diffusion experiments reveal that structural relaxation does not cause any significant intermixing of the isotope interfaces whereas self-diffusion is significant before the structure recrystallizes. The temperature dependence of self-diffusion is described by an Arrhenius law with an activation enthalpy Q =(2.70 ±0.11 ) eV and preexponential factor D0=(5.5-3.7+11.1)×10-2 cm2 s-1 . Remarkably, Q equals the activation enthalpy of hydrogen diffusion in amorphous Si, the migration of bond defects determining boron diffusion, and the activation enthalpy of solid phase epitaxial recrystallization reported in the literature. This close agreement provides strong evidence that self-diffusion is mediated by local bond rearrangements rather than by the migration of extended defects as suggested by Strauß et al. (Phys. Rev. Lett. 116, 025901 (2016), 10.1103/PhysRevLett.116.025901).

Bond lifetime and diffusion coefficient in colloids with short-range interactions.

PubMed

Ndong Mintsa, E; Germain, Ph; Amokrane, S

2015-03-01

We use molecular dynamics simulations to study the influence of short-range structures in the interaction potential between hard-sphere-like colloidal particles. Starting from model potentials and effective potentials in binary mixtures computed from the Ornstein-Zernike equations, we investigate the influence of the range and strength of a possible tail beyond the usual core repulsion or the presence of repulsive barriers. The diffusion coefficient and mean "bond" lifetimes are used as indicators of the effect of this structure on the dynamics. The existence of correlations between the variations of these quantities with the physical parameters is discussed to assess the interpretation of dynamics slowing down in terms of long-lived bonds. We also discuss the question of a universal behaviour determined by the second virial coefficient B ((2)) and the interplay of attraction and repulsion. While the diffusion coefficient follows the B ((2)) law for purely attractive tails, this is no longer true in the presence of repulsive barriers. Furthermore, the bond lifetime shows a dependence on the physical parameters that differs from that of the diffusion coefficient. This raises the question of the precise role of bonds on the dynamics slowing down in colloidal gels.

Exhibition of veiled features in diffusion bonding of titanium alloy and stainless steel via copper

NASA Astrophysics Data System (ADS)

Thirunavukarasu, Gopinath; Kundu, Sukumar; Laha, Tapas; Roy, Deb; Chatterjee, Subrata

2017-11-01

An investigation was carried out to know the extent of influence of bonding-time on the interface structure and mechanical properties of diffusion bonding (DB) of TiA|Cu|SS. DB of Ti6Al4V (TiA) and 304 stainless steel (SS) using pure copper (Cu) of 200-μm thickness were processed in vacuum using 4-MPa bonding-pressure at 1123 K from 15 to 120 min in steps of 15 min. Preparation of DB was not possible when bonding-time was less than 60 min as the bonding at Cu|SS interface was unsuccessful in spite of effective bonding at TiA|Cu interface; however, successful DB were produced when the bonding-time was 60 min and beyond. DB processed for 60 and 75 min (classified as shorter bonding-time interval) showed distinctive characteristics (structural, mechanical, and fractural) as compared to the DB processed for 90, 105, and 120 min (classified as longer bonding-time interval). DB processed for 60 and 75 min exhibited layer-wise Cu-Ti-based intermetallics at TiA|Cu interface, whereas Cu|SS interface was completely free from reaction products. The layer-wise structure of Cu-Ti-based intermetallics were not observed at TiA|Cu interface in the DB processed for longer bonding-time; however, the Cu|SS interface had layer-wise ternary intermetallic compounds (T1, T2, and T3) of Cu-Fe-Ti-based along with σ phase depending upon the bonding-time chosen. Diffusivity of Ti-atoms in Cu-layer (DTi in Cu-layer) was much greater than the diffusivity of Fe-atoms in Cu-layer (DFe in Cu-layer). Ti-atoms reached Cu|SS interface but Fe-atoms were unable to reach TiA|Cu interface. It was observed that DB fractured at Cu|SS interface when processed for shorter bonding-time interval, whereas the DB processed for longer bonding-time interval fractured apparently at the middle of Cu-foil region predominantly due to the existence of brittle Cu-Fe-Ti-based intermetallics.

Experimental analysis of two-layered dissimilar metals by roll bonding

NASA Astrophysics Data System (ADS)

Zhao, Guanghui; Li, Yugui; Li, Juan; Huang, Qingxue; Ma, Lifeng

2018-02-01

Rolling reduction and base layers thickness have important implications for rolling compounding. A two-layered 304 stainless steel/Q345R low alloyed steel was roll bonded. The roll bonding was performed at the three thickness reductions of 25%, 40% and 55% with base layers of various thicknesses (Q345R). The microstructures of the composite were investigated by the ultra-deep microscope (OM) and scanning electron microscope (SEM) and Transmission electron microscope (TEM). Simultaneously, the mechanical properties of the composite were experimentally measured and the tensile fracture surfaces were observed by SEM. The interfaces were successfully bonded without any cracking or voids, which indicated a good fabrication of the 304/Q345R composite. The rolling reduction rate and thinning increase of the substrate contributed to the bonding effects appearance of the roll bonded sheet. The Cr and Ni enriched diffusion layer was formed by the interface elements diffusion. The Cr and Ni diffusion led to the formation of ˜10 μm wide Cr and Ni layers on the carbon steel side.

Morphology, topography, and hardness of diffusion bonded sialon to AISI 420 at different bonding time

NASA Astrophysics Data System (ADS)

Ibrahim, Nor Nurulhuda Md.; Hussain, Patthi; Awang, Mokhtar

2015-07-01

Sialon and AISI 420 martensitic stainless steel were diffusion bonded in order to study the effect of bonding time on reaction layer's growth. Joining of these materials was conducted at 1200°C under a uniaxial pressure of 17 MPa in a vacuum ranging from 5.0 to 8.0×10-6 Torr with bonding time varied for 0.5, 2, and 3 h. Thicker reaction layer was formed in longer bonded sample since the elements from sialon could diffuse further into the steel. Sialon retained its microstructure but it was affected at the initial contact with the steel to form the new interface layer. Diffusion layer grew toward the steel and it was segregated with the parent steel as a result of the difference in properties between these regions. The segregation formed a stream-like structure and its depth decreased when the bonding time was increased. The microstructure of the steel transformed into large grain size with precipitates. Prolonging the bonding time produced more precipitates in the steel and reduced the steel thickness as well. Interdiffusions of elements occurred between the joined materials and the concentrations were decreasing toward the steel and vice versa. Silicon easily diffused into the steel because it possessed lower ionization potential compared to nitrogen. Formation of silicide and other compounds such as carbides were detected in the interface layer and steel grain boundary, respectively. These compounds were harmful due to silicide brittleness and precipitation of carbides in the grain boundary might cause intergranular corrosion cracking. Sialon retained its hardness but it dropped very low at the interface layer. The absence of crack at the joint in all samples could be contributed from the ductility characteristic of the reaction layer which compensated the residual stress that was formed upon the cooling process.

Biology for the Visually Impaired Student.

ERIC Educational Resources Information Center

Cooperman, Susan

1980-01-01

This is a description of a beginning college biology course for visually impaired students. Equipment for instruction is discussed and methods for using the materials are included. Topics included in the course are chemical bonding, diffusion and osmosis, cell structure, meiosis and mitosis, reproduction, behavior, nutrition, and circulation. (SA)

Silver plating ensures reliable diffusion bonding of dissimilar metals

NASA Technical Reports Server (NTRS)

1967-01-01

Dissimilar metals are reliably joined by diffusion bonding when the surfaces are electroplated with silver. The process involves cleaning and etching, anodization, silver striking, and silver plating with a conventional plating bath. It minimizes the formation of detrimental intermetallic phases and provides greater tolerance of processing parameters.

Diffusion bonding between W and EUROFER97 using V interlayer

NASA Astrophysics Data System (ADS)

Basuki, Widodo Widjaja; Aktaa, Jarir

2012-10-01

Diffusion bonding is selected to join W to EUROFER97 for the manufacturing of some components in the fusion technology. A direct bonding does not seem feasible due to the high interfacial residual stress induced by the large mismatch of the coefficient of thermal expansions of both materials to be bonded. To reduce the residual stress, a V plate with a thickness of 1 mm was introduced as an interlayer. The diffusion bonding was conducted at 1050 °C for 1 h. The uniaxial applied compression stress was calculated considering the 5% allowable creep deformation on the EUROFER97's side. Investigations on bonded specimens showed defect free interfaces. Microstructure alterations were detected just at the EUROFER97/V interface. A very hard layer assumed to be a σ phase with a thickness of about 4 μm was found on the EUROFER97's side along the bond interface. A 6 μm carbide layer containing V2C with also a high hardness value was identified on the V interlayer's side. The impact toughness of the bonded specimens was low, however comparable to that of tungsten especially if the specimens were tested at RT. Tensile test at 550 °C showed a relatively high tensile strength of bonded specimens, which achieved about 50% of the tensile strength of EUROFER97.

The rate constant of a quantum-diffusion-controlled bimolecular reaction

NASA Astrophysics Data System (ADS)

Bondarev, B. V.

1986-04-01

A quantum-mechanical equation is derived in the tight-bond approximation which describes the motion and chemical interaction of a pair of species A and B when their displacement in the matrix is caused by tunnelling. Within the framework of the discrete model of random walks, definitions are given of the probability and rate constant of a reaction A + B → P (products) proceeding in a condensed medium. A method is suggested for calculating the rate constant of a quantum-diffusion-controlled bimolecular reaction. By this method, an expression is obtained for the rate constant in the stationary spherically symmetrical case. An equation for the density matrix is also proposed which describes the motion and chemical interaction of a pair of species when the quantum and classical diffusion are competitive.

Thermal Diffusivity Measurement for Thermal Spray Coating Attached to Substrate Using Laser Flash Method

NASA Astrophysics Data System (ADS)

Akoshima, Megumi; Tanaka, Takashi; Endo, Satoshi; Baba, Tetsuya; Harada, Yoshio; Kojima, Yoshitaka; Kawasaki, Akira; Ono, Fumio

2011-11-01

Ceramic-based thermal barrier coatings are used as heat and wear shields of gas turbine blades. There is a strong need to evaluate the thermal conductivity of coating for thermal design and use. The thermal conductivity of a bulk material is obtained as the product of thermal diffusivity, specific heat capacity, and density above room temperature in many cases. Thermal diffusivity and thermal conductivity are unique for a given material because they are sensitive to the structure of the material. Therefore, it is important to measure them in each sample. However it is difficult to measure the thermal diffusivity and thermal conductivity of coatings because coatings are attached to substrates. In order to evaluate the thermal diffusivity of a coating attached to the substrate, we have examined the laser flash method with the multilayer model on the basis of the response function method. We carried out laser flash measurements in layered samples composed of a CoNiCrAlY bond coating and a 8YSZ top coating by thermal spraying on a Ni-based superalloy substrate. It was found that the procedure using laser flash method with the multilayer model is useful for the thermal diffusivity evaluation of a coating attached to a substrate.

Experimental Design for Evaluation of Co-extruded Refractory Metal/Nickel Base Superalloy Joints

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

ME Petrichek

2005-12-16

Prior to the restructuring of the Prometheus Program, the NRPCT was tasked with delivering a nuclear space reactor. Potential NRPCT nuclear space reactor designs for the Prometheus Project required dissimilar materials to be in contact with each other while operating at extreme temperatures under irradiation. As a result of the high reactor core temperatures, refractory metals were the primary candidates for many of the reactor structural and cladding components. They included the tantalum-base alloys ASTAR-811C and Ta-10W, the niobium-base alloy FS-85, and the molybdenum base alloys Moly 41-47.5 Rhenium. The refractory metals were to be joined to candidate nickel basemore » alloys such as Haynes 230, Alloy 617, or Nimonic PE 16 either within the core if the nickel-base alloys were ultimately selected to form the outer core barrel, or at a location exterior to the core if the nickel-base alloys were limited to components exterior to the core. To support the need for dissimilar metal joints in the Prometheus Project, a co-extrusion experiment was proposed. There are several potential methods for the formation of dissimilar metal joints, including explosive bonding, friction stir welding, plasma spray, inertia welding, HIP, and co-extrusion. Most of these joining methods are not viable options because they result in the immediate formation of brittle intermetallics. Upon cooling, intermetallics form in the weld fusion zone between the joined metals. Because brittle intermetallics do not form during the initial bonding process associated with HIP, co-extrusion, and explosive bonding, these three joining procedures are preferred for forming dissimilar metal joints. In reference to a Westinghouse Astronuclear Laboratory report done under a NASA sponsored program, joints that were fabricated between similar materials via explosive bonding had strengths that were directly affected by the width of the diffusion barrier. It was determined that the diffusion zone should not exceed a critical thickness (0.0005 in.). A diffusion barrier that exceeded this thickness would likely fail. The joint fabrication method must therefore mechanically bond the two materials causing little or no interdiffusion upon formation. Co-extrusion fits this description since it forms a mechanical joint between two materials by using heat and pressure. The two materials to be extruded are first assembled and sealed within a co-extrusion billet which is subsequently heated and then extruded through a die. For a production application, once the joint is formed, it is dejacketed to remove the outer canister. The remaining piece consists of two materials bonded together with a thin diffusion barrier. Therefore, the long-term stability of the joint is determined primarily by the kinetics of interdiffusion reaction between the two materials. An experimental design for co-extrusion of refractory metals and nickel-based superalloys was developed to evaluate this joining process and determine the long-term stability of the joints.« less

Fabrication of high aspect grating using bonded substrate for X-ray refraction imaging by Talbot-Lau interferometer

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

Tada, Takuji; Murakoshi, Dai; Ishii, Hiroyasu

2012-07-31

In order to improve the image quality of X-ray refraction images using a Talbot-Lau interferometer, we have been attempting to fabricate gratings with high aspect ratio. In our attempt, deep grooves of grating structure were channeled on a Si substrate bonded by Au diffusion bonding method, and the grooves were filled with Au where the Au layer used for the bonding Si substrate was acting as a seed layer of Au electroplating. From the results of a visibility measurement and a cross sectional SEM image, it was confirmed that the grooves with a pitch of 5.8 {mu}m and a depthmore » of 100 {mu}m could be successfully filled with Au over a large area of 72 Multiplication-Sign 80 mm{sup 2}. Using this grating, the X-ray refraction images for the cartilage of a knee joint of a livestock pig could be obtained where SPS method was employed for the single-shot image acquisition.« less

Diffusion bonding of titanium to 304 stainless steel

NASA Astrophysics Data System (ADS)

Ghosh, M.; Bhanumurthy, K.; Kale, G. B.; Krishnan, J.; Chatterjee, S.

2003-11-01

Diffusion bonding between commercially pure titanium and an austenitic stainless steel (AISI 304) has been carried out in the temperature range of 850-950 °C for 2 h at uniaxial pressure of 3 MPa in vacuum. The microstructure of the diffusion zone has been analysed by optical and scanning electron microscopy (SEM). The interdiffusion of the diffusing species across the interface has been evaluated by electron probe microanalysis (EPMA). The reaction products formed at the interface have been identified by X-ray diffraction technique. It has been observed that the diffusion zone is dominated by the presence of the σ phase close to the stainless steel side and the solid solution of β-Ti (solutes are Fe, Cr and Ni) close to the titanium. The presence of Fe 2Ti and FeTi has been found in the reaction zone. It has been observed that the bond strength (˜222 MPa) is highest for the couple processed at 850 °C and this value decreases with rise in joining temperature. The variation of strength of the transition joints is co-related with the microstructural characteristics of the diffusion zone.

Diffusion anisotropy of poor metal solute atoms in hcp-Ti

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

Scotti, Lucia, E-mail: lxs234@bham.ac.uk; Mottura, Alessandro, E-mail: a.mottura@bham.ac.uk

2015-05-28

Atom migration mechanisms influence a wide range of phenomena: solidification kinetics, phase equilibria, oxidation kinetics, precipitation of phases, and high-temperature deformation. In particular, solute diffusion mechanisms in α-Ti alloys can help explain their excellent high-temperature behaviour. The purpose of this work is to study self- and solute diffusion in hexagonal close-packed (hcp)-Ti, and its anisotropy, from first-principles using the 8-frequency model. The calculated diffusion coefficients show that diffusion energy barriers depend more on bonding characteristics of the solute rather than the size misfit with the host, while the extreme diffusion anisotropy of some solute elements in hcp-Ti is a resultmore » of the bond angle distortion.« less

Introduction to Shaped Charges

DTIC Science & Technology

2007-03-01

Figure 144. Late time collapse of a hemispherical depleted uranium liner. COPPER 430MM(17") LEAD-TIN EUTECTIC Figure 145. Comparison between...46 Figure 91. Setup for diffusion bonding of copper- nickel assemblies, temperature is 982 °C, time is 1–3 hr, argon atmosphere...46 Figure 92. Diffusion-bonded alternately layered copper- nickel

The effect of silicon on the interaction between metallic uranium and aluminum: A 50 year long diffusion experiment

NASA Astrophysics Data System (ADS)

Leenaers, A.; Detavernier, C.; Van den Berghe, S.

2008-11-01

The core of the BR1 research reactor at SCK•CEN, Mol (Belgium) has a graphite matrix loaded with fuel rods consisting of a natural uranium slug in aluminum cladding. The BR1 reactor has been in operation since 1956 and still contains its original fuel rods. After more than 50 years irradiation at low temperature, some of the fuel rods have been examined. Fabrication reports indicate that a so-called AlSi bonding layer and an U(Al,Si) 3 anti-diffusion layer on the natural uranium fuel slug were applied to limit the interaction between the uranium fuel and aluminum cladding. The microstructure of the fuel, bonding and anti-diffusion layer and cladding were analysed using optical microscopy, scanning electron microscopy and electron microprobe analysis. It was found that the AlSi bonding layer does provide a tight bond between fuel and cladding but that it is a thin USi layer that acts as effective anti-diffusion layer and not the intended U(Al,Si) 3 layer.

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

Ranjan, Devesh

Diffusion bonded heat exchangers are the leading candidates for the sCO 2 Brayton cycles in next generation nuclear power plants. Commercially available diffusion bonded heat exchangers utilize set of continuous semi-circular zigzag micro channels to increase the heat transfer area and enhance heat transfer through increased turbulence production. Such heat exchangers can lead to excessive pressure drop as well as flow maldistribution in the case of poorly designed flow distribution headers. The goal of the current project is to fabricate and test potential discontinuous fin patterns for diffusion bonded heat exchangers; which can achieve desired thermal performance at lower pressuremore » drops. Prototypic discontinuous offset rectangular and Airfoil fin surface geometries were chemically etched on to 316 stainless steel plate and sealed against an un-etched flat pate using O-ring seal emulating diffusion bonded heat exchangers. Thermal-hydraulic performance of these prototypic discontinuous fin geometries was experimentally evaluated and compared to the existing data for the continuous zigzag channels. The data generated from this project will serve as the database for future testing and validation of numerical models.« less

Boson peak and Ioffe-Regel criterion in amorphous siliconlike materials: The effect of bond directionality.

PubMed

Beltukov, Y M; Fusco, C; Parshin, D A; Tanguy, A

2016-02-01

The vibrational properties of model amorphous materials are studied by combining complete analysis of the vibration modes, dynamical structure factor, and energy diffusivity with exact diagonalization of the dynamical matrix and the kernel polynomial method, which allows a study of very large system sizes. Different materials are studied that differ only by the bending rigidity of the interactions in a Stillinger-Weber modelization used to describe amorphous silicon. The local bending rigidity can thus be used as a control parameter, to tune the sound velocity together with local bonds directionality. It is shown that for all the systems studied, the upper limit of the Boson peak corresponds to the Ioffe-Regel criterion for transverse waves, as well as to a minimum of the diffusivity. The Boson peak is followed by a diffusivity's increase supported by longitudinal phonons. The Ioffe-Regel criterion for transverse waves corresponds to a common characteristic mean-free path of 5-7 Å (which is slightly bigger for longitudinal phonons), while the fine structure of the vibrational density of states is shown to be sensitive to the local bending rigidity.

The Effects of Borides on the Mechanical Properties of TLPB Repaired Inconel 738 Superalloy

NASA Astrophysics Data System (ADS)

Wei, J.; Ye, Y.; Sun, Z.; Zou, G.; Bai, H.; Wu, A.; Liu, L.

2017-10-01

The transient liquid phase diffusion bonding (TLPB) method was used to repair an artificial crack in Inconel 738, which was notched by a femtosecond laser. Mixed ratios of BNi-1a:DF-4B were investigated at the bonding temperature of 1373 K (1100 °C) for 2 to 36 hours. The effect of borides on the mechanical properties of TLPB repaired joints was studied through analysis of the microstructure, fracture path, and morphology observations. The borides formation, morphology, distribution, and joints strength were studied in detail. The results showed that the diffusion of B can either increase or decrease the joint strength, depending on its distribution and morphology. The amount of large blocky Ni-B compounds in the precipitate zone were reduced with increasing holding time, which resulted in an increase in joint strength. Nevertheless, further increasing the holding time led to a decrease in joint strength because of the formation of continuous acicular borides in the diffusion-affected zone. The fracture modes of TLPB joints were also discussed on the basis of the microstructure and fractography.

Transient Liquid-Phase Diffusion Bonding of Aluminum Metal Matrix Composite Using a Mixed Cu-Ni Powder Interlayer

NASA Astrophysics Data System (ADS)

Maity, Joydeep; Pal, Tapan Kumar

2012-07-01

In the present study, the transient liquid-phase diffusion bonding of an aluminum metal matrix composite (6061-15 wt.% SiCp) has been investigated for the first time using a mixed Cu-Ni powder interlayer at 560 °C, 0.2 MPa, for different holding times up to 6 h. The microstructure of the isothermally solidified zone contains equilibrium precipitate CuAl2, metastable precipitate Al9Ni2 in the matrix of α-solid solution along with the reinforcement particles (SiC). On the other hand, the microstructure of the central bond zone consists of equilibrium phases such as NiAl3, Al7Cu4Ni and α-solid solution along with SiC particles (without any segregation) and the presence of microporosities. During shear test, the crack originates from microporosities and propagates along the interphase interfaces resulting in poor bond strength for lower holding times. As the bonding time increases, with continual diffusion, the structural heterogeneity is diminished, and the microporosities are eliminated at the central bond zone. Accordingly, after 6-h holding, the microstructure of the central bond zone mainly consists of NiAl3 without any visible microporosity. This provides a joint efficiency of 84% with failure primarily occurring through decohesion at the SiC particle/matrix interface.

Preparation and testing of corrosion and spallation-resistant coatings

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

Hurley, John P.; Cavalli, Matthew N.

2016-06-30

The goal of this project was to take a recently developed method of bonding oxide dispersion-strengthened (ODS) FeCrAl plating to nickel superalloys closer to commercial use in syngas-fired turbines. The project was designed to better understand and develop the bonding process and to determine if plating APMT®, a specific highly oxidation-resistant ODS FeCrAl alloy made by Kanthal, onto nickel-based superalloy turbine parts is a viable method for substantially improving the lifetimes and maximum use temperatures of the parts. The superalloys investigated for protection were CM247LC and Rene® 80, both alumina scale-forming alloys. The method for bonding the APMT plate tomore » the superalloys is called evaporative metal bonding, which involves placing a thin foil of zinc between the plate and the superalloy, clamping them together, and heating in an atmosphere-controlled furnace. Upon heating, the zinc melts and dissolves the oxide skins of the alloys at the bond line, allowing the two alloys to diffuse into each other. The zinc then diffuses through the alloys and evaporates from their surfaces, creating a bond between the APMT and the superalloy that is stronger than the APMT itself. Testing showed that the diffusivity of zinc in both APMT and CM247LC is quite similar at 700°C but 15 times higher in the APMT at 1214°C. Coefficients of thermal expansion were determined for each of the alloys as a function of temperature. This information was entered into a finite-element model using ANSYS, which was used to design a clamping jig for pressing the APMT to the superalloys at the bonding temperature. Scanning electron microscopy analyses of representative joints showed that no zinc remained in the alloys after bonding Unfortunately, the analyses also showed some small pieces of broken aluminum oxide scale near the bond lines, indicating that its scale was not sufficiently removed during prebonding cleaning. Samples from each of the bonded blocks were sent to Siemens for its standard oxidation, spallation, and corrosion testing, which was scheduled for completion in the spring of 2016. However, because of commercial demands, the tests were not completed by the time of this report except some initial spallation tests at 1150°C. In those tests, several of the APMT plates separated from the CM247LC, likely because of the remaining aluminum oxide scale on the surface of the CM247LC. This implies that surface preparation may need to include machining to remove the oxide scale before bonding rather than just sandblasting. In previous tensile testing at 950°C, the breaks in the tensile samples always occurred in the APMT and not at the joints. Gasifier sampling was completed to determine what types of trace contaminants may occur in cleaned and combusted syngas and that could lead to corrosion or deposition in turbines firing coal syngas. The sampling was done from a pressurized fluidized-bed gasifier and a pressurized entrained-flow gasifier. The particles captured on a filter from syngas were typically 0.2 to 0.5 μm in diameter, whereas those captured from the combusted syngas were slightly larger and more spherical. X-ray photoelectron spectroscopy done at Oak Ridge National Laboratory showed that the particles do not contain any metals and have an atomic composition almost identical to that of the polycarbonate filter. This indicates that the particles are primarily soot-based and not formed from volatilization of metals in the gasifiers.« less

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

Chen, Yinshan; Zhu, Men; Laventure, Audrey

Surface grating decay measurements have been performed on three closely related molecular glasses to study the effect of intermolecular hydrogen bonds on surface diffusion. The three molecules are derivatives of bis(3,5-dimethyl-phenylamino)-1,3,5-triazine and differ only in the functional group R at the 2-position, with R being C 2H 5, OCH 3, and NHCH 3, and referred to as “Et”, “OMe”, and “NHMe”, respectively. Of the three molecules, NHMe forms more extensive intermolecular hydrogen bonds than Et and OMe and was found to have slower surface diffusion. For Et and OMe, surface diffusion is so fast that it replaces viscous flow asmore » the mechanism of surface grating decay as temperature is lowered. In contrast, no such transition was observed for NHMe under the same conditions, indicating significantly slower surface diffusion. This result is consistent with the previous finding that extensive intermolecular hydrogen bonds slow down surface diffusion in molecular glasses and is attributed to the persistence of hydrogen bonds even in the surface environment. Here, this result is also consistent with the lower stability of the vapor-deposited glass of NHMe relative to those of Et and OMe and supports the view that surface mobility controls the stability of vapor-deposited glasses.« less

Application of superplastically formed and diffusion bonded aluminum to a laminar flow control leading edge

NASA Technical Reports Server (NTRS)

Goodyear, M. D.

1987-01-01

NASA sponsored the Aircraft Energy Efficiency (ACEE) program in 1976 to develop technologies to improve fuel efficiency. Laminar flow control was one such technology. Two approaches for achieving laminar flow were designed and manufactured under NASA sponsored programs: the perforated skin concept used at McDonnell Douglas and the slotted design used at Lockheed-Georgia. Both achieved laminar flow, with the slotted design to a lesser degree (JetStar flight test program). The latter design had several fabrication problems concerning springback and adhesive flow clogging the air flow passages. The Lockheed-Georgia Company accomplishments is documented in designing and fabricating a small section of a leading edge article addressing a simpler fabrication method to overcome the previous program's manufacturing problems, i.e., design and fabrication using advanced technologies such as diffusion bonding of aluminum, which has not been used on aerospace structures to date, and the superplastic forming of aluminum.

The effect of diffuse basis functions on valence bond structural weights

NASA Astrophysics Data System (ADS)

Galbraith, John Morrison; James, Andrew M.; Nemes, Coleen T.

2014-03-01

Structural weights and bond dissociation energies have been determined for H-F, H-X, and F-X molecules (-X = -OH, -NH2, and -CH3) at the valence bond self-consistent field (VBSCF) and breathing orbital valence bond (BOVB) levels of theory with the aug-cc-pVDZ and 6-31++G(d,p) basis sets. At the BOVB level, the aug-cc-pVDZ basis set yields a counterintuitive ordering of ionic structural weights when the initial heavy atom s-type basis functions are included. For H-F, H-OH, and F-X, the ordering follows chemical intuition when these basis functions are not included. These counterintuitive weights are shown to be a result of the diffuse polarisation function on one VB fragment being spatially located, in part, on the other VB fragment. Except in the case of F-CH3, this problem is corrected with the 6-31++G(d,p) basis set. The initial heavy atom s-type functions are shown to make an important contribution to the VB orbitals and bond dissociation energies and, therefore, should not be excluded. It is recommended to not use diffuse basis sets in valence bond calculations unless absolutely necessary. If diffuse basis sets are needed, the 6-31++G(d,p) basis set should be used with caution and the structural weights checked against VBSCF values which have been shown to follow the expected ordering in all cases.

Using Diffusion Bonding in Making Piezoelectric Actuators

NASA Technical Reports Server (NTRS)

Sager, Frank E.

2003-01-01

A technique for the fabrication of piezoelectric actuators that generate acceptably large forces and deflections at relatively low applied voltages involves the stacking and diffusion bonding of multiple thin piezoelectric layers coated with film electrodes. The present technique stands in contrast to an older technique in which the layers are bonded chemically, by use of urethane or epoxy agents. The older chemical-bonding technique entails several disadvantages, including the following: It is difficult to apply the bonding agents to the piezoelectric layers. It is difficult to position the layers accurately and without making mistakes. There is a problem of disposal of hazardous urethane and epoxy wastes. The urethane and epoxy agents are nonpiezoelectric materials. As such, they contribute to the thickness of a piezoelectric laminate without contributing to its performance; conversely, for a given total thickness, the performance of the laminate is below that of a unitary piezoelectric plate of the same thickness. The figure depicts some aspects of the fabrication of a laminated piezoelectric actuator by the present diffusion- bonding technique. First, stock sheets of the piezoelectric material are inspected and tested. Next, the hole pattern shown in the figure is punched into the sheets. Alternatively, if the piezoelectric material is not a polymer, then the holes are punched in thermoplastic films. Then both faces of each punched piezoelectric sheet or thermoplastic film are coated with a silver-ink electrode material by use of a silkscreen printer. The electrode and hole patterns are designed for minimal complexity and minimal waste of material. After a final electrical test, all the coated piezoelectric layers (or piezoelectric layers and coated thermoplastic films) are stacked in an alignment jig, which, in turn, is placed in a curved press for the diffusion-bonding process. In this process, the stack is pressed and heated at a specified curing temperature and pressure for a specified curing time. The pressure, temperature, and time depend on the piezoelectric material selected. At the end of the diffusion-bonding process, the resulting laminated piezoelectric actuator is tested to verify the adequacy of the mechanical output as a function of an applied DC voltage.

X-Ray Fluorescence Solvent Detection at the Substrate-Adhesive Interface

NASA Technical Reports Server (NTRS)

Wurth, Laura; Evans, Kurt; Weber, Bart; Headrick, Sarah

2005-01-01

With environmental regulations limiting the use of volatile organic compounds, low-vapor pressure solvents have replaced traditional degreasing solvents for bond substrate preparation. When used to clean and prepare porous bond substrates such as phenolic composites, low vapor pressure solvents can penetrate deep into substrate pore networks and remain there for extended periods. Trapped solvents can interact with applied adhesives either prior to or during cure, potentially compromising bond properties. Currently, methods for characterizing solvent time-depth profiles in bond substrates are limited to bulk gravimetric or sectioning techniques. While sectioning techniques such as microtome allow construction of solvent depth profiles, their depth resolution and reliability are limited by substrate type. Sectioning techniques are particularly limited near the adhesive-substrate interface where depth resolution is further limited by adhesive-substrate hardness and, in the case of a partially cured adhesive, mechanical properties differences. Additionally, sectioning techniques cannot provide information about lateral solvent diffusion. Cross-section component mapping is an alternative method for measuring solvent migration in porous substrates that eliminates the issues associated with sectioning techniques. With cross-section mapping, the solvent-wiped substrate is sectioned perpendicular rather than parallel to the wiped surface, and the sectioned surface is analyzed for the solvent or solvent components of interest using a two-dimensional mapping or imaging technique. Solvent mapping can be performed using either direct or indirect methods. With a direct method, one or more solvent components are mapped using red or Raman spectroscopy together with a moveable sample stage and/or focal plane array detector. With an indirect method, an elemental "tag" not present in the substrate is added to the solvent before the substrate is wiped. Following cross sectioning, the tag element can then be mapped by its characteristic x-ray emission using either x-ray fluorescence, or electron-beam energy-and wavelength-dispersive x-ray spectrometry. The direct mapping techniques avoid issues of different diffusion or migration rates of solvents and elemental tags, while the indirect techniques avoid spectral resolution issues in cases where solvents and substrates have adjacent or overlapping peaks. In this study, cross-section component indirect mapping is being evaluated as a method for measuring migration of d-limonene based solvents in glass-cloth phenolic composite (GCP) prior to and during subsequent bonding and epoxy adhesive cure.

Effect of a microstructure and surface hydrogen alloying of a VT6 alloy on diffusion welding

NASA Astrophysics Data System (ADS)

Senkevich, K. S.; Skvortsova, S. V.; Kudelina, I. M.; Knyazev, M. I.; Zasypkin, V. V.

2014-01-01

The effect of a structural type (lamellar, fine, gradient) and additional surface alloying with hydrogen on the diffusion bonding of titanium alloy VT6 samples is studied. It is shown that the surface alloying of VT6 alloy parts with hydrogen allows one to decrease the diffusion welding temperature by 50-100°C, to obtain high-quality pore-free bonding, and to remove the "structural" boundary between materials to be welded that usually forms during welding of titanium alloys with a lamellar structure.

Kinetic Monte Carlo Simulations of Diffusion in Environmental Barrier Coating Materials

NASA Technical Reports Server (NTRS)

Good, Brian

2017-01-01

Ceramic Matrix Components (CMC) components for use in turbine engines offer a number of advantages compared with current practice. However, such components are subject to degradation through a variety of mechanisms. In particular, in the hot environment inside a turbine in operation a considerable amount of water vapor is present, and this can lead to corrosion and recession. Environmental Barrier Coating (EBC) systems that limit the amount of oxygen and water reaching the component are required to reduce this degradation and extend component life. A number of silicate-based materials are under consideration for use in such coating systems, including Yttterbium and Yttrium di- and monosilicates. In this work, we present results of kinetic Monte Carlo computer simulations of oxygen diffusion in Yttrium disilicate, and compare with previous work on Yttterbium disilicate. Coatings may also exhibit cracking, and the cracks can provide a direct path for oxygen to reach the component. There is typically a bond coat between the coating and component surface, but the bond coat material is generally chosen for properties other than low oxygen diffusivity. Nevertheless, the degree to which the bond coat can inhibit oxygen diffusion is of interest, as it may form the final defense against oxygen impingement on the component. We have therefore performed similar simulations of oxygen diffusion through HfSiO4, a proposed bond coat material.

Non-opioid analgesic drug flupirtine: Spectral analysis, DFT computations, in vitro bioactivity and molecular docking study

NASA Astrophysics Data System (ADS)

Leenaraj, D. R.; Hubert Joe, I.

2017-06-01

Spectral features of non-opioid analgesic drug flupirtine have been explored by the Fourier transform infrared, Raman and Nuclear magnetic resonance spectroscopic techniques combined with density functional theory computations. The bioactive conformer of flupirtine is stabilized by an intramolecular Csbnd H⋯N hydrogen bonding resulting by the steric strain of hydrogen atoms. Natural bond orbital and natural population analysis support this result. The charge redistribution also has been analyzed. Antimicrobial activities of flupirtine have been screened by agar well disc diffusion and molecular docking methods, which exposes the importance of triaminopyridine in flupirtine.

Measurement of diffusion coefficients of parabens and steroids in water and 1-octanol.

PubMed

Seki, Toshinobu; Mochida, Junko; Okamoto, Maiko; Hosoya, Osamu; Juni, Kazuhiko; Morimoto, Kazuhiro

2003-06-01

Diffusion coefficients (D) of parabens and steroids in water and 1-octanol were determined by using the chromatographic broadening method at 37 degrees C, and the relationships between the D values and the physicochemical properties of the drugs were discussed. The D values in 1-octanol were lower than those in water because of the higher viscosity of 1-octanol. The D values depend on not only the molecular weight (MW), but also the lipophilicity of the drugs in water and on the ability for hydrogen-bonding in 1-octanol. When the lipophilic index (LI), calculated from the retention time using in a reverse-phase column, was used as a parameter of drug lipophilicity, the following equation was obtained for D in water (D(w)); log D(w)=-0.215.log MW-0.077.log LI-4.367. When the hydrogen bond index (HI), the logarithm of the ratio of the partition coefficient of the drugs in 1-octanol and cyclohexane, was used as an index of hydrogen-bonding, the following equation was obtained for D in 1-octanol (D(o)); log D(o)=-0.690.log MW-0.074.log HI-4.085.

Enantioselective Cyanation of Benzylic C–H Bonds via Copper-Catalyzed Radical Relay

PubMed Central

Zhang, Wen; Wang, Fei; McCann, Scott D.; Wang, Dinghai; Chen, Pinhong; Stahl, Shannon; Liu, Guosheng

2017-01-01

Direct methods for stereoselective functionalization of C(sp3)–H bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp3)–CN bond upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90-99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. Mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and C–H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways. PMID:27701109

Supramolecular architecture based on [Fe(CN)6]3- metallotectons and melaminium synthons

NASA Astrophysics Data System (ADS)

Krichen, Firas; Walha, Siwar; Lhoste, Jérôme; Bulou, Alain; Kabadou, Ahlem; Goutenoire, François

2017-10-01

Assembly involving [Fe(CN)6]3- metallotectons as building units and melaminium organic cation has been envisioned in order to elaborate a hybrid supramolecular based on ionic H-bonds with formula {(H-mel)4[Fe(CN)6]Cl} (H-mel+: melaminium cation). The compound has been prepared by diffusion method and characterized by single-crystal X-ray diffraction, EDX analysis, and Raman-IR spectroscopies with assignment from ab initio calculations. The melaminium exhibit self cationic coupling with cyclic hydrogen bonds to give a one dimensional {[H-mel]+}∝ synthon. Therefore, these cationic ribbons are inter-linked via hydrogen bonds by the anionic tectons [Fe(CN)6]3- and chlorine anion resulting on a 3D network. Molecular hirshfeld surfaces revealed that the crystal structure has been supported mainly by Nsbnd H⋯N and Nsbnd H⋯Cl intermolecular Hydrogen bonds and by favoured C⋯C and C⋯N weak interactions.

Direct, CMOS In-Line Process Flow Compatible, Sub 100 °C Cu-Cu Thermocompression Bonding Using Stress Engineering

NASA Astrophysics Data System (ADS)

Panigrahi, Asisa Kumar; Ghosh, Tamal; Kumar, C. Hemanth; Singh, Shiv Govind; Vanjari, Siva Rama Krishna

2018-05-01

Diffusion of atoms across the boundary between two bonding layers is the key for achieving excellent thermocompression Wafer on Wafer bonding. In this paper, we demonstrate a novel mechanism to increase the diffusion across the bonding interface and also shows the CMOS in-line process flow compatible Sub 100 °C Cu-Cu bonding which is devoid of Cu surface treatment prior to bonding. The stress in sputtered Cu thin films was engineered by adjusting the Argon in-let pressure in such a way that one film had a compressive stress while the other film had tensile stress. Due to this stress gradient, a nominal pressure (2 kN) and temperature (75 °C) was enough to achieve a good quality thermocompression bonding having a bond strength of 149 MPa and very low specific contact resistance of 1.5 × 10-8 Ω-cm2. These excellent mechanical and electrical properties are resultant of a high quality Cu-Cu bonding having grain growth between the Cu films across the boundary and extended throughout the bonded region as revealed by Cross-sectional Transmission Electron Microscopy. In addition, reliability assessment of Cu-Cu bonding with stress engineering was demonstrated using multiple current stressing and temperature cycling test, suggests excellent reliable bonding without electrical performance degradation.

Fabrication of All-SiC Fiber-Optic Pressure Sensors for High-Temperature Applications

PubMed Central

Jiang, Yonggang; Li, Jian; Zhou, Zhiwen; Jiang, Xinggang; Zhang, Deyuan

2016-01-01

Single-crystal silicon carbide (SiC)-based pressure sensors can be used in harsh environments, as they exhibit stable mechanical and electrical properties at elevated temperatures. A fiber-optic pressure sensor with an all-SiC sensor head was fabricated and is herein proposed. SiC sensor diaphragms were fabricated via an ultrasonic vibration mill-grinding (UVMG) method, which resulted in a small grinding force and low surface roughness. The sensor head was formed by hermetically bonding two layers of SiC using a nickel diffusion bonding method. The pressure sensor illustrated a good linearity in the range of 0.1–0.9 MPa, with a resolution of 0.27% F.S. (full scale) at room temperature. PMID:27763494

Fabrication of All-SiC Fiber-Optic Pressure Sensors for High-Temperature Applications.

PubMed

Jiang, Yonggang; Li, Jian; Zhou, Zhiwen; Jiang, Xinggang; Zhang, Deyuan

2016-10-17

Single-crystal silicon carbide (SiC)-based pressure sensors can be used in harsh environments, as they exhibit stable mechanical and electrical properties at elevated temperatures. A fiber-optic pressure sensor with an all-SiC sensor head was fabricated and is herein proposed. SiC sensor diaphragms were fabricated via an ultrasonic vibration mill-grinding (UVMG) method, which resulted in a small grinding force and low surface roughness. The sensor head was formed by hermetically bonding two layers of SiC using a nickel diffusion bonding method. The pressure sensor illustrated a good linearity in the range of 0.1-0.9 MPa, with a resolution of 0.27% F.S. (full scale) at room temperature.

Evaluation of adhesive penetration of wood fibre by nanoindentation and microscopy

Treesearch

Christopher G. Hunt; Joseph E. Jakes; Warren Grigsby

2010-01-01

Adhesives used in wood products sometimes infiltrate, or diffuse into the solid material of, wood cell walls, potentially modifying their properties. These changes in cell wall properties are likely to impact the performance of adhesive bonds. While adhesive infiltration has been observed by multiple methods, the effect on cell wall properties is not well understood....

[The influence of surface conditioning on the shear bond strength of La-Porcelain and titanium].

PubMed

Mo, Anchun; Cen, Yuankun; Liao, Yunmao

2003-04-20

To determine the influence of different surface conditioning methods on bonding strength of low fusing porcelain (La-Porcelain) and titanium. The surface of the samples were sandblasted for 2 min with 80-250 microns Al2O3 or coated for two times with Si-couple agent or conditioned by pre-oxidation. The shear bond strength was examined by push-type shear test with a speed of 0.5 mm/min in a universal testing machine. Scanning electron microscopy (SEM) and electron probe micro-analyzer (EPMA) were employed to explore the relationship between bonding strength and microstructures, as well as the element diffusion at the interface between porcelain coating and titanium when heated at 800 degrees C. Bonding strength was not statistically different (P > 0.05) after sandblasting with Al2O3 in particle size ranged from 80 microns to 250 microns. When a Si-couple agent was used, bond of porcelain to titanium was significantly lower (P < 0.05). The shear bond strength of the porcelain to the pre-oxidized titanium surface remained unchanged after heating (P > 0.05). The SEM results revealed integrity of porcelain and titanium. La-Porcelain showed a small effect of surface coarseness. Sandblasting the titanium surface with 150-180 microns Al2O3 can be recommended as a method for better bonding between La-Porcelain and titanium. The Si-couple agent coating and pre-oxidation of titanium surface is unnecessary.

Method for improving the oxidation-resistance of metal substrates coated with thermal barrier coatings

DOEpatents

Thompson, Anthony Mark; Gray, Dennis Michael; Jackson, Melvin Robert

2002-01-01

A method for providing a protective coating on a metal-based substrate is disclosed. The method involves the application of an aluminum-rich mixture to the substrate to form a discontinuous layer of aluminum-rich particles, followed by the application of a second coating over the discontinuous layer of aluminum-rich particles. Aluminum diffuses from the aluminum-rich layer into the substrate, and into any bond coat layer which is subsequently applied. Related articles are also described.

Diffusion of aqueous solutions of ionic, zwitterionic, and polar solutes

NASA Astrophysics Data System (ADS)

Teng, Xiaojing; Huang, Qi; Dharmawardhana, Chamila Chathuranga; Ichiye, Toshiko

2018-06-01

The properties of aqueous solutions of ionic, zwitterionic, and polar solutes are of interest to many fields. For instance, one of the many anomalous properties of aqueous solutions is the behavior of water diffusion in different monovalent salt solutions. In addition, solutes can affect the stabilities of macromolecules such as proteins in aqueous solution. Here, the diffusivities of aqueous solutions of sodium chloride, potassium chloride, tri-methylamine oxide (TMAO), urea, and TMAO-urea are examined in molecular dynamics simulations. The decrease in the diffusivity of water with the concentration of simple ions and urea can be described by a simple model in which the water molecules hydrogen bonded to the solutes are considered to diffuse at the same rate as the solutes, while the remainder of the water molecules are considered to be bulk and diffuse at almost the same rate as pure water. On the other hand, the decrease in the diffusivity of water with the concentration of TMAO is apparently affected by a decrease in the diffusion rate of the bulk water molecules in addition to the decrease due to the water molecules hydrogen bonded to TMAO. In other words, TMAO enhances the viscosity of water, while urea barely affects it. Overall, this separation of water molecules into those that are hydrogen bonded to solute and those that are bulk can provide a useful means of understanding the short- and long-range effects of solutes on water.

Autohesive strength development in polysulfone resin and graphite-polysulfone composites

NASA Technical Reports Server (NTRS)

Howes, Jeremy C.; Loos, Alfred C.

1988-01-01

The effects of bonding temperature and contact time on autohesive strength development in thermoplastic polysulfone resin and graphite-polysulfone composites were investigated. Two test methods were examined to measure autohesion in the neat resin samples. These included an interfacial tension test and a compact tension fracture toughness test. Autohesive strength development in fiber-reinforced composites was measured using a double cantilever beam interlaminar fracture toughness test. The results of the tests were compared with current diffusion theories explaining crack healing and welding of glassy polymers. Discrepancies between the results of the present investigation and the diffusion theories are discussed.

Antibacterial activity of resin adhesives, glass ionomer and resin-modified glass ionomer cements and a compomer in contact with dentin caries samples.

PubMed

Herrera, M; Castillo, A; Bravo, M; Liébana, J; Carrión, P

2000-01-01

A total of 103 clinical samples of carious dentin were used to study the antibacterial action of different dental resin adhesive materials (Gluma 2000, Syntac, Prisma Universal Bond 3, Scotchbond Multi-Purpose and Prime&Bond 2.0) glass ionomer cements (Ketac-Cem, Ketac-Bond, Ketac-Silver, Ketac-Fil) resin-modified glass ionomer cements (Fuji II LC, Vitremer and Vitrebond) and a compomer (Dyract). The agar plate diffusion method was used for the microbial cultures and a chlorhexidine control. The growth of the caries-producing microorganisms was effectively inhibited by the Vitremer and Vitrebond cements, and to a lesser extent by the Scotchbond Multi-Purpose adhesive system. Overall, there were statistically significant differences in the antibacterial activity of the products tested.

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.

TEM Observation of the Ti Interlayer Between SiC Substrates During Diffusion Bonding

NASA Technical Reports Server (NTRS)

Tsuda, Hiroshi; Mori, Shigeo; Halbig, Michael C.; Singh, Mori

2012-01-01

Diffusion bonding was carried out to join SiC to SiC substrates using titanium interlayers. In this study, 10 m and 20 m thick physical vapor deposited (PVD) Ti surface coatings, and 10 and 20 m thick Ti foils were used. Diffusion bonding was performed at 1250 C for PVD Ti coatings and 1200 C for Ti foil. This study investigates the microstructures of the phases formed during diffusion bonding through TEM and selected-area diffraction analysis of a sample prepared with an FIB, which allows samples to be taken from the reacted area. In all samples, Ti3SiC2, Ti5Si3Cx and TiSi2 phases were identified. In addition, TiC and unknown phases also appeared in the samples in which Ti foils were used as interlayers. Furthermore, Ti3SiC2 phases show high concentration and Ti5Si3Cx formed less when samples were processed at a higher temperature and thinner interlayer samples were used. It appears that the formation of microcracks is caused by the presence of intermediate phase Ti5Si3Cx, which has anisotropic thermal expansion, and by the presence of an unidentified Ti-Si-C ternary phase with relatively low Si content.

Differential Microscopic Mobility of Components within a Deep Eutectic Solvent

DOE PAGES

Wagle, Durgesh V.; Baker, Gary A.; Mamontov, Eugene

2015-07-13

From macroscopic measurements of deep eutectic solvents such as glyceline (1:2 molar ratio of choline chloride to glycerol), the long-range translational diffusion of the larger cation (choline) is known to be slower compared to that of the smaller hydrogen bond donor (glycerol). However, when the diffusion dynamics are analyzed on the subnanometer length scale, we discover that the displacements associated with the localized diffusive motions are actually larger for choline. This counterintuitive diffusive behavior can be understood as follows. The localized diffusive motions confined in the transient cage of neighbor particles, which precede the cage-breaking long-range diffusion jumps, are moremore » spatially constrained for glycerol than for choline because of the stronger hydrogen bonds the former makes with chloride anions. The implications of differential localized mobility of the constituents should be especially important for applications where deep eutectic solvents are confined on the nanometer length scale and their long-range translational diffusion is strongly inhibited (e.g., within microporous media).« less

Interlaminar Toughening of Fiber Reinforced Polymers

NASA Astrophysics Data System (ADS)

Bian, Dakai

Modification in the resin-rich region between plies, also known as the interlaminar region, was investigated to increase the toughness of laminate composites structures. To achieve suitable modifications, the complexities of the physical and chemical processes during the resin curing procedure must be studied. This includes analyses of the interactions among the co-dependent microstructure, process parameters, and material responses. This dissertation seeks to investigate these interactions via a series of experimental and numerical analyses of the geometric- and temperature-based effects on locally interleaving toughening methods and further interlaminar synergistic toughening without interleaf. Two major weaknesses in composite materials are the brittle resin-rich interlaminar region which forms between the fiber plies after resin infusion, and the ply dropoff region which introduces stress concentration under loads. To address these weaknesses and increase the delamination resistance of the composite specimens, a dual bonding process was explored to alleviate the dropoff effect and toughen the interlaminar region. Hot melt bonding was investigated by applying clamping pressure to ductile thermoplastic interleaf and fiber fabric at an elevated temperature, while diffusion bonding between thermoplastic interleaf and thermoset resin is performed during the resin infusion. This method increased the fracture energy level and thus delamination resistance in the interlaminar region because of deep interleaf penetration into fiber bundles which helped confining crack propagation in the toughened area. The diffusion and precipitation between thermosets and thermoplastics also improved the delamination resistance by forming a semi-interpenetration networks. This phenomenon was investigated in concoctions of low-concentration polystyrene additive modified epoxy system, which facilitates diffusion and precipitation without increasing the viscosity of the system. Additionally, chemical reaction induced phase separation, concentration of polystyrene, and various curing temperatures are used to evaluate their effects on diffusion and precipitation. These effects were directly investigated by performing attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The diffusivity and curing kinetics experiments are performed to quantify the diffusivity coefficient of epoxy, hardener and thermoplastics, as well as the reaction rate constant of curing epoxy at various temperatures. Finally, mechanical testing and fracture surface imaging were used to quantify the improvements and characterize the toughening mechanism. Further improvement on delamination resistance was studied through the synergistic effect of combining different modification methods without the interleaf. Polysulfone molecules are end-capped with epoxide groups. Fiber surface is functionalized with amino groups to generate micro-mechanical interlocks. The interaction between two individual modifications chemically links the modified semi-interpenetration networks to the improved interfacial strength between fiber and epoxy to. The impact of the additive on the crosslinking density was examined through glass transition temperatures, and the chemical modification was characterized by Raman spectroscopy. Mode I and II fracture tests were performed to quantify the improvement of delamination resistance under pure opening and shear loads. The mechanism of synergistic effect was explained based on the fracture surface morphology and the interactions between the modification methods.

Power module packaging with double sided planar interconnection and heat exchangers

DOEpatents

Liang, Zhenxian; Marlino, Laura D.; Ning, Puqi; Wang, Fei

2015-05-26

A double sided cooled power module package having a single phase leg topology includes two IGBT and two diode semiconductor dies. Each IGBT die is spaced apart from a diode semiconductor die, forming a switch unit. Two switch units are placed in a planar face-up and face-down configuration. A pair of DBC or other insulated metallic substrates is affixed to each side of the planar phase leg semiconductor dies to form a sandwich structure. Attachment layers are disposed on outer surfaces of the substrates and two heat exchangers are affixed to the substrates by rigid bond layers. The heat exchangers, made of copper or aluminum, have passages for carrying coolant. The power package is manufactured in a two-step assembly and heating process where direct bonds are formed for all bond layers by soldering, sintering, solid diffusion bonding or transient liquid diffusion bonding, with a specially designed jig and fixture.

Development and Characterization of the Bonding and Integration Technologies Needed for Fabricating Silicon Carbide Based Injector Components

NASA Technical Reports Server (NTRS)

Halbig,Michael C.; Singh, Mrityunjay

2008-01-01

Advanced ceramic bonding and integration technologies play a critical role in the fabrication and application of silicon carbide based components for a number of aerospace and ground based applications. One such application is a lean direct injector for a turbine engine to achieve low NOx emissions. Ceramic to ceramic diffusion bonding and ceramic to metal brazing technologies are being developed for this injector application. For the diffusion bonding technology, titanium interlayers (coatings and foils) were used to aid in the joining of silicon carbide (SiC) substrates. The influence of such variables as surface finish, interlayer thickness, and processing time were investigated. Electron microprobe analysis was used to identify the reaction formed phases. In the diffusion bonds, an intermediate phase, Ti5Si3Cx, formed that is thermally incompatible in its thermal expansion and caused thermal stresses and cracking during the processing cool-down. Thinner interlayers of pure titanium and/or longer processing times resulted in an optimized microstructure. Tensile tests on the joined materials resulted in strengths of 13-28 MPa depending on the SiC substrate material. Nondestructive evaluation using ultrasonic immersion showed well formed bonds. For the joining technology of brazing Kovar fuel tubes to silicon carbide, preliminary development of the joining approach has begun. Various technical issues and requirements for the injector application are addressed.

Short-lived K2S Molecules in Superionic Potassium Sulfide

NASA Astrophysics Data System (ADS)

Okeya, Yusuke; Tsumuraya, Kazuo

2015-03-01

The first principles molecular dynamics method allows us to elucidate the formation of short-lived K2S molecular states in superionic potassium sulfide. The covalent and the Coulomb bonds exist between the ionized mobile potassiums and the ionized immobile sulfurs. Both the bonds induces indirect covalent and indirect Coulomb attractions between the di-interstitial potassiums on the mid-sulfurs, which forms the short-lived K2S molecular states. The covalent electron density also exists between short-lived potassium dimers. The three attractions reduce Haven's ratios of the potassiums in the conductor. The molecule formation indicates the electronic state of the conductor is intermediate between the ionic and covalent crystals. The absence of the long-lived potassium dimers implies a failure of the caterpillar diffusion model or the Frenkel-Kontorova chain model for the superionic diffusion of the potassiums in the sulfide. The incompletely ionized cations and anions reduce the Coulomb attractions between them which induces the sublattice melting of smaller size of the potassiums than the sulfurs.

Antibacterial Effect and Tensile Bond Strength of Self-etching Adhesive Resins with and without Methacryloyloxydodecylpyridinium Bromide: An in vitro Study.

PubMed

Krishnamurthy, Madhuram; Kumar, V Naveen; Leburu, Ashok; Dhanavel, Chakravarthy; Selvendran, Kasiswamy E; Praveen, Nehrudhas

2018-04-01

Aim: The aim of the present study was to compare the antibacterial activity of a self-etching primer containing antibacterial monomer methacryloyloxydodecylpyridinium bromide (MDPB) (Clearfil protect bond) with a conventional self-etching primer without MDPB (Clearfil SE bond) against Streptococcus mutans and the effect of incorporation of MDPB on the tensile bond strength of the experimental self-etching primer (Clearfil protect bond). Materials and methods: The antibacterial activity of the self-etching primers was assessed using agar disk diffusion method and the diameters of the zones of inhibition were measured and ranked. For tensile bond strength testing, 20 noncarious human molars were selected and randomly divided into two groups comprising 10 teeth in each group. Group I specimens were treated with Clearfil SE bond (without MDPB). Group II specimens were treated with Clearfil protect bond (with MDPB). Composite material was placed incrementally and cured for 40 seconds in all the specimens. Tensile bond strength was estimated using the Instron Universal testing machine at a crosshead speed of 1 mm/min. Results: The addition of MDPB into a self-etching primer exerts potential antibacterial effect against S. mutans. The tensile bond strength of MDPB containing self-etching primer was slightly lower than that of the conventional self-etching Clearfil protect bond primer, but the difference was not statistically significant. Conclusion: Thus, a self-etching primer containing MDPB will be a boon to adhesive dentistry as it has bactericidal property with adequate tensile bond strength. Clinical significance: The concept of prevention of extension in adhesive dentistry would result in micro/nanoleakage due to the presence of residual bacteria in the cavity. Self-etching primers with MDPB would improve the longevity of such restorations by providing adequate antibacterial activity without compromising the bond strength. Keywords: Antibacterial property, Methacryloyloxydodecy-lpyridinium bromide, Self-etching primers, Tensile bond strength.

Investigation of the feasibility of developing low permeability polymeric films

NASA Technical Reports Server (NTRS)

Hoggatt, J. T.

1971-01-01

The feasibility of reducing the gas permeability rate of Mylar and Kapton films without drastically effecting their flexibility characteristics at cryogenic temperatures was considered. This feasibility was established using a concept of diffusion bonding two layers of metallized films together forming a film-metal-film sandwich laminate. The permeability of kapton film to gaseous helium was reduced from a nominal ten = to the minus 9 power cc-mm/sq cm sec. cm Hg to ten to the minus 13 power cc-mm/ sq cm - sec. cm Hg with some values as low as ten to the minus 15 power cc - mm/sq cm m-sec - cm Hg being obtained. Similar reductions occurred in the liquid hydrogen permeability at -252 C. In the course of the program the permeability, flexibility and bond strength of plain, metalized and diffusion bond film were determined at +25 C, -195 C and -252 C. The cryogenic flexibility of Kapton film was reduced slightly due to the metallization process but no additional loss in flexibility resulted from the diffusion bonding process.

Effect of Bonding Temperature on Interfacial Reaction and Mechanical Properties of Diffusion-Bonded Joint Between Ti-6Al-4V and 304 Stainless Steel Using Nickel as an Intermediate Material

NASA Astrophysics Data System (ADS)

Thirunavukarasu, Gopinath; Kundu, Sukumar; Mishra, Brajendra; Chatterjee, Subrata

2014-04-01

An investigation was carried out on the solid-state diffusion bonding between Ti-6Al-4V (TiA) and 304 stainless steel (SS) using pure nickel (Ni) of 200- μm thickness as an intermediate material prepared in vacuum in the temperature range from 973 K to 1073 K (700 °C to 800 °C) in steps of 298 K (25 °C) using uniaxial compressive pressure of 3 MPa and 60 minutes as bonding time. Scanning electron microscopy images, in backscattered electron mode, had revealed existence of layerwise Ti-Ni-based intermetallics such as either Ni3Ti or both Ni3Ti and NiTi at titanium alloy-nickel (TiA/Ni) interface, whereas nickel-stainless steel (Ni/SS) diffusion zone was free from intermetallic phases for all joints processed. Chemical composition of the reaction layers was determined in atomic percentage by energy dispersive spectroscopy and confirmed by X-ray diffraction study. Room-temperature properties of the bonded joints were characterized using microhardness evaluation and tensile testing. The maximum hardness value of ~800 HV was observed at TiA/Ni interface for the bond processed at 1073 K (800 °C). The hardness value at Ni/SS interface for all the bonds was found to be ~330 HV. Maximum tensile strength of ~206 MPa along with ~2.9 pct ductility was obtained for the joint processed at 1023 K (750 °C). It was observed from the activation study that the diffusion rate at TiA/Ni interface is lesser than that at the Ni/SS interface. From microhardness profile, fractured surfaces and fracture path, it was demonstrated that failure of the joints was initiated and propagated apparently at the TiA/Ni interface near Ni3Ti intermetallic phase.

Laser properties of Fe2+:ZnSe fabricated by solid-state diffusion bonding

NASA Astrophysics Data System (ADS)

Balabanov, S. S.; Firsov, K. N.; Gavrishchuk, E. M.; Ikonnikov, V. B.; Kazantsev, S. Yu; Kononov, I. G.; Kotereva, T. V.; Savin, D. V.; Timofeeva, N. A.

2018-04-01

The characteristics of an Fe2+:ZnSe laser at room temperature and its active elements with undoped faces were studied. Polycrystalline elements with one or two diffusion-doped internal layers were obtained by the solid-state diffusion bonding technique applied to chemical vapor deposition grown ZnSe plates preliminary doped with Fe2+ ions in the process of hot isostatic pressing. A non-chain electric-discharge HF laser was used to pump the crystals. It was demonstrated that increasing the number of doped layers allows increasing the maximum diameter of the pump radiation spot and the pump energy without the appearance of transversal parasitic oscillation. For the two-layer-doped active element with a diameter of 20 mm an output energy of 480 mJ was achieved with 37% total efficiency with respect to the absorbed energy. The obtained results demonstrate the potential of the developed technology for fabrication of active elements by the solid-state diffusion bonding technique combined with the hot isostatic pressing treatment for efficient IR lasers based on chalcogenides doped with transition metal ions.

New Method for Super Hydrophobic Treatment of Gas Diffusion Layers for Proton Exchange Membrane Fuel Cells Using Electrochemical Reduction of Diazonium Salts.

PubMed

Thomas, Yohann R J; Benayad, Anass; Schroder, Maxime; Morin, Arnaud; Pauchet, Joël

2015-07-15

The purpose of this article is to report a new method for the surface functionalization of commercially available gas diffusion layers (GDLs) by the electrochemical reduction of diazonium salt containing hydrophobic functional groups. The method results in superhydrophobic GDLs, over a large area, without pore blocking. An X-ray photoelectron spectroscopy study based on core level spectra and chemical mapping has demonstrated the successful grafting route, resulting in a homogeneous distribution of the covalently bonded hydrophobic molecules on the surface of the GDL fibers. The result was corroborated by contact angle measurement, showing similar hydrophobicity between the grafted and PTFE-modified GDLs. The electrochemically modified GDLs were tested in proton exchange membrane fuel cells under automotive, wet, and dry conditions and demonstrated improved performance over traditional GDLs.

First Principles Study for Proton Transport and Diffusion Behavior in Hydrous Hexagonal WO3

NASA Astrophysics Data System (ADS)

Liu, Chi-Ping; Zhou, Fei; Ozolins, Vidvuds; QPAM Team

2013-03-01

Proton transport is of great importance in biological species and energy storage and conversion systems. Previous studies have shown fast proton conduction in liquids and polymers but seldom in inorganic materials. In this work, first principles density functional theory (DFT) reveals that the formation of hydronium and water chains inside the hexagonal channels plays the key roles for the anomalously fast proton transport, by following modified Grotthuss mechanism. Our DFT study shows the detailed microscopic proton diffusion mechanism along the channel in hydrous WO3 with 50% water composition, which is proper for water chain formation. The water chain in the channel serves as a possible diffusion media for hydronium (H3O +) . With the continuous formation and cleavage of hydrogen bonds in the channel, the hydronium diffuses by hydrogen bonds exchange between water molecules. This mechanism is very similar with Grotthuss relay mechanism for proton transport in liquid. The possible proton diffusion were studied for hydronium is either far away from the water chain bond defect or next to H2O defect at the end of water chain. The diffusion barriers for both conditions are around 150 meV to 200 meV, and water defects reorganization in the chain is the rate-limited step for proton diffusion. These small diffusion barriers could explain the fast 1-D proton transport in hydrous WO3 channel. Further studies about fast proton transport in other inorganic materials could be an important topic in not only biochemistry but also clean energy applications like fuel cell applications.

Superplastic forming and diffusion bonding of rapidly solidified, dispersion strengthened aluminum alloys for elevated temperature structural applications

NASA Technical Reports Server (NTRS)

Ting, E. Y.; Kennedy, J. R.

1989-01-01

Rapidly solidified alloys, based upon the Al-Fe-V-Si system and designed for elevated temperature applications, were evaluated for superplasticity and diffusion bonding behavior. Alloys with 8, 16, 27, and 36 volume percent silicide dispersoids were produced; dispersoid condition was varied by rolling at 300, 400, and 500 C (572, 752, and 932 F). Superplastic behavior was evaluated at strain rates from 1 x 10(exp -6)/s to 8.5/s at elevated temperatures. The results indicate that there was a significant increase in elongation at higher strain rates and at temperatures above 600 C (1112 F). However, the exposure of the alloys to temperatures greater than 600 C (1112 F) resulted in the coarsening of the strengthening dispersoid and the degradation of mechanical properties. Diffusion bonding was possible using low gas pressure at temperatures greater than 600 C (1112 F) which also resulted in degraded properties. The bonding of Al-Fe-V-Si alloys to 7475 aluminum alloy was performed at 516 C (960 F) without significant degradation in microstructure. Bond strengths equal to 90 percent that of the base metal shear strength were achieved. The mechanical properties and microstructural characteristics of the alloys were investigated.

Water Molecules and Hydrogen-Bonded Networks in Bacteriorhodopsin—Molecular Dynamics Simulations of the Ground State and the M-Intermediate

PubMed Central

Grudinin, Sergei; Büldt, Georg; Gordeliy, Valentin; Baumgaertner, Artur

2005-01-01

Protein crystallography provides the structure of a protein, averaged over all elementary cells during data collection time. Thus, it has only a limited access to diffusive processes. This article demonstrates how molecular dynamics simulations can elucidate structure-function relationships in bacteriorhodopsin (bR) involving water molecules. The spatial distribution of water molecules and their corresponding hydrogen-bonded networks inside bR in its ground state (G) and late M intermediate conformations were investigated by molecular dynamics simulations. The simulations reveal a much higher average number of internal water molecules per monomer (28 in the G and 36 in the M) than observed in crystal structures (18 and 22, respectively). We found nine water molecules trapped and 19 diffusive inside the G-monomer, and 13 trapped and 23 diffusive inside the M-monomer. The exchange of a set of diffusive internal water molecules follows an exponential decay with a 1/e time in the order of 340 ps for the G state and 460 ps for the M state. The average residence time of a diffusive water molecule inside the protein is ∼95 ps for the G state and 110 ps for the M state. We have used the Grotthuss model to describe the possible proton transport through the hydrogen-bonded networks inside the protein, which is built up in the picosecond-to-nanosecond time domains. Comparing the water distribution and hydrogen-bonded networks of the two different states, we suggest possible pathways for proton hopping and water movement inside bR. PMID:15731388

Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

DOE PAGES

Greathouse, Jeffery A.; Cygan, Randall T.; Fredrich, Joanne T.; ...

2016-01-20

In this study, the diffusion of water and ions in the interlayer region of smectite clay minerals represents a direct probe of the type and strength of clay–fluid interactions. Interlayer diffusion also represents an important link between molecular simulation and macroscopic experiments. Here we use molecular dynamics simulation to investigate trends in cation and water diffusion in montmorillonite interlayers, looking specifically at the effects of layer charge, interlayer cation and cation charge (sodium or calcium), water content, and temperature. For Na-montmorillonite, the largest increase in ion and water diffusion coefficients occurs between the one-layer and two-layer hydrates, corresponding to themore » transition from inner-sphere to outer-sphere surface complexes. Calculated activation energies for ion and water diffusion in Na-montmorillonite are similar to each other and to the water hydrogen bond energy, suggesting the breaking of water–water and water–clay hydrogen bonds as a likely mechanism for interlayer diffusion. A comparison of interlayer diffusion with that of bulk electrolyte solutions reveals a clear trend of decreasing diffusion coefficient with increasing electrolyte concentration, and in most cases the interlayer diffusion results are nearly coincident with the corresponding bulk solutions. Trends in electrical conductivities computed from the ion diffusion coefficients are also compared.« less

CO2 diffusion in champagne wines: a molecular dynamics study.

PubMed

Perret, Alexandre; Bonhommeau, David A; Liger-Belair, Gérard; Cours, Thibaud; Alijah, Alexander

2014-02-20

Although diffusion is considered as the main physical process responsible for the nucleation and growth of carbon dioxide bubbles in sparkling beverages, the role of each type of molecule in the diffusion process remains unclear. In the present study, we have used the TIP5P and SPC/E water models to perform force field molecular dynamics simulations of CO2 molecules in water and in a water/ethanol mixture respecting Champagne wine proportions. CO2 diffusion coefficients were computed by applying the generalized Fick's law for the determination of multicomponent diffusion coefficients, a law that simplifies to the standard Fick's law in the case of champagnes. The CO2 diffusion coefficients obtained in pure water and water/ethanol mixtures composed of TIP5P water molecules were always found to exceed the coefficients obtained in mixtures composed of SPC/E water molecules, a trend that was attributed to a larger propensity of SPC/E water molecules to form hydrogen bonds. Despite the fact that the SPC/E model is more accurate than the TIP5P model to compute water self-diffusion and CO2 diffusion in pure water, the diffusion coefficients of CO2 molecules in the water/ethanol mixture are in much better agreement with the experimental values of 1.4 - 1.5 × 10(-9) m(2)/s obtained for Champagne wines when the TIP5P model is employed. This difference was deemed to rely on the larger propensity of SPC/E water molecules to maintain the hydrogen-bonded network between water molecules and form new hydrogen bonds with ethanol, although statistical issues cannot be completely excluded. The remarkable agreement between the theoretical CO2 diffusion coefficients obtained within the TIP5P water/ethanol mixture and the experimental data specific to Champagne wines makes us infer that the diffusion coefficient in these emblematic hydroalcoholic sparkling beverages is expected to remain roughly constant whathever their proportions in sugars, glycerol, or peptides.

Interfacial characterization of SLM parts in multi-material processing: Metallurgical diffusion between 316L stainless steel and C18400 copper alloy

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

Liu, Z.H., E-mail: AZHLIU@ntu.edu.sg; Zhang, D.Q., E-mail: ZHANGDQ@ntu.edu.sg; Sing, S.L., E-mail: SING0011@e.ntu.edu.sg

2014-08-15

Multi-material processing in selective laser melting using a novel approach, by the separation of two different materials within a single dispensing coating system was investigated. 316L stainless steel and UNS C18400 Cu alloy multi-material samples were produced using selective laser melting and their interfacial characteristics were analyzed using focused ion beam, scanning electron microscopy, energy dispersive spectroscopy and electron back scattered diffraction techniques. A substantial amount of Fe and Cu element diffusion was observed at the bond interface suggesting good metallurgical bonding. Quantitative evidence of good bonding at the interface was also obtained from the tensile tests where the fracturemore » was initiated at the copper region. Nevertheless, the tensile strength of steel/Cu SLM parts was evaluated to be 310 ± 18 MPa and the variation in microhardness values was found to be gradual along the bonding interface from the steel region (256 ± 7 HV{sub 0.1}) to the copper region (72 ± 3 HV{sub 0.1}). - Highlights: • Multi-material processing was successfully implemented and demonstrated in SLM. • Bi-metallic laminates of steel/Cu were successfully produced with the SLM process. • A substantial amount of Fe and Cu diffusion was observed at the bond interface. • Good metallurgical bonding was obtained at the interface of the steel/Cu laminates. • Highly refined microstructure was obtained due to rapid solidification in SLM.« less

Vanadium diffusion coating on HT-9 cladding for mitigating the fuel cladding chemical interactions

NASA Astrophysics Data System (ADS)

Lo, Wei-Yang; Yang, Yong

2014-08-01

Fuel cladding chemical interaction (FCCI) has been identified as one of the crucial issues for developing Ferritic/Martensitic (F/M) stainless steel claddings for metallic fuels in a fast reactor. The anticipated elevated temperature and high neutron flux can significantly aggravate the FCCI, in terms of formation of inter-diffusion and lower melting point eutectic phases. To mitigate the FCCI, vanadium carbide coating as a diffusion barrier was deposited on the HT-9 substrate using a pack cementation diffusion coating (PCDC) method, and the processing temperature was optimized down to 730 °C. A solid metallurgical bonding between the coating layer and substrate was achieved, and the coating is free from through depth cracks. The microstructural characterizations using SEM and TEM show a nanostructured grain structure. EDS/WDS and XRD analysis confirm the phase of coating layer as V2C. Diffusion couple tests at 660 °C for 100 h demonstrate that V2C layer with a thickness of less than 5 μm can effectively eliminate the inter-diffusion between the lanthanide cerium and HT-9 steel.

SIEST-A-RT: a study of vacancy diffusion in crystalline silicon using a local-basis first-principle (SIESTA) activation technique (ART).

NASA Astrophysics Data System (ADS)

El Mellouhi, Fedwa; Mousseau, Normand; Ordejón, Pablo

2003-03-01

We report on a first-principle study of vacancy-induced self-diffusion in crystalline silicon. Our simulations are performed on supercells containing 63 and 215 atoms. We generate the diffusion paths using the activation-relaxation technique (ART) [1], which can sample efficiently the energy landscape of complex systems. The forces and energy are evaluated using SIESTA [2], a selfconsistent density functional method using standard norm-conserving pseudopotentials and a flexible numerical linear combination of atomic orbitals basis set. Combining these two methods allows us to identify diffusion paths that would not be reachable with this degree of accuracy, using other methods. After a full relaxation of the neutral vacancy, we proceed to search for local diffusion paths. We identify various mechanisms like the formation of the four fold coordinated defect, and the recombination of dangling bonds by WWW process. The diffusion of the vacancy proceeds by hops to first nearest neighbor with an energy barrier of 0.69 eV. This work is funded in part by NSERC and NATEQ. NM is a Cottrell Scholar of the Research Corporation. [1] G. T. Barkema and N. Mousseau, Event-based relaxation of continuous disordered systems, Phys. Rev. Lett. 77, 4358 (1996); N. Mousseau and G. T. Barkema, Traveling through potential energy landscapes of disordered materials: ART, Phys. Rev. E 57, 2419 (1998). [2] Density functional method for very large systems with LCAO basis sets D. Sánchez-Portal, P. Ordejón, E. Artacho and J. M. Soler, Int. J. Quant. Chem. 65, 453 (1997).

Nondestructive test of regenerative chambers

NASA Technical Reports Server (NTRS)

Malone, G. A.; Stauffis, R.; Wood, R.

1972-01-01

Flat panels simulating internally cooled regenerative thrust chamber walls were fabricated by electroforming, brazing and diffusion bonding to evaluate the feasibility of nondestructive evaluation techniques to detect bonds of various strength integrities. Ultrasonics, holography, and acoustic emission were investigated and found to yield useful and informative data regarding the presence of bond defects in these structures.

Diffusion bonding of Ti-48Ni-2Mn-2Nb (at.%)

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

Godfrey, S.P.; Strangwood, M.; Threadgill, P.L.

The diffusion bonding behavior of Ti-48at. % Al-2at. % Mn-2at. %Nb has been studied as a function of temperature (in the range 1,200--1,350C), time (15--45 minutes) and starting microstructure (lamellar, duplex and near {gamma}) at constant bonding pressure of 10 MPa. It was found, that under the above conditions, small twin related {gamma} grains, approximately 10-20 {mu}m in size, nucleated at the original interface and grew into the matrix forming a double necklace grain structure. Particles of {alpha}{sub 2} were observed around the interface, the formation of {alpha}{sub 2} particles was believed to be related to oxygen partitioning and stabilizationmore » effects from dissolved oxide films during the bonding process. Evidence for this mechanism was obtained from parallel electron energy loss spectroscopy (PEELS), which identified oxygen partitioning in the (X2) particles. For the fully lamellar structure bonded at 1,250 C for 45 minutes the failure strength of the bond was found to be 250 MPa, approximately 50 MPa lower than the failure strength of the base material.« less

Mesoscopic Modeling of Blood Clotting: Coagulation Cascade and Platelets Adhesion

NASA Astrophysics Data System (ADS)

Yazdani, Alireza; Li, Zhen; Karniadakis, George

2015-11-01

The process of clot formation and growth at a site on a blood vessel wall involve a number of multi-scale simultaneous processes including: multiple chemical reactions in the coagulation cascade, species transport and flow. To model these processes we have incorporated advection-diffusion-reaction (ADR) of multiple species into an extended version of Dissipative Particle Dynamics (DPD) method which is considered as a coarse-grained Molecular Dynamics method. At the continuum level this is equivalent to the Navier-Stokes equation plus one advection-diffusion equation for each specie. The chemistry of clot formation is now understood to be determined by mechanisms involving reactions among many species in dilute solution, where reaction rate constants and species diffusion coefficients in plasma are known. The role of blood particulates, i.e. red cells and platelets, in the clotting process is studied by including them separately and together in the simulations. An agonist-induced platelet activation mechanism is presented, while platelets adhesive dynamics based on a stochastic bond formation/dissociation process is included in the model.

Diffusion Bonding Beryllium to Reduced Activation Ferritic Martensitic Steel: Development of Processes and Techniques

NASA Astrophysics Data System (ADS)

Hunt, Ryan Matthew

Only a few materials are suitable to act as armor layers against the thermal and particle loads produced by magnetically confined fusion. These candidates include beryllium, tungsten, and carbon fiber composites. The armor layers must be joined to the plasma facing components with high strength bonds that can withstand the thermal stresses resulting from differential thermal expansion. While specific joints have been developed for use in ITER (an experimental reactor in France), including beryllium to CuCrZr as well as tungsten to stainless steel interfaces, joints specific to commercially relevant fusion reactors are not as well established. Commercial first wall components will likely be constructed front Reduced Activation Ferritic Martensitic (RAFM) steel, which will need to be coating with one of the three candidate materials. Of the candidates, beryllium is particularly difficult to bond, because it reacts during bonding with most elements to form brittle intermetallic compounds. This brittleness is unacceptable, as it can lead to interface crack propagation and delamination of the armor layer. I have attempted to overcome the brittle behavior of beryllium bonds by developing a diffusion bonding process of beryllium to RAFM steel that achieves a higher degree of ductility. This process utilized two bonding aids to achieve a robust bond: a. copper interlayer to add ductility to the joint, and a titanium interlayer to prevent beryllium from forming unwanted Be-Cu intermetallics. In addition, I conducted a series of numerical simulations to predict the effect of these bonding aids on the residual stress in the interface. Lastly, I fabricated and characterized beryllium to ferritic steel diffusion bonds using various bonding parameters and bonding aids. Through the above research, I developed a process to diffusion bond beryllium to ferritic steel with a 150 M Pa tensile strength and 168 M Pa shear strength. This strength was achieved using a Hot Isostatic Pressing (HIP) process (at a temperature between 700 °C and 750 °C for 2 hours at 103 M Pa) with 10 mu m of titanium and 20 mum of copper deposited between substrates. Without the copper and titanium interlayers, the bond formed an intermetallic that lead to fracture from internal residual stresses. Also, slowing the rate of cooling and adding an intermediate hold temperature during cool-down significantly increased bond strength. These beneficial effects were confirmed by the numerical simulations, which showed reduced residual stress resulting from all bonding techniques. Both metals interlayers, as well as the reduced cooling rate were critical in overcoming the otherwise brittle quality of the beryllium to ferritic steel joint. However, the introduced interlayers are not an ideal solution to the problem. They introduced both Be-Ti and Cu-Ti compounds, which proved to be the eventual failure location in the bond. Further optimization of this joint is necessary, and can potentially be achieved with variation of cooling rates. To make the joint ready for implementation will require larger scale fabrication to verify reliability and to test the joint under operational loads.

Hydration of Li+ -ion in atom-bond electronegativity equalization method-7P water: a molecular dynamics simulation study.

PubMed

Li, Xin; Yang, Zhong-Zhi

2005-02-22

We have carried out molecular dynamics simulations of a Li(+) ion in water over a wide range of temperature (from 248 to 368 K). The simulations make use of the atom-bond electronegativity equalization method-7P water model, a seven-site flexible model with fluctuating charges, which has accurately reproduced many bulk water properties. The recently constructed Li(+)-water interaction potential through fitting to the experimental and ab initio gas-phase binding energies and to the measured structures for Li(+)-water clusters is adopted in the simulations. ABEEM was proposed and developed in terms of partitioning the electron density into atom and bond regions and using the electronegativity equalization method (EEM) and the density functional theory (DFT). Based on a combination of the atom-bond electronegativity equalization method and molecular mechanics (ABEEM/MM), a new set of water-water and Li(+)-water potentials, successfully applied to ionic clusters Li(+)(H(2)O)(n)(n=1-6,8), are further investigated in an aqueous solution of Li(+) in the present paper. Two points must be emphasized in the simulations: first, the model allows for the charges on the interacting sites fluctuating as a function of time; second, the ABEEM-7P model has applied the parameter k(lp,H)(R(lp,H)) to explicitly describe the short-range interaction of hydrogen bond in the hydrogen bond interaction region, and has a new description for the hydrogen bond. The static, dynamic, and thermodynamic properties have been studied in detail. In addition, at different temperatures, the structural properties such as radial distribution functions, and the dynamical properties such as diffusion coefficients and residence times of the water molecules in the first hydration shell of Li(+), are also simulated well. These simulation results show that the ABEEM/MM-based water-water and Li(+)-water potentials appear to be robust giving the overall characteristic hydration properties in excellent agreement with experiments and other molecular dynamics simulations on similar system.

Solute-solvent complex switching dynamics of chloroform between acetone and dimethylsulfoxide-two-dimensional IR chemical exchange spectroscopy.

PubMed

Kwak, Kyungwon; Rosenfeld, Daniel E; Chung, Jean K; Fayer, Michael D

2008-11-06

Hydrogen bonds formed between C-H and various hydrogen bond acceptors play important roles in the structure of proteins and organic crystals, and the mechanisms of C-H bond cleavage reactions. Chloroform, a C-H hydrogen bond donor, can form weak hydrogen-bonded complexes with acetone and with dimethylsulfoxide (DMSO). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO, both types of hydrogen-bonded complexes exist. The two complexes, chloroform-acetone and chloroform-DMSO, are in equilibrium, and they rapidly interconvert by chloroform exchanging hydrogen bond acceptors. This fast hydrogen bond acceptor substitution reaction is probed using ultrafast two-dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy. Deuterated chloroform is used in the experiments, and the 2D-IR spectrum of the C-D stretching mode is measured. The chemical exchange of the chloroform hydrogen bonding partners is tracked by observing the time-dependent growth of off-diagonal peaks in the 2D-IR spectra. The measured substitution rate is 1/30 ps for an acetone molecule to replace a DMSO molecule in a chloroform-DMSO complex and 1/45 ps for a DMSO molecule to replace an acetone molecule in a chloroform-acetone complex. Free chloroform exists in the mixed solvent, and it acts as a reactive intermediate in the substitution reaction, analogous to a SN1 type reaction. From the measured rates and the equilibrium concentrations of acetone and DMSO, the dissociation rates for the chloroform-DMSO and chloroform-acetone complexes are found to be 1/24 ps and 1/5.5 ps, respectively. The difference between the measured rate for the complete substitution reaction and the rate for complex dissociation corresponds to the diffusion limited rate. The estimated diffusion limited rate agrees well with the result from a Smoluchowski treatment of diffusive reactions.

Elastic constants for superplastically formed/diffusion-bonded corrugated sandwich core

NASA Technical Reports Server (NTRS)

Ko, W. L.

1980-01-01

Formulas and associated graphs for evaluating the effective elastic constants for a superplastically formed/diffusion bonded (SPF/DB) corrugated sandwich core, are presented. A comparison of structural stiffnesses of the sandwich core and a honeycomb core under conditions of equal sandwich core density was made. The stiffness in the thickness direction of the optimum SPF/DB corrugated core (that is, triangular truss core) is lower than that of the honeycomb core, and that the former has higher transverse shear stiffness than the latter.

Microstructure of Reaction Zone Formed During Diffusion Bonding of TiAl with Ni/Al Multilayer

NASA Astrophysics Data System (ADS)

Simões, Sónia; Viana, Filomena; Koçak, Mustafa; Ramos, A. Sofia; Vieira, M. Teresa; Vieira, Manuel F.

2012-05-01

In this article, the characterization of the interfacial structure of diffusion bonding a TiAl alloy is presented. The joining surfaces were modified by Ni/Al reactive multilayer deposition as an alternative approach to conventional diffusion bonding. TiAl substrates were coated with alternated Ni and Al nanolayers. The nanolayers were deposited by dc magnetron sputtering with 14 nm of period (bilayer thickness). Joining experiments were performed at 900 °C for 30 and 60 min with a pressure of 5 MPa. Cross sections of the joints were prepared for characterization of their interfaces by scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), high resolution TEM (HRTEM), energy dispersive x-ray spectroscopy (EDS), and electron backscatter diffraction (EBSD). Several intermetallic compounds form at the interface, assuring the bonding of the TiAl. The interface can be divided into three distinct zones: zone 1 exhibits elongated nanograins, very small equiaxed grains are observed in zone 2, while zone 3 has larger equiaxed grains. EBSD analysis reveals that zone 1 corresponds to the intermetallic Al2NiTi and AlNiTi, and zones 2 and 3 to NiAl.

The Effect of CuO Nanoparticles on Antimicrobial Effects and Shear Bond Strength of Orthodontic Adhesives

PubMed Central

Toodehzaeim, Mohammad Hossein; Zandi, Hengameh; Meshkani, Hamidreza; Hosseinzadeh Firouzabadi, Azadeh

2018-01-01

Statement of the Problem: Orthodontic appliances facilitate microbial plaque accumulation and increase the chance of white spot lesions. There is a need for new plaque control methods independent of patient's cooperation. Purpose: The aim of this study was to determine the effects of incorporating copper oxide (CuO) nanoparticles on antimicrobial properties and bond strength of orthodontic adhesive. Materials and Method: CuO nanoparticles were added to the composite transbond XT at concentrations of 0.01, 0.5 and 1 wt.%. To evaluate the antimicrobial properties of composites containing nanoparticles, the disk agar diffusion test was used. For this purpose, 10 discs from each concentration of nano-composites (totally 30 discs) and 10 discs from conventional composite (as the control group) were prepared. Then the diameter of streptococcus mutans growth inhibition around each disc was determined in blood agar medium. To evaluate the shear bond strength, with each concentration of nano-composites as well as the control group (conventional composite), 10 metal brackets were bonded to the human premolars and shear bond strength was determined using a universal testing machine. Results: Nano-composites in all three concentrations showed significant antimicrobial effect compared to the control group (p< 0.001). With increasing concentration of nanoparticles, antimicrobial effect showed an upward trend, although statistically was not significant. There was no significant difference between the shear bond strength of nano-composites compared to control group (p= 0.695). Conclusion: Incorporating CuO nanoparticles into adhesive in all three studied concentrations added antimicrobial effects to the adhesive with no adverse effects on shear bond strength. PMID:29492409

Subcontract Report: Diffusion Mechanisms and Bond Dynamics in Solid Electrolyte Ion-Conductors

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

Zevgolis, A.; Hall, A.; Alvez, T.

2017-10-03

We employ first-principles molecular dynamics simulations and Maximally Localized Wannier Function (MLWF) analysis to explore how halide substitution and nano-phase microstructures affect diffusivity, through the activation energy barrier - E a and D 0, in the solid electrolyte Li 3InBr 6-xCl x. We find that nano-phase microstructures with x=3 (50-50 Br-Cl) mixed composition have a higher diffusivity compared to x=2 and x=3 solid solutions. There is a positive linear relationship between ln(D 0.) and E a, which suggests that for superionic conductivity optimizing both the activation energy and the D 0 is important. Bond frustration due to mismatch in crystalmore » geometry and ideal coordination number leads to especially high diffusivity through a high D 0 in the x=3 composition.« less

The role of hypothetico-deductive reasoning and physical analogues of molecular interactions in conceptual change

NASA Astrophysics Data System (ADS)

Lawson, Anton E.; Baker, William P.; Didonato, Lisa; Verdi, Michael P.; Johnson, Margaret A.

Two hypotheses about theoretical concept acquisition, application, and change were tested. College biology students classified as intuitive, transitional, or reflective (hypothetico-deductive) reasoners were first taught two theoretical concepts (molecular polarity and bonding) to explain the mixing of dye with water, but not with oil, when all three were shaken in a container. The students were then tested in a context in which they misapplied the concepts in an attempt to explain the gradual spread of blue dye in standing water. Next students were taught another theoretical concept (diffusion), with and without the use of physical analogues. They were retested to see which students acquired the concept of diffusion and which students changed from use of the incorrect polarity and bonding concepts (i.e., the misconceptions) to use of the diffusion concept to correctly explain the dye's gradual spread. As predicted, the experimental/analogy group scored significantly higher than the control group on a posttest question that required the definition of diffusion. Also as predicted, hypothetico-deductive reasoning skill was significantly related to correct application of the diffusion concept and to a change from the misapplication of the polarity and bonding concepts to the correct application of the diffusion concept to explain the gradual spread of the blue dye. Thus, the results support the hypotheses that physical analogues are helpful in theoretical concept acquisition and that hypothetico-deductive reasoning is needed for successful concept application and change. Educational implications are drawn.

Understanding Lithium Solvation and Diffusion through Topological Analysis of First-Principles Molecular Dynamics

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

Bhatia, Harsh; Gyulassy, Attila; Ong, Mitchell

2016-09-27

The performance of lithium-ion batteries is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact, both, the solvation and diffusivity of Li ions. In this work, we present our application of the topological techniques to extract and predict such behavior in the data generated by the first-principles molecular dynamics simulation of Li ions in an important organic solvent -ethylene carbonate. More specifically, we use the scalar topology of the electron charge density field tomore » analyze the evolution of the solvation structures. This allows us to derive a parameter-free bond definition for lithium-oxygen bonds, to provide a quantitative measure for bond strength, and to understand the regions of influence of each atom in the simulation. This has provided new insights into how and under what conditions certain bonds may form and break. As a result, we can identify and, more importantly, predict, unstable configurations in solvation structures. This can be very useful in understanding when small changes to the atoms' movements can cause significantly different bond structures to evolve. Ultimately, this promises to allow scientists to explore lithium ion solvation and diffusion more systematically, with the aim of new insights and potentially accelerating the calculations themselves.« less

Pyridine adsorption and diffusion on Pt(111) investigated with density functional theory

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

Kolsbjerg, Esben L.; Groves, Michael N.; Hammer, Bjørk, E-mail: hammer@phys.au.dk

2016-04-28

The adsorption, diffusion, and dissociation of pyridine, C{sub 5}H{sub 5}N, on Pt(111) are investigated with van der Waals-corrected density functional theory. An elaborate search for local minima in the adsorption potential energy landscape reveals that the intact pyridine adsorbs with the aromatic ring parallel to the surface. Piecewise interconnections of the local minima in the energy landscape reveal that the most favourable diffusion path for pyridine has a barrier of 0.53 eV. In the preferred path, the pyridine remains parallel to the surface while performing small single rotational steps with a carbon-carbon double bond hinged above a single Pt atom.more » The origin of the diffusion pathway is discussed in terms of the C{sub 2}–Pt π-bond being stronger than the corresponding CN–Pt π-bond. The energy barrier and reaction enthalpy for dehydrogenation of adsorbed pyridine into an adsorbed, upright bound α-pyridyl species are calculated to 0.71 eV and 0.18 eV, respectively (both zero-point energy corrected). The calculations are used to rationalize previous experimental observations from the literature for pyridine on Pt(111).« less

Technical and Economical Aspects of Current Thermal Barrier Coating Systems for Gas Turbine Engines by Thermal Spray and EBPVD: A Review

NASA Astrophysics Data System (ADS)

Feuerstein, Albert; Knapp, James; Taylor, Thomas; Ashary, Adil; Bolcavage, Ann; Hitchman, Neil

2008-06-01

The most advanced thermal barrier coating (TBC) systems for aircraft engine and power generation hot section components consist of electron beam physical vapor deposition (EBPVD) applied yttria-stabilized zirconia and platinum modified diffusion aluminide bond coating. Thermally sprayed ceramic and MCrAlY bond coatings, however, are still used extensively for combustors and power generation blades and vanes. This article highlights the key features of plasma spray and HVOF, diffusion aluminizing, and EBPVD coating processes. The coating characteristics of thermally sprayed MCrAlY bond coat as well as low density and dense vertically cracked (DVC) Zircoat TBC are described. Essential features of a typical EBPVD TBC coating system, consisting of a diffusion aluminide and a columnar TBC, are also presented. The major coating cost elements such as material, equipment and processing are explained for the different technologies, with a performance and cost comparison given for selected examples.

Thermal Pyrolytic Graphite Enhanced Components

NASA Technical Reports Server (NTRS)

Hardesty, Robert E. (Inventor)

2015-01-01

A thermally conductive composite material, a thermal transfer device made of the material, and a method for making the material are disclosed. Apertures or depressions are formed in aluminum or aluminum alloy. Plugs are formed of thermal pyrolytic graphite. An amount of silicon sufficient for liquid interface diffusion bonding is applied, for example by vapor deposition or use of aluminum silicon alloy foil. The plugs are inserted in the apertures or depressions. Bonding energy is applied, for example by applying pressure and heat using a hot isostatic press. The thermal pyrolytic graphite, aluminum or aluminum alloy and silicon form a eutectic alloy. As a result, the plugs are bonded into the apertures or depressions. The composite material can be machined to produce finished devices such as the thermal transfer device. Thermally conductive planes of the thermal pyrolytic graphite plugs may be aligned in parallel to present a thermal conduction path.

Studies of dispersion energy in hydrogen-bonded systems. H2O-HOH, H2O-HF, H3N-HF, HF-HF

NASA Astrophysics Data System (ADS)

Szcześniak, M. M.; Scheiner, Steve

1984-02-01

Dispersion energy is calculated in the systems H2O-HOH, H2O-HF, H3N-HF, and HF-HF as a function of the intermolecular separation using a variety of methods. M≂ller-Plesset perturbation theory to second and third orders is applied in conjunction with polarized basis sets of 6-311G** type and with an extended basis set including a second set of polarization functions (DZ+2P). These results are compared to a multipole expansion of the dispersion energy, based on the Unsöld approximation, carried out to the inverse tenth power of the intermolecular distance. Pairwise evaluation is also carried out using both atom-atom and bond-bond formulations. The MP3/6-311G** results are in generally excellent accord with the leading R-6 term of the multipole expansion. This expansion, if carried out to the R-10 term, reproduces extremely well previously reported dispersion energies calculated via variation-perturbation theory. Little damping of the expansion is required for intermolecular distances equal to or greater than the equilibrium separation. Although the asymptotic behavior of the MP2 dispersion energy is somewhat different than that of the other methods, augmentation of the basis set by a second diffuse set of d functions leads to quite good agreement in the vicinity of the minima. Both the atom-atom and bond-bond parametrization schemes are in good qualitative agreement with the other methods tested. All approaches produce similar dependence of the dispersion energy upon the angular orientation between the two molecules involved in the H bond.

Thermal fatigue testing of a diffusion-bonded beryllium divertor mock-up under ITER-relevant conditions

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

Youchison, D.L.; Watson, R.D.; McDonald, J.M.

Thermal response and thermal fatigue tests of four 5-mm-thick beryllium tiles on a Russian Federation International Thermonuclear Experimental Reactor (ITER)-relevant divertor mock-up were completed on the electron beam test system at Sandia National Laboratories. Thermal response tests were performed on the tiles to an absorbed heat flux of 5 MW/m{sup 2} and surface temperatures near 300{degree}C using 1.4 MPa water at 5 m/s flow velocity and an inlet temperature of 8 to 15{degree}C. One tile was exposed to incrementally increasing heat fluxes up to 9.5 MW/m{sup 2} and surface temperatures up to 690{degree}C before debonding at 10MW/m{sup 2}. A secondmore » tile debonded in 25 to 30 cycles at <0.5 MW/m{sup 2}. However, a third tile debonded after 9200 thermal fatigue cycles at 5 MW/m{sup 2}, while another debonded after 6800 cycles. Posttest surface analysis indicated that fatigue failure occurred in the intermetallic layers between the beryllium and copper. No fatigue cracking of the bulk beryllium was observed. It appears that microcracks growing at the diffusion bond produced the observed gradual temperature increases during thermal cycling. These experiments indicate that diffusion-bonded beryllium tiles can survive several thousand thermal cycles under ITER-relevant conditions. However, the reliability of the diffusion-bonded joint remains a serious issue. 17 refs., 25 figs., 6 tabs.« less

Review of Graphene as a Solid State Diffusion Barrier.

PubMed

Morrow, Wayne K; Pearton, Stephen J; Ren, Fan

2016-01-06

Conventional thin-film diffusion barriers consist of 3D bulk films with high chemical and thermal stability. The purpose of the barrier material is to prevent intermixing or penetration from the two materials that encase it. Adhesion to both top and bottom materials is critical to the success of the barrier. Here, the effectiveness of a single atomic layer of graphene as a solid-state diffusion barrier for common metal schemes used in microelectronics is reviewed, and specific examples are discussed. Initial studies of electrical contacts to graphene show a distinct separation in behavior between metallic groups that strongly or weakly bond to it. The two basic classes of metal reactions with graphene are either physisorbed metals, which bond weakly with graphene, or chemisorbed metals, which bond strongly to graphene. For graphene diffusion barrier testing on Si substrates, an effective barrier can be achieved through the formation of a carbide layer with metals that are chemisorbed. For physisorbed metals, the barrier failure mechanism is loss of adhesion at the metal–graphene interface. A graphene layer encased between two metal layers, in certain cases, can increase the binding energy of both films with graphene, however, certain combinations of metal films are detrimental to the bonding with graphene. While the prospects for graphene's future as a solid-state diffusion barrier are positive, there are open questions, and areas for future research are discussed. A better understanding of the mechanisms which influence graphene's ability to be an effective diffusion barrier in microelectronic applications is required, and additional experiments are needed on a broader range of metals, as well as common metal stack contact structures used in microelectronic applications. The role of defects in the graphene is also a key area, since they will probably influence the barrier properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonideality in diffusion of ionic and hydrophobic solutes and pair dynamics in water-acetone mixtures of varying composition.

PubMed

Gupta, Rini; Chandra, Amalendu

2007-07-14

We have performed a series of molecular dynamics simulations of water-acetone mixtures containing either an ionic solute or a neutral hydrophobic solute to study the extent of nonideality in the dynamics of these solutes with variation of composition of the mixtures. The diffusion coefficients of the charged solutes, both cationic and anionic, are found to change nonmonotonically with the composition of the mixtures showing strong nonideality of their dynamics. Also, the extent of nonideality in the diffusion of these charged solutes is found to be similar to the nonideality that is observed for the diffusion and orientational relaxation of water and acetone molecules in these mixtures which show a somewhat similar changes in the solvation characteristics of charged and dipolar solutes with changes of composition of water-acetone mixtures. The diffusion of the hydrophobic solute, however, shows a monotonic increase with increase of acetone concentration showing its different solvation characteristics as compared to the charged and dipolar solutes. The links between the nonideality in diffusion and solvation structures are further confirmed through calculations of the relevant solute-solvent and solvent-solvent radial distribution functions for both ionic and hydrophobic solutes. We have also calculated various pair dynamical properties such as the relaxation of water-water and acetone-water hydrogen bonds and residence dynamics of water molecules in water and acetone hydration shells. The lifetimes of both water-water and acetone-water hydrogen bonds and also the residence times of water molecules are found to increase steadily with increase in acetone concentration. No maximum or minimum was found in the composition dependence of these pair dynamical quantities. The lifetimes of water-water hydrogen bonds are always found to be longer than that of acetone-water hydrogen bonds in these mixtures. The residence times of water molecules are also found to follow a similar trend.

Effect of Bonding Time on Interfacial Reaction and Mechanical Properties of Diffusion-Bonded Joint Between Ti-6Al-4V and 304 Stainless Steel Using Nickel as an Intermediate Material

NASA Astrophysics Data System (ADS)

Thirunavukarasu, Gopinath; Kundu, Sukumar; Mishra, Brajendra; Chatterjee, Subrata

2014-04-01

In the current study, solid-state diffusion bonding between Ti-6Al-4V (TiA) and 304 stainless steel (SS) using pure nickel (Ni) of 200- μm thickness as an intermediate material was carried out in vacuum. Uniaxial compressive pressure and temperature were kept at 4 MPa and 1023 K (750 °C), respectively, and the bonding time was varied from 30 to 120 minutes in steps of 15 minutes. Scanning electron microscopy images, in backscattered electron mode, revealed the layerwise Ti-Ni-based intermetallics like either Ni3Ti or both Ni3Ti and NiTi at titanium alloy-nickel (TiA/Ni) interface, whereas nickel-stainless steel (Ni/SS) interface was free from intermetallic phases for all the joints. Chemical composition of the reaction layers was determined by energy dispersive spectroscopy (SEM-EDS) and confirmed by X-ray diffraction study. Maximum tensile strength of ~382 MPa along with ~3.7 pct ductility was observed for the joints processed for 60 minutes. It was found that the extent of diffusion zone at Ni/SS interface was greater than that of TiA/Ni interface. From the microhardness profile, fractured surfaces, and fracture path, it was demonstrated that the failure of the joints was initiated and propagated apparently at TiA/Ni interface near Ni3Ti intermetallic for bonding time less than 90 minutes, and through Ni for bonding time 90 minutes and greater.

Chemical effect on diffusion in intermetallic compounds

NASA Astrophysics Data System (ADS)

Chen, Yi-Ting

With the trend of big data and the Internet of things, we live in a world full of personal electronic devices and small electronic devices. In order to make the devices more powerful, advanced electronic packaging such as wafer level packaging or 3D IC packaging play an important role. Furthermore, ?-bumps, which connect silicon dies together with dimension less than 10 ?m, are crucial parts in advanced packaging. Owing to the dimension of ?-bumps, they transform into intermetallic compound from tin based solder after the liquid state bonding process. Moreover, many new reliability issues will occur in electronic packaging when the bonding materials change; in this case, we no longer have tin based solder joint, instead, we have intermetallic compound ?-bumps. Most of the potential reliability issues in intermetallic compounds are caused by the chemical reactions driven by atomic diffusion in the material; thus, to know the diffusivities of atoms inside a material is significant and can help us to further analyze the reliability issues. However, we are lacking these kinds of data in intermetallic compound because there are some problems if used traditional Darken's analysis. Therefore, we considered Wagner diffusivity in our system to solve the problems and applied the concept of chemical effect on diffusion by taking the advantage that large amount of energy will release when compounds formed. Moreover, by inventing the holes markers made by Focus ion beam (FIB), we can conduct the diffusion experiment and obtain the tracer diffusivities of atoms inside the intermetallic compound. We applied the technique on Ni3Sn4 and Cu3Sn, which are two of the most common materials in electronic packaging, and the tracer diffusivities are measured under several different temperatures; moreover, microstructure of the intermetallic compounds are investigated to ensure the diffusion environment. Additionally, the detail diffusion mechanism was also discussed in aspect of diffusion activation enthalpy and diffusion pre-factor by using lattice structure simulation. Last but not the least, X-ray photoelectron spectroscopy and First principal calculation simulation were used to observe the electron binding energies in the intermetallic compound and illustrate the partial covalent bonding behavior in the intermetallic compounds.

The molecular basis of the solution properties of hyaluronan investigated by confocal fluorescence recovery after photobleaching.

PubMed Central

Gribbon, P; Heng, B C; Hardingham, T E

1999-01-01

Hyaluronan (HA) is a highly hydrated polyanion, which is a network-forming and space-filling component in the extracellular matrix of animal tissues. Confocal fluorescence recovery after photobleaching (confocal-FRAP) was used to investigate intramolecular hydrogen bonding and electrostatic interactions in hyaluronan solutions. Self and tracer lateral diffusion coefficients within hyaluronan solutions were measured over a wide range of concentrations (c), with varying electrolyte and at neutral and alkaline pH. The free diffusion coefficient of fluoresceinamine-labeled HA of 500 kDa in PBS was 7.9 x 10(-8) cm(2) s(-1) and of 830 kDa HA was 5.6 x 10(-8) cm(2) s(-1). Reductions in self- and tracer-diffusion with c followed a stretched exponential model. Electrolyte-induced polyanion coil contraction and destiffening resulted in a 2.8-fold increase in self-diffusion between 0 and 100 mM NaCl. Disruption of hydrogen bonds by strong alkali (0.5 M NaOH) resulted in further larger increases in self- and tracer-diffusion coefficients, consistent with a more dynamic and permeable network. Concentrated hyaluronan solution properties were attributed to hydrodynamic and entanglement interactions between domains. There was no evidence of chain-chain associations. At physiological electrolyte concentration and pH, the greatest contribution to the intrinsic stiffness of hyaluronan appeared to be due to hydrogen bonds between adjacent saccharides. PMID:10512840

Rapid ultrasound-induced transient-liquid-phase bonding of Al-50Si alloys with Zn interlayer in air for electrical packaging application.

PubMed

Wang, Qian; Chen, Xiaoguang; Zhu, Lin; Yan, Jiuchun; Lai, Zhiwei; Zhao, Pizhi; Bao, Juncheng; Lv, Guicai; You, Chen; Zhou, Xiaoyu; Zhang, Jian; Li, Yuntao

2017-01-01

Al-50Si alloys were joined by rapid ultrasound-induced transient-liquid-phase bonding method using Zn foil as interlayer at 390°C in air, below the melt point of interlayer. The fracture of oxide films along the edge of Si particles led to contact and inter-diffusion between aluminum substrate and Zn interlayer, and liquefied Zn-Al alloys were developed. The width of Zn-Al alloys gradually decreased with increasing the ultrasonic vibration time due to liquid squeezing out and accelerated diffusion. A stage of isothermal solidification existed, and the completion time was significantly shortened. In the liquid metal, the acoustic streaming and ultrasonic cavitations were induced. As the process developed, much more Si particles, which were particulate-reinforced phases of Al-50Si, gradually migrated to the center of soldering seam. The highest average shear strength of joints reached to 94.2MPa, and the fracture mainly occurred at the base metal. Copyright © 2016 Elsevier B.V. All rights reserved.

Anisotropic Thermal Diffusivities of Plasma-Sprayed Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Akoshima, Megumi; Takahashi, Satoru

2017-09-01

Thermal barrier coatings (TBCs) are used to shield the blades of gas turbines from heat and wear. There is a pressing need to evaluate the thermal conductivity of TBCs in the thermal design of advanced gas turbines with high energy efficiency. These TBCs consist of a ceramic-based top coat and a bond coat on a superalloy substrate. Usually, the focus is on the thermal conductivity in the thickness direction of the TBC because heat tends to diffuse from the surface of the top coat to the substrate. However, the in-plane thermal conductivity is also important in the thermal design of gas turbines because the temperature distribution within the turbine cannot be ignored. Accordingly, a method is developed in this study for measuring the in-plane thermal diffusivity of the top coat. Yttria-stabilized zirconia top coats are prepared by thermal spraying under different conditions. The in-plane and cross-plane thermal diffusivities of the top coats are measured by the flash method to investigate the anisotropy of thermal conduction in a TBC. It is found that the in-plane thermal diffusivity is higher than the cross-plane one for each top coat and that the top coats have significantly anisotropic thermal diffusivity. The cross-sectional and in-plane microstructures of the top coats are observed, from which their porosities are evaluated. The thermal diffusivity and its anisotropy are discussed in detail in relation to microstructure and porosity.

AFWAL FY80 Technical Accomplishments Report.

DTIC Science & Technology

1981-12-01

through cooperative effort of the Materials and Certain compositions in the titanium aluminide Propulsion Laboratories. In addition to an extensive system...Bonded Structures Technology Transitioned .................................................. 43 Superplastically Formed and Diffusion Bonded Titanium ...Technology ................................................................................................. 75 First RSR Radial Wafer Blade Engine Test

Surface morphology and molecular bonding of CaCO3 nanocrystallites by gas diffusion method

NASA Astrophysics Data System (ADS)

Sulimai, N. H.; Rani, Rozina Abdul; Khusaimi, Z.; Abdullah, S.; Salifairus, M. J.; Alrokayan, Salman; Khan, Haseeb; Rusop, M.

2018-05-01

Calcium carbonate with the chemical formula of (CaCO3) is the most abundant element in the world. Its usage on certain applications is largely affected by its properties. The best means to control its properties is through controlled preparation of CaCO3. This study uses diffusion method between the precursors Calcium Chloride and Ammonium Carbonate. Instead of using water, ethanol was used to prepare the salt. Reaction was done in room temperature (RT) for 6h-24h. Smallest average crystallite size measured by FESEM micrograph is 500nm produced by synthesis of CaCO3 reacted for 168 hours. From energy-dispersive X-ray spectrum also indicated the smallest particle size is by CaCO3 reacted for 168 hours. Changes was seen for element Ca at 3.7keV.

Evaluation of Rhenium Joining Methods

NASA Technical Reports Server (NTRS)

Reed, Brian D.; Morren, Sybil H.

1995-01-01

Coupons of rhenium-to-Cl03 flat plate joints, formed by explosive and diffusion bonding, were evaluated in a series of shear tests. Shear testing was conducted on as-received, thermally-cycled (100 cycles, from 21 to 1100 C), and thermally-aged (3 and 6 hrs at 1100 C) joint coupons. Shear tests were also conducted on joint coupons with rhenium and/or Cl03 electron beam welded tabs to simulate the joint's incorporation into a structure. Ultimate shear strength was used as a figure of merit to assess the effects of the thermal treatment and the electron beam welding of tabs on the joint coupons. All of the coupons survived thermal testing intact and without any visible degradation. Two different lots of as-received, explosively-bonded joint coupons had ultimate shear strengths of 281 and 310 MPa and 162 and 223 MPa, respectively. As-received, diffusion-bonded coupons had ultimate shear strengths of 199 and 348 MPa. For the most part, the thermally-treated and rhenium weld tab coupons had shear strengths slightly reduced or within the range of the as-received values. Coupons with Cl03 weld tabs experienced a significant reduction in shear strength. The degradation of strength appeared to be the result of a poor heat sink provided during the electron beam welding. The Cl03 base material could not dissipate heat as effectively as rhenium, leading to the formation of a brittle rhenium-niobium intermetallic.

Influence of Cholesterol on the Dynamics of Hydration in Phospholipid Bilayers.

PubMed

Elola, M Dolores; Rodriguez, Javier

2018-06-07

We investigate the dynamics of interfacial waters in dipalmitoylphosphatidylcholine (DPPC) bilayers upon the addition of cholesterol, by molecular dynamics simulations. Our data reveal that the inclusion of cholesterol modifies the membrane aqueous interfacial dynamics: waters diffuse faster, their rotational decay time is shorter, and the DPPC/water hydrogen bond dynamics relaxes faster than in the pure DPPC membrane. The observed acceleration of the translational water dynamics agrees with recent experimental results, in which, by means of NMR techniques, an increment of the surface water diffusivity is measured upon the addition of cholesterol. A microscopic analysis of the lipid/water hydrogen bond network at the interfacial region suggests that the mechanism underlying the observed water mobility enhancement is given by the rupture of a fraction of interlipid water bridge hydrogen bonds connecting two different DPPC molecules, concomitant to the formation of new lipid/solvent bonds, whose dynamics is faster than that of the former. The consideration of a simple two-state model for the decay of the hydrogen bond correlation function yielded excellent results, obtaining two well-separated characteristic time scales: a slow one (∼250 ps) associated with bonds linking two DPPC molecules, and a fast one (∼15 ps), related to DPPC/solvent bonds.

Microstructure, Tensile Adhesion Strength and Thermal Shock Resistance of TBCs with Different Flame-Sprayed Bond Coat Materials Onto BMI Polyimide Matrix Composite

NASA Astrophysics Data System (ADS)

Abedi, H. R.; Salehi, M.; Shafyei, A.

2017-10-01

In this study, thermal barrier coatings (TBCs) composed of different bond coats (Zn, Al, Cu-8Al and Cu-6Sn) with mullite top coats were flame-sprayed and air-plasma-sprayed, respectively, onto bismaleimide matrix composites. These polyimide matrix composites are of interest to replace PMR-15, due to concerns about the toxicity of the MDA monomer from which PMR-15 is made. The results showed that pores and cracks appeared at the bond coat/substrate interface for the Al-bonded TBC because of its high thermal conductivity and diffusivity resulting in transferring of high heat flux and temperature to the polymeric substrate during top coat deposition. The other TBC systems due to the lower conductivity and diffusivity of bonding layers could decrease the adverse thermal effect on the polymer substrate during top coat deposition and exhibited adhesive bond coat/substrate interfaces. The tensile adhesion test showed that the adhesion strength of the coatings to the substrate is inversely proportional to the level of residual stress in the coatings. However, the adhesion strength of Al bond-coated sample decreased strongly after mullite top coat deposition due to thermal damage at the bond coat/substrate interface. TBC system with the Cu-6Sn bond coat exhibited the best thermal shock resistance, while Al-bonded TBC showed the lowest. It was inferred that thermal mismatch stresses and oxidation of the bond coats were the main factors causing failure in the thermal shock test.

Shearography for Non-destructive Inspection with applications to BAT Mask Tile Adhesive Bonding and Specular Surface Honeycomb Panels

NASA Technical Reports Server (NTRS)

Lysak, Daniel B.

2003-01-01

The applicability of shearography techniques for non-destructive evaluation in two unique application areas is examined. In the first application, shearography is used to evaluate the quality of adhesive bonds holding lead tiles to the B.4T gamma ray mask for the NASA Swift program. Using a vibration excitation, the more poorly bonded tiles are readily identifiable in the shearography image. A quantitative analysis is presented that compares the shearography results with a destructive pull test measuring the force at bond failure. The second application is to evaluate the bonding between the skin and core of a honeycomb structure with a specular (mirror-like) surface. In standard shearography techniques, the object under test must have a diffuse surface to generate the speckle patterns in laser light, which are then sheared. A novel configuration using the specular surface as a mirror to image speckles from a diffuser is presented, opening up the use of shearography to a new class of objects that could not have been examined with the traditional approach. This new technique readily identifies large scale bond failures in the panel, demonstrating the validity of this approach.

Interfacial Microstructure and Mechanical Strength of 93W/Ta Diffusion-Bonded Joints with Ni Interlayer

NASA Astrophysics Data System (ADS)

Luo, Guoqiang; Zhang, Jian; Li, Meijuan; Wei, Qinqin; Shen, Qiang; Zhang, Lianmeng

2013-02-01

93W alloy and Ta metal were successfully diffusion bonded using a Ni interlayer. Ni4W was found at the W-Ni interface, and Ni3Ta and Ni2Ta were formed at the Ni-Ta interface. The shear strength of the joints increases with increasing holding time, reaching a value of 202 MPa for a joint prepared using a 90-minute holding time at 1103 K (830 °C) and 20 MPa. The fracture of this joint occurred within the Ni/Ta interface.

Method of transferring a thin crystalline semiconductor layer

DOEpatents

Nastasi, Michael A [Sante Fe, NM; Shao, Lin [Los Alamos, NM; Theodore, N David [Mesa, AZ

2006-12-26

A method for transferring a thin semiconductor layer from one substrate to another substrate involves depositing a thin epitaxial monocrystalline semiconductor layer on a substrate having surface contaminants. An interface that includes the contaminants is formed in between the deposited layer and the substrate. Hydrogen atoms are introduced into the structure and allowed to diffuse to the interface. Afterward, the thin semiconductor layer is bonded to a second substrate and the thin layer is separated away at the interface, which results in transferring the thin epitaxial semiconductor layer from one substrate to the other substrate.

MD simulation study of the diffusion and local structure of n-alkanes in liquid and supercritical methanol at infinite dilution.

PubMed

Feng, Huajie; Gao, Wei; Su, Li; Sun, Zhenfan; Chen, Liuping

2017-06-01

The diffusion coefficients of 14 n-alkanes (ranging from methane to n-tetradecane) in liquid and supercritical methanol at infinite dilution (at a pressure of 10.5 MPa and at temperatures of 299 K and 515 K) were deduced via molecular dynamics simulations. Values for the radial distribution function, coordination number, and number of hydrogen bonds were then calculated to explore the local structure of each fluid. The flexibility of the n-alkane (as characterized by the computed dihedral distribution, end-to-end distance, and radius of gyration) was found to be a major influence and hydrogen bonding to be a minor influence on the local structure. Hydrogen bonding reduces the flexibility of the n-alkane, whereas increasing the temperature enhances its flexibility, with temperature having a greater effect than hydrogen bonding on flexibility. Graphical abstract The flexibility of the alkane is a major influence and the hydrogen bonding is a minor influence on the first solvation shell; the coordination numbers of long-chain n-alkanes in the first solvation shell are rather low.

Development of a Novel Ni-Fe-Cr-B-Si Interlayer Material for Transient Liquid Phase Bonding of Inconel 718

NASA Astrophysics Data System (ADS)

Tarai, U. K.; Robi, P. S.; Pal, Sukhomay

2018-04-01

A Ni-Cr-Fe-Si-B based interlayer material was developed by mechanical alloying (MA) process in a high-energy planetary ball mill. Equiaxed alloy powders of size 12 µm was obtained after milling for 50 hours. X-ray diffraction analysis of the milled powder revealed that milling of elemental powders initially resulted in microcrystalline alloy powder having face centered cubic structure, which on subsequent milling resulted in nano-crystallice alloy powder with a crystallite size of 3.2 nm. XRD analysis also reveals formation of metastable eutectic alloys resulting in lowering of the melting point of the interlayer material to 1025 °C. IN 718 superalloy samples were joined at 1050°C using the developed interlayer. A homogeneous joint was formed by the newly developed interlayer material. Three different zones were observed at the bond (i) isothermally solidified zone, (ii) diffusion affected zone and (iii) unaffected base metal. In the diffusion-affected zone, boron was present at the grain boundaries of Ni γ matrix in bulky metal borides form. The diffusion of boron from interlayer material into the base material was mechanism of isothermal solidification and bond formation in transient liquid phase bonding of IN 718.

Suppression of interfacial voids formation during silane (SiH4)-based silicon oxide bonding with a thin silicon nitride capping layer

NASA Astrophysics Data System (ADS)

Lee, Kwang Hong; Bao, Shuyu; Wang, Yue; Fitzgerald, Eugene A.; Seng Tan, Chuan

2018-01-01

The material properties and bonding behavior of silane-based silicon oxide layers deposited by plasma-enhanced chemical vapor deposition were investigated. Fourier transform infrared spectroscopy was employed to determine the chemical composition of the silicon oxide films. The incorporation of hydroxyl (-OH) groups and moisture absorption demonstrates a strong correlation with the storage duration for both as-deposited and annealed silicon oxide films. It is observed that moisture absorption is prevalent in the silane-based silicon oxide film due to its porous nature. The incorporation of -OH groups and moisture absorption in the silicon oxide films increase with the storage time (even in clean-room environments) for both as-deposited and annealed silicon oxide films. Due to silanol condensation and silicon oxidation reactions that take place at the bonding interface and in the bulk silicon, hydrogen (a byproduct of these reactions) is released and diffused towards the bonding interface. The trapped hydrogen forms voids over time. Additionally, the absorbed moisture could evaporate during the post-bond annealing of the bonded wafer pair. As a consequence, defects, such as voids, form at the bonding interface. To address the problem, a thin silicon nitride capping film was deposited on the silicon oxide layer before bonding to serve as a diffusion barrier to prevent moisture absorption and incorporation of -OH groups from the ambient. This process results in defect-free bonded wafers.

Two-dimensional infrared spectroscopy of intermolecular hydrogen bonds in the condensed phase.

PubMed

Elsaesser, Thomas

2009-09-15

Hydrogen bonding plays a key role in the structural, physical, and chemical properties of liquids such as water and in macromolecular structures such as proteins. Vibrational spectroscopy is an important tool for understanding hydrogen bonding because it provides a way to observe local molecular geometries and their interaction with the environment. Linear vibrational spectroscopy has mapped characteristic changes of vibrational spectra and the occurrence of new bands that form upon hydrogen bonding. However, linear vibrational spectroscopy gives very limited insight into ultrafast dynamics of the underlying molecular interactions, such as the motions of hydrogen-bonded groups, energy dissipation and delocalization, and the fluctuations within hydrogen-bonded structures that occur in the ultrafast time domain. Nonlinear vibrational spectroscopy with its femtosecond time resolution can discern these dynamic processes in real time and has emerged as an important tool for unraveling molecular dynamics and for quantifying interactions that govern the vibrational and structural dynamics of hydrogen bonds. This Account reviews recent progress originating from third-order nonlinear methods of coherent multidimensional vibrational spectroscopy. Ultrafast dynamics of intermolecular hydrogen bonds are addressed for a number of prototype systems: hydrogen-bonded carboxylic acid dimers in an aprotic liquid environment, the disordered fluctuating hydrogen-bond network of liquid water, and DNA oligomers interacting with water. Cyclic carboxylic acid dimers display a rich scheme of vibrational couplings, resulting in OH stretching absorption bands with highly complex spectral envelopes. Two-dimensional spectroscopy of acetic acid dimers in a nonpolar liquid environment demonstrates that multiple Fermi resonances of the OH stretching mode with overtones and combination tones of fingerprint vibrations dominate both the 2D and linear absorption spectra. The coupling of the OH stretching mode with low-frequency hydrogen-bonding modes leads to additional progressions and coherent low-frequency hydrogen-bond motions in the subpicosecond time domain. In water, the 2D spectra reveal ultrafast spectral diffusion on a sub-100 fs time scale caused by the ultrafast structural fluctuations of the strongly coupled hydrogen-bond network. Librational motions play a key role for the ultrafast loss of structural memory. Spectral diffusion rates are enhanced by resonant transfer of OH stretching quanta between water molecules, typically occurring on a 100 fs time scale. In DNA oligomers, femtosecond nonlinear vibrational spectroscopy resolves NH and OH stretching bands in the highly congested infrared spectra of these molecules, which contain alternating adenine-thymine pairs. Studies at different levels of hydration reveal the spectral signatures of water molecules directly interacting with the phosphate groups of DNA and of a second water species forming a fluctuating environment around the DNA oligomers. We expect that the application of 2D infrared spectroscopy in an extended spectral range will reveal the intrinsic coupling between water and specific functional units of DNA.

Hydrothermal corrosion of silicon carbide joints without radiation

DOE PAGES

Koyanagi, Takaaki; Katoh, Yutai; Terrani, Kurt A.; ...

2016-09-28

In this paper, hydrothermal corrosion of four types of the silicon carbide (SiC) to SiC plate joints were investigated under pressurized water reactor and boiling water reactor relevant chemical conditions without irradiation. The joints were formed by metal diffusion bonding using molybdenum or titanium interlayer, reaction sintering using Ti—Si—C system, and SiC nanopowder sintering. Most of the joints withstood the corrosion tests for five weeks. The recession of the SiC substrates was limited. Based on the recession of the bonding layers, it was concluded that all the joints except for the molybdenum diffusion bond are promising under the reducing environmentsmore » without radiation. Finally, the SiC nanopowder sintered joint was the most corrosion tolerant under the oxidizing environment among the four joints.« less

Importance of hydrophobic traps for proton diffusion in lyotropic liquid crystals

DOE PAGES

McDaniel, Jesse G.; Yethiraj, Arun

2016-03-04

The diffusion of protons in self-assembled systems is potentially important for the design of efficient proton exchange membranes. In this work, we study proton dynamics in a low-water content, lamellar phase of an sodium-carboxylate gemini surfactant/water system using computer simulations. The hopping of protons via the Grotthuss mechanism is explicity allowed through the multi-state empirical valence bond (MS-EVB) method. We find that the hydronium ion is trapped on the hydrophobic side of the surfactant-water interface, and proton diffusion then proceeds by hopping between surface sites. The importance of hydrophobic traps is surprising, because one would expect the hydronium ions tomore » be trapped at the charged head-groups. Finally, the physics illustrated in this system should be relevant to the proton dynamics in other amphiphilic membrane systems, whenever there exists exposed hydrophobic surface regions.« less

Diffusion Bonding of Microduplex Stainless Steel and Ti Alloy with and without Interlayer: Interface Microstructure and Strength Properties

NASA Astrophysics Data System (ADS)

Kundu, S.; Sam, S.; Mishra, B.; Chatterjee, S.

2014-01-01

The interface microstructure and strength properties of solid state diffusion bonding of microduplex stainless steel (MDSS) to Ti alloy (TiA) with and without a Ni alloy (NiA) intermediate material were investigated at 1173 K (900 °C) for 0.9 to 5.4 ks in steps of 0.9 ks in vacuum. The effects of bonding time on the microstructure of the bonded joint have been analyzed by light optical microscopy and scanning electron microscopy in the backscattered mode. In the direct bonded joints of MDSS and TiA, the layer-wise σ phase and the λ + FeTi phase mixture were observed at the bond interface when the joint was processed for 2.7 ks and above holding times. However, when NiA was used as an intermediate material, the results indicated that TiNi3, TiNi, and Ti2Ni are formed at the NiA-TiA interface, and the irregular shaped particles of Fe22Mo20Ni45Ti13 have been observed within the TiNi3 intermetallic layer. The stainless steel-NiA interface is free from intermetallics and the layer of austenitic phase was observed at the stainless steel side. A maximum tensile strength of ~520 MPa, shear strength of ~405 MPa, and impact toughness of ~18 J were obtained for the directly bonded joint when processed for 2.7 ks. However, when nickel base alloy was used as an intermediate material in the same materials, the bond tensile and shear strengths increase to ~640 and ~479 MPa, respectively, and the impact toughness to ~21 J when bonding was processed for 4.5 ks. Fracture surface observations in scanning electron microscopy using energy dispersive spectroscopy demonstrate that in MDSS-TiA joints, failure takes place through the FeTi + λ phase when bonding was processed for 2.7 ks; however, failure takes place through σ phase for the diffusion joints processed for 3.6 ks and above processing times. However, in MDSS-NiA-TiA joints, the fracture takes place through NiTi2 layer at the NiA-TiA interface for all bonding times.

The structure of hydrophobic gas diffusion electrodes.

NASA Technical Reports Server (NTRS)

Giner, J.

1972-01-01

The 'flooded agglomerate' model of the Teflon-bonded gas diffusion electrode is discussed. A mathematical treatment of the 'flooded agglomerate' model is given; it can be used to predict the performance of the electrode as a function of measurable physical parameters.

Reactions between palladium and gallium arsenide: Bulk versus thin-film studies

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

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

1988-01-01

Reactions between Pd and GaAs have been studied using bulk-diffusion couples of Pd (approx.0.6 mm thick)/GaAs and thin-film Pd (50 and 160 nm)/GaAs samples. The sequence of phase formation at 600 /sup 0/C between bulk Pd and GaAs was established. Initial formation of the solution phase ..mu.. and the ternary phase T does not represent the stable configuration. The stable configuration is GaAs chemically bondepsilonchemically bondlambdachemically bond..gamma..chemically bond..nu..chemically bondPd and is termed the diffusion path between GaAs and Pd. The sequence of phase formation for the bulk-diffusion couples is similar at 500 /sup 0/C. Phase formation for the thin-film Pd/GaAsmore » specimens was studied at 180, 220, 250, 300, 350, 400, 450, 600, and 1000 /sup 0/C for various annealing times. The sequence of phase formation obtained from the thin-film experiments is rationalized readily from the known ternary phase equilibria of Ga--Pd--As and the results from the bulk-diffusion couples of Pd/GaAs. The thin-film results reported in the literature are likewise rationalized. The diffusion path concept provides a useful guide in understanding the phase formation in Pd--GaAs interface or any other M--GaAs interface. This information is important in designing a uniform, stable contact for the metallization of GaAs.« less

Ga originated kink-and-tail Zn diffusion profiles in InGaAsP and InGaAlAs alloys during MOVPE regrowth

NASA Astrophysics Data System (ADS)

Kitatani, T.; Okamoto, K.; Uchida, K.; Tanaka, S.

2017-12-01

We investigated the diffusion characteristics of Zn in ternary and quaternary alloys of InGaAsP and InGaAlAs, which are important materials in long-wavelength optical communication devices. The measured Zn diffusion profiles of InGaAs, InGaAsP, and InGaAlAs showed kink-and-tail shapes in which Zn concentration fell abruptly at first and then decreased slowly, whereas those of InP and InAlAs showed only abrupt decreases. Thus, only Ga-containing alloys had tail-like profiles. Since this tail was well described by the group-V vacancy related defect model, we deduced that its mechanism is closely related with group-V vacancies in Ga-related bonds such as GaP or GaAs. Furthermore, we demonstrated the possibility that many more group-V vacancies originated from GaP bonds than from GaAs bonds, indicating the difficulty in crystal growth of high quality alloys that have GaP components.

[Effects of laser welding on bond of porcelain fused cast pure titanium].

PubMed

Zhu, Juan-fang; He, Hui-ming; Gao, Bo; Wang, Zhong-yi

2006-04-01

To investigate the influence of the laser welding on bond of porcelain fused to cast pure titanium. Twenty cast titanium plates were divided into two groups: laser welded group and control group. The low-fusing porcelain was fused to the laser welded cast pure titanium plates at fusion zone. The bond strength of the porcelain to laser welded cast pure titanium was measured by the three-point bending test. The interface of titanium and porcelain was investigated by scanning electron microscopy (SEM) and energy depressive X-ray detector (EDX). The non-welded titanium plates were used as comparison. No significant difference of the bond strength was found between laser-welded samples [(46.85 +/- 0.76) MPa] and the controls [(41.71 +/- 0.55) MPa] (P > 0.05). The SEM displayed the interface presented similar irregularities with a predominance. The titanium diffused to low-fusing porcelain, while silicon and aluminum diffused to titanium basement. Laser welding does not affect low-fusing porcelain fused to pure titanium.

Iodine versus Bromine Functionalization for Bottom-Up Graphene Nanoribbon Growth: Role of Diffusion

DOE PAGES

Bronner, Christopher; Marangoni, Tomas; Rizzo, Daniel J.; ...

2017-08-08

Deterministic bottom-up approaches for synthesizing atomically well-defined graphene nanoribbons (GNRs) largely rely on the surface-catalyzed activation of selected labile bonds in a molecular precursor followed by step-growth polymerization and cyclodehydrogenation. While the majority of successful GNR precursors rely on the homolytic cleavage of thermally labile C–Br bonds, the introduction of weaker C–I bonds provides access to monomers that can be polymerized at significantly lower temperatures, thus helping to increase the flexibility of the GNR synthesis process. Scanning tunneling microscopy imaging of molecular precursors, activated intermediates, and polymers resulting from stepwise thermal annealing of both Br and I substituted precursors formore » chevron GNRs reveals that the polymerization of both precursors proceeds at similar temperatures on Au(111). Finally, this surprising observation is consistent with diffusion-controlled polymerization of the surface-stabilized radical intermediates that emerge from homolytic cleavage of either the C–Br or the C–I bonds.« less

Molecular dynamics of acetamide based ionic deep eutectic solvents

NASA Astrophysics Data System (ADS)

Srinivasan, H.; Dubey, P. S.; Sharma, V. K.; Biswas, R.; Mitra, S.; Mukhopadhyay, R.

2018-04-01

Deep eutectic solvents are multi-component mixtures that have freezing point lower than their individual components. Mixture of acetamide+ lithium nitrate in the molar ratio 78:22 and acetamide+ lithium perchlorate in the molar ratio 81:19 are found to form deep eutectic solvents with melting point lower than the room temperature. It is known that the depression in freezing point is due to the hydrogen bond breaking ability of anions in the system. Quasielastic neutron scattering experiments on these systems were carried out to study the dynamics of acetamide molecules which may be influenced by this hydrogen bond breaking phenomena. The motion of acetamide molecules is modeled using jump diffusion mechanism to demonstrate continuous breaking and reforming hydrogen bonds in the solvent. Using the jump diffusion model, it is inferred that the jump lengths of acetamide molecules are better approximated by a Gaussian distribution. The shorter residence time of acetamide in presence of perchlorate ions suggest that the perchlorate ions have a higher hydrogen bond breaking ability compared to nitrate ions.

Fluorescence Correlation Spectroscopy to Study Diffusion of Polymer Chains within Layered Hydrogen-Bonded Polymer Films

NASA Astrophysics Data System (ADS)

Pristinski, Denis; Kharlampieva, Evguenia; Sukhishvili, Svetlana

2002-03-01

Fluorescence Correlation Spectroscopy (FCS) has been used to probe molecular motions within polymer multilayers formed by hydrogen-bonding sequential self-assembly. Polyethylene glycol (PEG) molecules were end-labeled with the fluorescent tags, and self-assembled with polymethacrylic acid (PMAA) using layer-by-layer deposition. We have found that molecules included in the top adsorbed layer have significant mobility at the millisecond time scale, probably due to translational diffusion. However, their dynamics deviate from classical Brownian motion with a single diffusion time. Possible reasons for the deviation are discussed. We found that motions were significantly slowed with increasing depth within the PEG/PMAA multilayer. This phenomena occured in a narrow pH range around 4.0 in which intermolecular interactions were relatively weak.

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique

PubMed Central

Yoon, Seokhyun; Kim, Si Joon; Tak, Young Jun; Kim, Hyun Jae

2017-01-01

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers. PMID:28230088

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique

NASA Astrophysics Data System (ADS)

Yoon, Seokhyun; Kim, Si Joon; Tak, Young Jun; Kim, Hyun Jae

2017-02-01

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers.

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique.

PubMed

Yoon, Seokhyun; Kim, Si Joon; Tak, Young Jun; Kim, Hyun Jae

2017-02-23

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers.

Demonstration of Subscale Cermet Fuel Specimen Fabrication Approach Using Spark Plasma Sintering and Diffusion Bonding

NASA Technical Reports Server (NTRS)

Barnes, Marvin W.; Tucker, Dennis S.; Benensky, Kelsa M.

2018-01-01

Nuclear thermal propulsion (NTP) has the potential to expand the limits of human space exploration by enabling crewed missions to Mars and beyond. The viability of NTP hinges on the development of a robust nuclear fuel material that can perform in the harsh operating environment (> or = 2500K, reactive hydrogen) of a nuclear thermal rocket (NTR) engine. Efforts are ongoing to develop fuel material and to assemble fuel elements that will be stable during the service life of an NTR. Ceramic-metal (cermet) fuels are being actively pursued by NASA Marshall Space Flight Center (MSFC) due to their demonstrated high-temperature stability and hydrogen compatibility. Building on past cermet fuel development research, experiments were conducted to investigate a modern fabrication approach for cermet fuel elements. The experiments used consolidated tungsten (W)-60vol%zirconia (ZrO2) compacts that were formed via spark plasma sintering (SPS). The consolidated compacts were stacked and diffusion bonded to assess the integrity of the bond lines and internal cooling channel cladding. The assessment included hot hydrogen testing of the manufactured surrogate fuel and pure W for 45 minutes at 2500 K in the compact fuel element environmental test (CFEET) system. Performance of bonded W-ZrO2 rods was compared to bonded pure W rods to access bond line integrity and composite stability. Bonded surrogate fuels retained structural integrity throughout testing and incurred minimal mass loss.

Thiolated polymers: evidence for the formation of disulphide bonds with mucus glycoproteins.

PubMed

Leitner, Verena M; Walker, Greg F; Bernkop-Schnürch, Andreas

2003-09-01

Disulphide bonds between thiolated polymers (thiomers) and cysteine-rich subdomains of mucus glycoproteins are supposed to be responsible for the enhanced mucoadhesive properties of thiomers. This study set out to provide evidence for these covalent interactions using poly(acrylic acid)-cysteine conjugates of 2 and 450 kDa (PAA2-Cys, PAA450-Cys) displaying 402.5-776.0 micromol thiol groups per gram polymer. The effect of the disulphide bond breaker cysteine on thiomer-mucin disulphide bonds was monitored by (1) mucoadhesion studies and (2) rheological studies. Furthermore, (3) diffusion studies and (4) gel filtration studies were performed with thiomer-mucus mixtures. The addition of cysteine significantly (P<0.01) reduced the adhesion of thiomer tablets to porcine mucosa and G'/G" values of thiomer-mucin mixtures, whereas unthiolated controls were not influenced. These results indicate the cleavage of disulphide bonds between thiomer and mucus glycoproteins. Diffusion studies demonstrated that a 12.8-fold higher concentration of the thiomer (PAA2-Cys) remains in the mucin gel than the corresponding unmodified polymer. Gel filtration studies showed that PAA2-Cys was able to form disulphide bonds with mucin glycoproteins resulting in an altered elution profile of the mucin/PAA2-Cys mixture in comparison to mucin alone or mucin/PAA2 mixture. According to these results, the study provides evidence for the formation of covalent bonds between thiomer and mucus glycoproteins.

Surface diffusion of CO on silica-supported Ru particles: 13C nuclear magnetic resonance studies

NASA Astrophysics Data System (ADS)

Duncan, T. M.; Thayer, A. M.; Root, T. W.

1990-02-01

Portions of CO adsorbed on Ru particles, selected by the orientation of the C-O bond relative to an external magnetic field, are labeled by inversion of the 13C nuclear magnetic dipole. Changes in the orientation of the CO bond of these labeled molecules are then observed with 13C NMR spectroscopy. The temperature dependence and rate of reorientation are consistent with surface diffusion on Ru particles with small numbers of flat faces. The insensitivity to CO pressure in the range 0.5-100 Torr discounts stimulated desorption by gas-phase CO.

COATED CARBON ELEMENT FOR USE IN NUCLEAR REACTORS AND THE PROCESS OF MAKING THE ELEMENT

DOEpatents

Pyle, R.J.; Allen, G.L.

1963-01-15

S>This patent relates to a carbide-nitride-carbide coating for carbon bodies that are to be subjected to a high temperature nuclear reactor atmosphere, and a method of applying the same. This coating is a highly efficient diffusion barrier and protects the C body from corrosion and erosion by the reactor atmosphere. Preferably, the innermost coating is Zr carbide, the middle coatlng is Zr nitride, and the outermost coating is a mixture of Zr and Nb carbide. The nitride coating acts as a diffusion barrier, while the innermost carbide bonds the nitride to the C body and prevents deleterious reaction between the nitride and C body. The outermost carbide coating protects the nitride coating from the reactor atmosphere. (AEC)

Microstructural characteristics of HIP-bonded monolithic nuclear fuels with a diffusion barrier

NASA Astrophysics Data System (ADS)

Jue, Jan-Fong; Keiser, Dennis D.; Breckenridge, Cynthia R.; Moore, Glenn A.; Meyer, Mitchell K.

2014-05-01

Due to the limitation of maximum uranium load achievable by dispersion fuel type, the Global Threat Reduction Initiative is developing an advanced monolithic fuel to convert US high-performance research reactors to low-enriched uranium. Hot-isostatic-press (HIP) bonding was the single process down-selected to bond monolithic U-Mo fuel meat to aluminum alloy cladding. A diffusion barrier was applied to the U-Mo fuel meat by roll-bonding process to prevent extensive interaction between fuel meat and aluminum-alloy cladding. Microstructural characterization was performed on fresh fuel plates fabricated at Idaho National Laboratory. Interfaces between the fuel meat, the cladding, and the diffusion barrier, as well as between the U-10Mo fuel meat and the Al-6061 cladding, were characterized by scanning electron microscopy. Preliminary results indicate that the interfaces contain many different phases while decomposition, second phases, and chemical banding were also observed in the fuel meat. The important attributes of the HIP-bonded monolithic fuel are:

Microstructural Characteristics of HIP-bonded Monolithic Nuclear Fuels with a Diffusion Barrier

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

Jan-Fong Jue; Dennis D. Keiser, Jr.; Cynthia R. Breckenridge

Due to the limitation of maximum uranium load achievable by dispersion fuel type, the Global Threat Reduction Initiative (GTRI) is developing an advanced monolithic fuel to convert US high performance research reactors to low-enriched uranium. Hot-isostatic-press bonding was the single process down-selected to bond monolithic U-Mo fuel meat to aluminum alloy cladding. A diffusion barrier was applied to the U–Mo fuel meat by roll-bonding process to prevent extensive interaction between fuel meat and aluminum-alloy cladding. Microstructural characterization was performed on fresh fuel plates fabricated at Idaho National Laboratory. Interfaces between fuel meat, cladding, and diffusion barrier, as well as U–10Momore » fuel meat and Al–6061 cladding were characterized by scanning electron microscopy. Preliminary results indicate that the interfaces contain many different phases while decomposition, second phases, and chemical banding were also observed in the fuel meat. The important attributes of the HIP-bonded monolithic fuel are • A typical Zr diffusion barrier of thickness 25 µm • Transverse cross section that exhibits relatively equiaxed grains with an average grain diameter of 10 µm • Chemical banding, in some areas more than 100 µm in length, that is very pronounced in longitudinal (i.e., rolling) direction with Mo concentration varying from 7–13 wt% • Decomposed areas containing plate-shaped low-Mo phase • A typical Zr/cladding interaction layer of thickness 1-2 µm • A visible UZr2 bearing layer of thickness 1-2 µm • Mo-rich precipitates (mainly Mo2Zr, forming a layer in some areas) followed by a Mo-depleted sub-layer between the visible UZr2-bearing layer and the U–Mo matrix • No excessive interaction between cladding and the uncoated fuel edge • Cladding-to-cladding bonding that exhibits no cracks or porosity with second phases high in Mg, Si, and O decorating the bond line. • Some of these attributes might be critical to the irradiation performance of monolithic U-10Mo nuclear fuel. There are several issues or concerns that warrant more detailed study, such as precipitation along cladding-to-cladding bond line, chemical banding, uncovered fuel-zone edge, and interaction layer between U–Mo fuel meat and zirconium. Future post-irradiation examination results will focus, among other things, on identifying in-reactor failure mechanisms and, eventually, directing further fresh fuel characterization efforts.« less

Indirect Versus Direct Heating of Sheet Materials: Superplastic Forming and Diffusion Bonding Using Lasers

NASA Astrophysics Data System (ADS)

Jocelyn, Alan; Kar, Aravinda; Fanourakis, Alexander; Flower, Terence; Ackerman, Mike; Keevil, Allen; Way, Jerome

2010-06-01

Many from within manufacturing industry consider superplastic forming (SPF) to be ‘high tech’, but it is often criticized as too complicated, expensive, slow and, in general, an unstable process when compared to other methods of manipulating sheet materials. Perhaps, the fundamental cause of this negative perception of SPF, and also of diffusion bonding (DB), is the fact that the current process of SPF/DB relies on indirect sources of heating to produce the conditions necessary for the material to be formed. Thus, heat is usually derived from the electrically heated platens of hydraulic presses, to a lesser extent from within furnaces and, sometimes, from heaters imbedded in ceramic moulds. Recent evaluations of these isothermal methods suggest they are slow, thermally inefficient and inappropriate for the process. In contrast, direct heating of only the material to be formed by modern, electrically efficient, lasers could transform SPF/DB into the first choice of designers in aerospace, automotive, marine, medical, architecture and leisure industries. Furthermore, ‘variable temperature’ direct heating which, in theory, is possible with a laser beam(s) may provide a means to control material thickness distribution, a goal of enormous importance as fuel efficient, lightweight structures for transportation systems are universally sought. This paper compares, and contrasts, the two systems and suggests how a change to laser heating might be achieved.

Performance of quantum Monte Carlo for calculating molecular bond lengths

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

Cleland, Deidre M., E-mail: deidre.cleland@csiro.au; Per, Manolo C., E-mail: manolo.per@csiro.au

2016-03-28

This work investigates the accuracy of real-space quantum Monte Carlo (QMC) methods for calculating molecular geometries. We present the equilibrium bond lengths of a test set of 30 diatomic molecules calculated using variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) methods. The effect of different trial wavefunctions is investigated using single determinants constructed from Hartree-Fock (HF) and Density Functional Theory (DFT) orbitals with LDA, PBE, and B3LYP functionals, as well as small multi-configurational self-consistent field (MCSCF) multi-determinant expansions. When compared to experimental geometries, all DMC methods exhibit smaller mean-absolute deviations (MADs) than those given by HF, DFT, and MCSCF.more » The most accurate MAD of 3 ± 2 × 10{sup −3} Å is achieved using DMC with a small multi-determinant expansion. However, the more computationally efficient multi-determinant VMC method has a similar MAD of only 4.0 ± 0.9 × 10{sup −3} Å, suggesting that QMC forces calculated from the relatively simple VMC algorithm may often be sufficient for accurate molecular geometries.« less

M3FT-16OR020202112 - Report on viability of hydrothermal corrosion resistant SiC/SiC Joint development

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

Katoh, Yutai; Koyanagi, Takaaki; Kiggans Jr, James O.

2016-06-30

Hydrothermal corrosion of four types of the silicon carbide (SiC) to SiC plate joints were investigated under PWR and BWR relevant chemical conditions without irradiation. The joints were formed by metal diffusion bonding using molybdenum or titanium interlayer, reaction sintering using Ti-Si-C system, and SiC nanopowder sintering. Most of the formed joints withstood the corrosion tests for five weeks. The recession of the SiC substrates was limited. Based on the recession rate of the bonding layers, it was concluded that all the joints except for the molybdenum diffusion bond are promising under the reducing activity environments. The SiC nanopowder sinteredmore » joint was the most corrosion tolerant under the oxidizing activity environment among the four joints.« less

Processing and Characterization of Liquid-Phase Sintered NiTi Woven Structures

NASA Astrophysics Data System (ADS)

Erdeniz, Dinc; Weidinger, Ryan P.; Sharp, Keith W.; Dunand, David C.

2018-03-01

Porous NiTi is of interest for bone implants because of its unique combination of biocompatibility (encouraging osseointegration), high strength (to prevent fracture), low stiffness (to reduce stress shielding), and shape memory or superelasticity (to deploy an implant). A promising method for creating NiTi structures with regular open channels is via 3D weaving of NiTi wires. This paper presents a processing method to bond woven NiTi wire structures at contact points between wires to achieve structural integrity: (i) a slurry consisting of a blend of NiTi and Nb powders is deposited on the surface of the NiTi wires after the weaving operation; (ii) the powders are melted to create a eutectic liquid phase which collects at contact points; and (iii) the liquid is solidified and binds the NiTi woven structures. The bonded NiTi wire structures exhibited lower transformation temperatures compared to the as-woven NiTi wires because of Nb diffusion into the NiTi wires. A bonded woven sample was deformed in bending and showed near-complete recovery up to 6% strain and recovered nearly half of the deformation up to 19% strain.

Role of large-scale slip in mode II fracture of bimaterial interface produced by diffusion bonding

NASA Astrophysics Data System (ADS)

Fox, M. R.; Ghosh, A. K.

2001-08-01

Bimaterial interfaces present in diffusion-bonded (and in-situ) composites are often not flat interfaces. The unevenness of the interface can result not only from interface reaction products but also from long-range waviness associated with the surfaces of the component phases bonded together. Experimental studies aimed at determining interface mechanical properties generally ignore the departure in the local stress due to waviness and assume a theoretically flat interface. Furthermore, the commonly used testing methods involving superimposed tension often renders the interface so extremely brittle that if microplastic effects were present it becomes impossible to perceive them. This article examines the role of waviness of the interface and microplastic effects on crack initiation. To do this, a test was selected that provides significant stability against crack growth by superimposing compressive stresses. Mode II interface fracture was studied for NiAl/Mo model laminates using a recently developed asymmetrically loaded shear (ALS) interface shear test. The ALS test may be viewed as opposite of the laminate bend test. In the bend test, shear at the interface is created via tension on one surface of the bend, while in the ALS test, shear is created by compression on one side of the interface relative to the other. Normal to the interface, near the crack tip, an initially compressive state is replaced by slight tension due to Poisson’s expansion of the unbonded part of the compressed beam.

Sodium ion diffusion in Al2O3: a distinct perspective compared with lithium ion diffusion.

PubMed

Jung, Sung Chul; Kim, Hyung-Jin; Choi, Jang Wook; Han, Young-Kyu

2014-11-12

Surface coating of active materials has been one of the most effective strategies to mitigate undesirable side reactions and thereby improve the overall battery performance. In this direction, aluminum oxide (Al2O3) is one of the most widely adopted coating materials due to its easy synthesis and low material cost. Nevertheless, the effect of Al2O3 coating on carrier ion diffusion has been investigated mainly for Li ion batteries, and the corresponding understanding for emerging Na ion batteries is currently missing. Using ab initio molecular dynamics calculations, herein, we first find that, unlike lithiation, sodiation of Al2O3 is thermodynamically unfavorable. Nonetheless, there can still exist a threshold in the Na ion content in Al2O3 before further diffusion into the adjacent active material, delivering a new insight that both thermodynamics and kinetics should be taken into account to describe ionic diffusion in any material media. Furthermore, Na ion diffusivity in NaxAl2O3 turns out to be much higher than Li ion diffusivity in LixAl2O3, a result opposite to the conventional stereotype based on the atomic radius consideration. While hopping between the O-rich trapping sites via an Na-O bond breaking/making process is identified as the main Na ion diffusion mechanism, the weaker Na-O bond strength than the Li-O counterpart turns out to be the origin of the superior diffusivity of Na ions.

A Low Temperature Co-fired Ceramics Manufactured Power Inductor Based on A Ternary Hybrid Material System

NASA Astrophysics Data System (ADS)

Xie, Yunsong; Chen, Ru

Low temperature co-fired ceramics (LTCC) is one of the most important techniques to produce circuits with high working frequency, multi-functionality and high integration. We have developed a methodology to enable a ternary hybrid material system being implemented into the LTCC manufacturing process. The co-firing sintering process can be divided into a densification and cooling process. In this method, a successful ternary hybrid material densification process is achieved by tuning the sintering profile of each material to match each other. The system integrity is maintained in the cooling process is obtained by develop a strong bonding at the interfaces of each materials. As a demonstration, we have construct a power inductor device made of the ternary material system including Ag, NiCuZn ferrite and non-magnetic ceramic. The power inductors well maintains its physical integrity after sintering. The microscopic images show no obvious sign of cracks or structural deformation. More importantly, despite the bonding between the ferrite and ceramic is enhanced by non-magnetic element diffusion, the undesired magnetic elements diffusion is effectively suppressed. The electric performance shows that the power handling capability is comparable to the current state of art device.

Bonding Diamond To Metal In Electronic Circuits

NASA Technical Reports Server (NTRS)

Jacquez, Andrew E.

1993-01-01

Improved technique for bonding diamond to metal evolved from older technique of soldering or brazing and more suitable for fabrication of delicate electronic circuits. Involves diffusion bonding, developed to take advantage of electrically insulating, heat-conducting properties of diamond, using small diamond bars as supports for slow-wave transmission-line structures in traveling-wave-tube microwave amplifiers. No fillets or side coats formed because metal bonding strips not melted. Technique also used to mount such devices as transistors and diodes electrically insulated from, but thermally connected to, heat sinks.

The covalently bound diazo group as an infrared probe for hydrogen bonding environments.

PubMed

You, Min; Liu, Liyuan; Zhang, Wenkai

2017-07-26

Covalently bound diazo groups are frequently found in biomolecular substrates. The C[double bond, length as m-dash]N[double bond, length as m-dash]N asymmetric stretching vibration (ν as ) of the diazo group has a large extinction coefficient and appears in an uncongested spectral region. To evaluate the solvatochromism of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band for studying biomolecules, we recorded the infrared (IR) spectra of a diazo model compound, 2-diazo-3-oxo-butyric acid ethyl ester, in different solvents. The width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band was linearly dependent on the Kamlet-Taft solvent parameter, which reflects the polarizability and hydrogen bond accepting ability of the solvent. Therefore, the width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band could be used to probe these properties for a solvent. We found that the position of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band was linearly correlated with the density of hydrogen bond donor groups in the solvent. We studied the relaxation dynamics and spectral diffusion of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band of a natural amino acid, 6-diazo-5-oxo-l-norleucine, in water using nonlinear IR spectroscopy. The relaxation and spectral diffusion time constants of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band were similar to those of the N[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band. We concluded that the position and width of the C[double bond, length as m-dash]N[double bond, length as m-dash]N ν as band of the diazo group could be used to probe the hydrogen bond donating and accepting ability of a solvent, respectively. These results suggest that the diazo group could be used as a site-specific IR probe for the local hydration environments.

Theoretical study of oxygen sorption and diffusion in the volume and on the surface of a γ-TiAl alloy

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

Bakulin, A. V., E-mail: bakulin@ispms.tsc.ru; Kulkova, S. E.; Hu, Q. M.

2015-02-15

The oxygen sorption on the low-index (001), (100), and (110) surfaces of a γ-TiAl alloy is studied by the pseudopotential method with the generalized gradient approximation for the exchange-correlation functional. The most preferred sites for oxygen sorption in the bulk and on the surface of the alloy are determined. The titanium-rich octahedral site is shown to be preferred for oxygen sorption in the bulk material. The effect of the oxygen concentration on the atomic and electronic structures of the stoichiometric TiAl(100) surface is studied. It is shown that, at the first stage of oxidation, oxygen prefers to form bonds withmore » titanium. The energy barriers for oxygen diffusion on the stoichiometric (100) surface and in the bulk of the material are calculated. The energy barriers are shown to depend substantially on the local environments of oxygen and to increase during diffusion from titanium-rich sites. The most possible mechanism of oxygen diffusion from the (100) surface to the bulk of the material is oxygen migration through tetrahedral sites.« less

Raman and CT scan mapping of chalcogenide glass diffusion generated gradient index profiles

NASA Astrophysics Data System (ADS)

Lindberg, G. P.; Berg, R. H.; Deegan, J.; Benson, R.; Salvaggio, P. S.; Gross, N.; Weinstein, B. A.; Gibson, D.; Bayya, S.; Sanghera, J.; Nguyen, V.; Kotov, M.

2016-05-01

Metrology of a gradient index (GRIN) material is non-trivial, especially in the realm of infrared and large refractive index. Traditional methods rely on index matching fluids which are not available for indexes as high as those found in the chalcogenide glasses (2.4-3.2). By diffusing chalcogenide glasses of similar composition one can blend the properties in a continuous way. In an effort to measure this we will present data from both x-ray computed tomography scans (CT scans) and Raman mapping scans of the diffusion profiles. Proof of concept measurements on undiffused bonded sheets of chalcogenide glasses were presented previously. The profiles measured will be of axially stacked sheets of chalcogenide glasses diffused to create a linear GRIN profile and nested tubes of chalcogenide glasses diffused to create a radial parabolic GRIN profile. We will show that the x-ray absorption in the CT scan and the intensity of select Raman peaks spatially measured through the material are indicators of the concentration of the diffusion ions and correlate to the spatial change in refractive index. We will also present finite element modeling (FEM) results and compare them to post precision glass molded (PGM) elements that have undergone CT and Raman mapping.

Multistate empirical valence bond study of temperature and confinement effects on proton transfer in water inside hydrophobic nanochannels.

PubMed

Tahat, Amani; Martí, Jordi

2016-07-01

Microscopic characteristics of an aqueous excess proton in a wide range of thermodynamic states, from low density amorphous ices (down to 100 K) to high temperature liquids under the critical point (up to 600 K), placed inside hydrophobic graphene slabs at the nanometric scale (with interplate distances between 3.1 and 0.7 nm wide) have been analyzed by means of molecular dynamics simulations. Water-proton and carbon-proton forces were modeled with a multistate empirical valence bond method. Densities between 0.07 and 0.02 Å(-3) have been considered. As a general trend, we observed a competition between effects of confinement and temperature on structure and dynamical properties of the lone proton. Confinement has strong influence on the local structure of the proton, whereas the main effect of temperature on proton properties is observed on its dynamics, with significant variation of proton transfer rates, proton diffusion coefficients, and characteristic frequencies of vibrational motions. Proton transfer is an activated process with energy barriers between 1 and 10 kJ/mol for both proton transfer and diffusion, depending of the temperature range considered and also on the interplate distance. Arrhenius-like behavior of the transfer rates and of proton diffusion are clearly observed for states above 100 K. Spectral densities of proton species indicated that in all states Zundel-like and Eigen-like complexes survive at some extent. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Fabrication of tungsten wire reinforced nickel-base alloy composites

NASA Technical Reports Server (NTRS)

Brentnall, W. D.; Toth, I. J.

1974-01-01

Fabrication methods for tungsten fiber reinforced nickel-base superalloy composites were investigated. Three matrix alloys in pre-alloyed powder or rolled sheet form were evaluated in terms of fabricability into composite monotape and multi-ply forms. The utility of monotapes for fabricating more complex shapes was demonstrated. Preliminary 1093C (2000F) stress rupture tests indicated that efficient utilization of fiber strength was achieved in composites fabricated by diffusion bonding processes. The fabrication of thermal fatigue specimens is also described.

Mechanical Testing of Ultra-High Temperature Ceramics at 1500 C in Air - Development of an Experimental Facility and Test Method

DTIC Science & Technology

2015-03-26

SiC. TEM micrograph courtesy of R. S . Hay (AFRL/RXCC). ...................33 Fig. 5. Schematic of HfB2-based UHTC test specimen...the early work performed by the U. S . Air force and NASA was the identification of hafnium diboride (HfB2) and zirconium diboride (ZrB2) as good high...sintering, reactive routes, and spark plasma sintering. ~ 14 ~ Because diborides exhibit strong covalent bonding and low self-diffusion, high

Bonding and Integration Technologies for Silicon Carbide Based Injector Components

NASA Technical Reports Server (NTRS)

Halbig, Michael C.; Singh, Mrityunjay

2008-01-01

Advanced ceramic bonding and integration technologies play a critical role in the fabrication and application of silicon carbide based components for a number of aerospace and ground based applications. One such application is a lean direct injector for a turbine engine to achieve low NOx emissions. Ceramic to ceramic diffusion bonding and ceramic to metal brazing technologies are being developed for this injector application. For the diffusion bonding, titanium interlayers (PVD and foils) were used to aid in the joining of silicon carbide (SiC) substrates. The influence of such variables as surface finish, interlayer thickness (10, 20, and 50 microns), processing time and temperature, and cooling rates were investigated. Microprobe analysis was used to identify the phases in the bonded region. For bonds that were not fully reacted an intermediate phase, Ti5Si3Cx, formed that is thermally incompatible in its thermal expansion and caused thermal stresses and cracking during the processing cool-down. Thinner titanium interlayers and/or longer processing times resulted in stable and compatible phases that did not contribute to microcracking and resulted in an optimized microstructure. Tensile tests on the joined materials resulted in strengths of 13-28 MPa depending on the SiC substrate material. Non-destructive evaluation using ultrasonic immersion showed well formed bonds. For the joining technology of brazing Kovar fuel tubes to silicon carbide, preliminary development of the joining approach has begun. Various technical issues and requirements for the injector application are addressed.

Laminar flow control SPF/08 feasibility demonstration

NASA Astrophysics Data System (ADS)

Ecklund, R. C.; Williams, N. R.

1981-10-01

The feasibility of applying superplastic forming/diffusion bonding (SPF/DB) technology to laminar flow control (LFC) system concepts was demonstrated. Procedures were developed to produce smooth, flat titanium panels, using thin -0.016 inch sheets, meeting LFC surface smoothness requirements. Two large panels 28 x 28 inches were fabricated as final demonstration articles. The first was flat on the top and bottom sides demonstrating the capability of the tooling and the forming and diffusion bonding procedures to produce flat, defect free surfaces. The second panel was configurated for LFC porous panel treatment by forming channels with dimpled projections on the top side. The projections were machined away leaving holes extending into the panel. A perforated titanium sheet was adhesively bonded over this surface to complete the LFC demonstration panel. The final surface was considered flat enough to meet LFC requirements for a jet transport aircraft in cruising flight.

Current-Assisted Diffusion Bonding of Extruded Ti-22Al-25Nb Alloy by Spark Plasma Sintering: Interfacial Microstructure and Mechanical Properties

NASA Astrophysics Data System (ADS)

Yang, Jianlei; Wang, Guofeng; Jiao, Xueyan; Gu, Yibin; Liu, Qing; Li, You

2018-05-01

Spark plasma sintering (SPS) technology was used to current-assisted bond extruded Ti-22Al-25Nb alloy. The effects of bonding temperature (920-980 °C) and bonding time (10-30 min) on the microstructure evolution and shear strength of this alloy were investigated systematically. The temperature distribution in the specimen during the current-assisted bonding process was also analyzed by numerical simulation. It is noted that the highest temperature was obtained at the bonding interface. As the bonding temperature and bonding time increased, the voids in the interface shrank increasingly until they vanished. A complete metallurgical bonding interface could be produced at 960 °C/20 min/10 MPa, exhibiting the highest shear strength of 269.3 MPa. In addition, the shear strength of the bonded specimen depended on its interfacial microstructure. With increased bonding temperature, the fracture mode transformed from the intergranular fracture at the bonding interface to the cleavage fracture in the substrate.

[The influences of crystallized compositions in the porcelain on bonding strength of titanium to porcelain].

PubMed

Mo, A; Wang, J; Liao, Y; Cen, Y; Shi, X

2001-12-01

Sufficient porcelain-titanium bond is a vital factor determining the clinical performance of titanium-porcelain restorations. The purpose of this study was to investigate the effects of self-preparation La-porcelain composition on the porcelain-titanium bonding strength and to compare with the Vita Titankeramik. The present study examines 5 different recipes of porcelain by weight%: SiO2, 12%-17%; LaO2, 7%-10%; Al2O3, 9%-14%; B2O3, 23%-31%; CaO, 6%-8%; K2O, 2%-3%; SrO, 2%-4%; Na2O, 1%-3%; SnO2, 8%-10%; ZrO2, 3%-5%; TiO2, 6%-8%. Specimens were tested in push type shear with a universal testing machine. Scanning electron microscopy (SEM) and electron probe microanalyzer (EPMA) were employed to reveal the microstructures and diffusion of elements in the interfacial regions between the porcelain coating and titanium to the bond strength when fired at 800 degrees C. The ratios of crystallized compositions had significant influences on the porcelain-titanium bond strength (P < 0.05). La-porcelain had the highest shear bond strength (37.76 MPa). The shear bond strength of the Vita Titankeramik to titanium was 20.18 MPa. The results of SEM revealed integrity of porcelain-titanium joints in La-porcelain and a greater amount of porosity in the interface of Vita Titankeramik to titanium. EPMA analysis demonstrated the aggregation of Si and Sn in the interfacial regions and their diffusion into the titanium. Chemical compositions of porcelain and ratios of crystallized compositions play the important role in the titanium porcelain bond. La-porcelain had the highest shear bond strength and good porcelain-titanium joints. La-porcelain is a new-style low fusing porcelain/titanium system.

Anisotropic 2H-nuclear magnetic resonance spin-lattice relaxation in cerebroside- and phospholipid-cholesterol bilayer membranes.

PubMed

Siminovitch, D J; Ruocco, M J; Olejniczak, E T; Das Gupta, S K; Griffin, R G

1988-09-01

The axially symmetric powder pattern 2H-nuclear magnetic resonance (NMR) lineshapes observed in the liquid crystalline phase of pure lipid or lipid/cholesterol bilayers are essentially invariant to temperature, or, equivalently, to variations in the correlation times characterizing C-2H bond reorientations. In either of these melted phases, where correlation times for C-2H bond motions are shorter than 10(-7) s, information on the molecular dynamics of the saturated hydrocarbon chain would be difficult to obtain using lineshape analyses alone, and one must resort to other methods, such as the measurement of 2H spin-lattice relaxation rates, in order to obtain dynamic information. In pure lipid bilayers, the full power of the spin-lattice relaxation technique has yet to be realized, since an important piece of information, namely the orientation dependence of the 2H spin-lattice relaxation rates is usually lost due to orientational averaging of T1 by rapid lateral diffusion. Under more favorable circumstances, such as those encountered in the lipid/cholesterol mixtures of this study, the effects of orientational averaging by lateral diffusion are nullified, due to either a marked reduction (by at least an order of magnitude) in the diffusion rate, or a marked increase in the radii of curvature of the liposomes. In either case, the angular dependence of 2H spin-lattice relaxation is accessible to experimental study, and can be used to test models of molecular dynamics in these systems. Simulations of the partially recovered lineshapes indicate that the observed T1 anisotropies are consistent with large amplitude molecular reorientation of the C-2H bond among a finite number of sites. Furthermore, from the observed orientation dependence of the 2H spin-lattice relaxation rates, we conclude that order director fluctuations cannot provide the dominant relaxation pathway for acyl chain deuterons.

Review of methyl methacrylate (MMA)/tributylborane (TBB)-initiated resin adhesive to dentin.

PubMed

Taira, Yohsuke; Imai, Yohji

2014-01-01

This review, focusing mainly on research related to methyl methacrylate/tributylborane (MMA/TBB) resin, presents the early history of dentin bonding and MMA/TBB adhesive resin, followed by characteristics of resin bonding to dentin. Bond strengths of MMA/TBB adhesive resin to different adherends were discussed and compared with other bonding systems. Factors affecting bond strength (such as conditioners, primers, and medicaments used for dental treatment), bonding mechanism, and polymerization characteristics of MMA/TBB resin were also discussed. This review further reveals the unique adhesion features between MMA/TBB resin and dentin: in addition to monomer diffusion into the demineralized dentin surface, graft polymerization of MMA onto dentin collagen and interfacial initiation of polymerization at the resin-dentin interface provide the key bonding mechanisms.

Behind the Mpemba paradox

PubMed Central

Sun, Chang Qing

2015-01-01

Mpemba paradox results from hydrogen-bond anomalous relaxation. Heating stretches the O:H nonbond and shortens the H‒O bond via Coulomb coupling; cooling reverses this process to emit heat at a rate depending on its initial storage. Skin ultra-low mass density raises the thermal diffusivity and favors outward heat flow from the liquid. PMID:27227000

Copper diffusion and mechanical toughness at Cu-silica interfaces glued with polyelectrolyte nanolayers

NASA Astrophysics Data System (ADS)

Gandhi, D. D.; Singh, A. P.; Lane, M.; Eizenberg, M.; Ramanath, G.

2007-04-01

We demonstrate the use of polyallylamine hydrochloride (PAH)-polystyrene sulfonate (PSS) nanolayers to block Cu transport into silica. Cu/PSS-PAH/SiO2 structures show fourfold enhancement in device failure times during bias thermal annealing at 200 °C at an applied electric field of 2 MV/cm, when compared with structures with pristine Cu-SiO2 interfaces. Although the bonding at both Cu-PSS and PAH-SiO2 interfaces are strong, the interfacial toughness measured by the four-point bend tests is ˜2 Jm-2. Spectroscopic analysis of fracture surfaces reveals that weak electrostatic bonding at the PSS-PAH interface is responsible for the low toughness. Similar behavior is observed for Cu-SiO2 interfaces modified with other polyelectrolyte bilayers that inhibit Cu diffusion. Thus, while strong bonding at Cu-barrier and barrier-dielectric interfaces may be sufficient for blocking copper transport across polyelectrolyte bilayers, strong interlayer molecular bonding is a necessary condition for interface toughening. These findings are of importance for harnessing MNLs for use in future device wiring applications.

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

McDaniel, Jesse G.; Yethiraj, Arun, E-mail: yethiraj@chem.wisc.edu

The diffusion of protons in self-assembled systems is potentially important for the design of efficient proton exchange membranes. In this work, we study proton dynamics in a low-water content, lamellar phase of a sodium-carboxylate gemini surfactant/water system using computer simulations. The hopping of protons via the Grotthuss mechanism is explicitly allowed through the multi-state empirical valence bond method. We find that the hydronium ion is trapped on the hydrophobic side of the surfactant-water interface, and proton diffusion then proceeds by hopping between surface sites. The importance of hydrophobic traps is surprising because one would expect the hydronium ions to bemore » trapped at the charged headgroups. The physics illustrated in this system should be relevant to the proton dynamics in other amphiphilic membrane systems, whenever there exist exposed hydrophobic surface regions.« less

Microstructure of arc brazed and diffusion bonded joints of stainless steel and SiC reinforced aluminum matrix composite

NASA Astrophysics Data System (ADS)

Elßner, M.; Weis, S.; Grund, T.; Wagner, G.; Habisch, S.; Mayr, P.

2016-03-01

Joint interfaces of aluminum and stainless steel often exhibit intermetallics of Al-Fe, which limit the joint strength. In order to reduce these brittle phases in joints of aluminum matrix composites (AMC) and stainless steel, diffusion bonding and arc brazing are used. Due to the absence of a liquid phase, diffusion welding can reduce the formation of these critical in- termetallics. For this joining technique, the influence of surface treatments and adjusted time- temperature-surface-pressure-regimes is investigated. On the other hand, arc brazing offers the advantage to combine a localized heat input with the application of a low melting filler and was conducted using the system Al-Ag-Cu. Results of the joining tests using both approaches are described and discussed with regard to the microstructure of the joints and the interfaces.

Annealing of gallium nitride under high-N 2 pressure

NASA Astrophysics Data System (ADS)

Porowski, S.; Jun, J.; Krukowski, S.; Grzegory, I.; Leszczynski, M.; Suski, T.; Teisseyre, H.; Foxon, C. T.; Korakakis, D.

1999-04-01

GaN is the key material for blue and ultraviolet optoelectronics. It is a strongly bonded wurztite structure semiconductor with the direct energy gap 3.5 eV. Due to strong bonding, the diffusion processes require high temperatures, above 1300 K. However at this temperature range at ambient pressure, GaN becomes unstable and dissociates into Ga and N 2. Therefore high pressure of N 2 is required to study the diffusion and other annealing related processes. We studied annealing of bulk GaN nitride single crystals grown under high pressure and also annealing of homo- and heteroepitaxial GaN layers grown by MOCVD technique. Annealing at temperatures above 1300 K influences strongly the structural and optical properties of GaN crystals and layers. At this temperature diffusion of the Mg and Zn acceptors have been observed. In spite of very interesting experimental observations the understanding of microscopic mechanisms of these processes is limited.

Between Scylla and Charybdis: Hydrophobic Graphene-Guided Water Diffusion on Hydrophilic Substrates

PubMed Central

Kim, Jin-Soo; Choi, Jin Sik; Lee, Mi Jung; Park, Bae Ho; Bukhvalov, Danil; Son, Young-Woo; Yoon, Duhee; Cheong, Hyeonsik; Yun, Jun-Nyeong; Jung, Yousung; Park, Jeong Young; Salmeron, Miquel

2013-01-01

The structure of water confined in nanometer-sized cavities is important because, at this scale, a large fraction of hydrogen bonds can be perturbed by interaction with the confining walls. Unusual fluidity properties can thus be expected in the narrow pores, leading to new phenomena like the enhanced fluidity reported in carbon nanotubes. Crystalline mica and amorphous silicon dioxide are hydrophilic substrates that strongly adsorb water. Graphene, on the other hand, interacts weakly with water. This presents the question as to what determines the structure and diffusivity of water when intercalated between hydrophilic substrates and hydrophobic graphene. Using atomic force microscopy, we have found that while the hydrophilic substrates determine the structure of water near its surface, graphene guides its diffusion, favouring growth of intercalated water domains along the C-C bond zigzag direction. Molecular dynamics and density functional calculations are provided to help understand the highly anisotropic water stripe patterns observed. PMID:23896759

A Finite Element Analysis of Adhesively Bonded Composite Joints Including Geometric Nonlinearity, Nonlinear Viscoelasticity, Moisture Diffusion, and Delayed Failure.

DTIC Science & Technology

1987-12-01

Review of the Literature Adhesive bonding has been in use for many years. Most of the0 early bonds used animal and vegetable glues , and the structural...use of these glues has been confined mostly to timber. The use of synthetic resins in the structural bonding of timber began in early 1930’s...Fiue72. Influence of Moisture Coefficient o Adhewtv N +.n,. "t,-, flour II! . _70 60".,.:’’ .:’ " S:"- _- ._ , ’ ’ ’ "" - r - INt 25 A FINITE ELE ENT

Reversible geminate recombination of hydrogen-bonded water molecule pair

NASA Astrophysics Data System (ADS)

Markovitch, Omer; Agmon, Noam

2008-08-01

The (history independent) autocorrelation function for a hydrogen-bonded water molecule pair, calculated from classical molecular dynamics trajectories of liquid water, exhibits a t-3/2 asymptotic tail. Its whole time dependence agrees quantitatively with the solution for reversible diffusion-influenced geminate recombination derived by Agmon and Weiss [J. Chem. Phys. 91, 6937 (1989)]. Agreement with diffusion theory is independent of the precise definition of the bound state. Given the water self-diffusion constant, this theory enables us to determine the dissociation and bimolecular recombination rate parameters for a water dimer. (The theory is indispensable for obtaining the bimolecular rate coefficient.) Interestingly, the activation energies obtained from the temperature dependence of these rate coefficients are similar, rather than differing by the hydrogen-bond (HB) strength. This suggests that recombination requires displacing another water molecule, which meanwhile occupied the binding site. Because these activation energies are about twice the HB strength, cleavage of two HBs may be required to allow pair separation. The autocorrelation function without the HB angular restriction yields a recombination rate coefficient that is larger than that for rebinding to all four tetrahedral water sites (with angular restrictions), suggesting the additional participation of interstitial sites. Following dissociation, the probability of the pair to be unbound but within the reaction sphere rises more slowly than expected, possibly because binding to the interstitial sites delays pair separation. An extended diffusion model, which includes an additional binding site, can account for this behavior.

Free-radicals and advanced chemistries involved in cell membrane organization influence oxygen diffusion and pathology treatment.

PubMed

Petersen, Richard C

2017-01-01

A breakthrough has been discovered in pathology chemistry related to increasing molecular structure that can interfere with oxygen diffusion through cell membranes. Free radicals can crosslink unsaturated low-viscosity fatty acid oils by chain-growth polymerization into more viscous liquids and even solids. Free radicals are released by mitochondria in response to intermittent hypoxia that can increase membrane molecular organization to reduce fluidity and oxygen diffusion in a possible continuing vicious cycle toward pathological disease. Alternate computational chemistry demonstrates molecular bond dynamics in free energy for cell membrane physiologic movements. Paired electrons in oxygen and nitrogen atoms require that oxygen bonds rotate and nitrogen bonds invert to seek polar nano-environments and hide from nonpolar nano-environments thus creating fluctuating instability at a nonpolar membrane and polar biologic fluid interface. Subsequent mechanomolecular movements provide free energy to increase diffusion by membrane transport of molecules and oxygen into the cell, cell-membrane signaling/recognition/defense in addition to protein movements for enzyme mixing. In other chemistry calcium bonds to membrane phosphates primarily on the outer plasma cell membrane surface to influence the membrane firing threshold for excitability and better seal out water permeation. Because calcium is an excellent metal conductor and membrane phosphate headgroups form a semiconductor at the biologic fluid interface, excess electrons released by mitochondria may have more broad dissipation potential by safe conduction through calcium atomic-sized circuits on the outer membrane surface. Regarding medical conditions, free radicals are known to produce pathology especially in age-related disease in addition to aging. Because cancer cell membranes develop extreme polymorphism that has been extensively followed in research, accentuated easily-visualized free-radical models are developed. In terms of treatment, use of vitamin nutrient supplements purported to be antioxidants that remove free radicals has not proved worthwhile in clinical trials presumably due to errors with early antioxidant measurements based on inaccurate colorimetry tests. However, newer covalent-bond shrinkage tests now provide accurate measurements for free-radical inhibitor hydroquinone and other molecules toward drug therapy.

Free-radicals and advanced chemistries involved in cell membrane organization influence oxygen diffusion and pathology treatment

PubMed Central

Petersen, Richard C

2017-01-01

A breakthrough has been discovered in pathology chemistry related to increasing molecular structure that can interfere with oxygen diffusion through cell membranes. Free radicals can crosslink unsaturated low-viscosity fatty acid oils by chain-growth polymerization into more viscous liquids and even solids. Free radicals are released by mitochondria in response to intermittent hypoxia that can increase membrane molecular organization to reduce fluidity and oxygen diffusion in a possible continuing vicious cycle toward pathological disease. Alternate computational chemistry demonstrates molecular bond dynamics in free energy for cell membrane physiologic movements. Paired electrons in oxygen and nitrogen atoms require that oxygen bonds rotate and nitrogen bonds invert to seek polar nano-environments and hide from nonpolar nano-environments thus creating fluctuating instability at a nonpolar membrane and polar biologic fluid interface. Subsequent mechanomolecular movements provide free energy to increase diffusion by membrane transport of molecules and oxygen into the cell, cell-membrane signaling/recognition/defense in addition to protein movements for enzyme mixing. In other chemistry calcium bonds to membrane phosphates primarily on the outer plasma cell membrane surface to influence the membrane firing threshold for excitability and better seal out water permeation. Because calcium is an excellent metal conductor and membrane phosphate headgroups form a semiconductor at the biologic fluid interface, excess electrons released by mitochondria may have more broad dissipation potential by safe conduction through calcium atomic-sized circuits on the outer membrane surface. Regarding medical conditions, free radicals are known to produce pathology especially in age-related disease in addition to aging. Because cancer cell membranes develop extreme polymorphism that has been extensively followed in research, accentuated easily-visualized free-radical models are developed. In terms of treatment, use of vitamin nutrient supplements purported to be antioxidants that remove free radicals has not proved worthwhile in clinical trials presumably due to errors with early antioxidant measurements based on inaccurate colorimetry tests. However, newer covalent-bond shrinkage tests now provide accurate measurements for free-radical inhibitor hydroquinone and other molecules toward drug therapy. PMID:29202036

Hydrogen bonding and transportation properties of water confined in the single-walled carbon nanotube in the pulse-field

NASA Astrophysics Data System (ADS)

Zhou, Min; Hu, Ying; Liu, Jian-chuan; Cheng, Ke; Jia, Guo-zhu

2017-10-01

In this paper, molecular dynamics simulations were performed to investigate the transportation and hydrogen bonding dynamics of water confined in (6, 6) single-walled carbon nanotube (SWCNT) in the absence and presence of time-dependent pulse-field. The effects of pulse-field range from microwave to ultraviolet frequency on the diffusivity and hydrogen bonding of confined water were analyzed. The significant confinement effect due to the narrow space inside SWCNT was observed.

Water Diffusion through a Titanium Dioxide/Poly(Carbonate Urethane) Nanocomposite for Protecting Cultural Heritage: Interactions and Viscoelastic Behavior

PubMed Central

Abbate, Mario; D’Orazio, Loredana

2017-01-01

Water diffusion through a TiO2/poly (carbonate urethane) nanocomposite designed for the eco-sustainable protection of outdoor cultural heritage stonework was investigated. Water is recognized as a threat to heritage, hence the aim was to gather information on the amount of water uptake, as well as of species of water molecules absorbed within the polymer matrix. Gravimetric and vibrational spectroscopy measurements demonstrated that diffusion behavior of the nanocomposite/water system is Fickian, i.e., diffusivity is independent of concentration. The addition of only 1% of TiO2 nanoparticles strongly betters PU barrier properties and water-repellency requirement is imparted. Defensive action against penetration of water free from, and bonded through, H-bonding association arises from balance among TiO2 hydrophilicity, tortuosity effects and quality of nanoparticle dispersion and interfacial interactions. Further beneficial to antisoiling/antigraffiti action is that water-free fraction was found to be desorbed at a constant rate. In environmental conditions, under which weathering processes are most likely to occur, nanocomposite Tg values remain suitable for heritage treatments. PMID:28902179

Development of beryllium-based neutron target system with three-layer structure for accelerator-based neutron source for boron neutron capture therapy.

PubMed

Kumada, Hiroaki; Kurihara, Toshikazu; Yoshioka, Masakazu; Kobayashi, Hitoshi; Matsumoto, Hiroshi; Sugano, Tomei; Sakurai, Hideyuki; Sakae, Takeji; Matsumura, Akira

2015-12-01

The iBNCT project team with University of Tsukuba is developing an accelerator-based neutron source. Regarding neutron target material, our project has applied beryllium. To deal with large heat load and blistering of the target system, we developed a three-layer structure for the target system that includes a blistering mitigation material between the beryllium used as the neutron generator and the copper heat sink. The three materials were bonded through diffusion bonding using a hot isostatic pressing method. Based on several verifications, our project chose palladium as the intermediate layer. A prototype of the neutron target system was produced. We will verify that sufficient neutrons for BNCT treatment are generated by the device in the near future. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Effect of CuO Nanoparticles on Antimicrobial Effects and Shear Bond Strength of Orthodontic Adhesives.

PubMed

Toodehzaeim, Mohammad Hossein; Zandi, Hengameh; Meshkani, Hamidreza; Hosseinzadeh Firouzabadi, Azadeh

2018-03-01

Orthodontic appliances facilitate microbial plaque accumulation and increase the chance of white spot lesions. There is a need for new plaque control methods independent of patient's cooperation. The aim of this study was to determine the effects of incorporating copper oxide (CuO) nanoparticles on antimicrobial properties and bond strength of orthodontic adhesive. CuO nanoparticles were added to the composite transbond XT at concentrations of 0.01, 0.5 and 1 wt.%. To evaluate the antimicrobial properties of composites containing nanoparticles, the disk agar diffusion test was used. For this purpose, 10 discs from each concentration of nano-composites (totally 30 discs) and 10 discs from conventional composite (as the control group) were prepared. Then the diameter of streptococcus mutans growth inhibition around each disc was determined in blood agar medium. To evaluate the shear bond strength, with each concentration of nano-composites as well as the control group (conventional composite), 10 metal brackets were bonded to the human premolars and shear bond strength was determined using a universal testing machine. Nano-composites in all three concentrations showed significant antimicrobial effect compared to the control group ( p < 0.001). With increasing concentration of nanoparticles, antimicrobial effect showed an upward trend, although statistically was not significant. There was no significant difference between the shear bond strength of nano-composites compared to control group ( p = 0.695). Incorporating CuO nanoparticles into adhesive in all three studied concentrations added antimicrobial effects to the adhesive with no adverse effects on shear bond strength.

Ion Transport via Structural Relaxations in Polymerized Ionic Liquids

NASA Astrophysics Data System (ADS)

Ganesan, Venkat; Mogurampelly, Santosh

We study the mechanisms underlying ion transport in poly(1-butyl-3-vinylimidazolium-hexafluorophosphate) polymer electrolytes. We consider polymer electrolytes of varying polymerized ionic liquid to ionic liquid (polyIL:IL) ratios and use atomistic molecular dynamics (MD) simulations to probe the dynamical and structural characteristics of the electrolyte. Our results reveal that anion diffusion along polymer backbone occurs primarily viathe formation and breaking of ion-pairs involving threepolymerized cationic monomers of twodifferent polymer chains. Moreover, we observe that the ionic diffusivities exhibit a direct correlation with the structural relaxation times of the ion-pairs and hydrogen bonds (H-bonds). These results provide new insights into the mechanisms underlying ion transport in polymerized ionic liquid electrolytes.

Extra-thermodynamic study on surface diffusion in reversed-phase liquid chromatography using silica gels bonded with alkyl ligands of different chain lengths

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

Miyabe, Kanji; Guiochon, Georges A

2005-06-01

Surface diffusion on adsorbents made of silica gels bonded to C{sub 1}, C{sub 4}, C{sub 8}, and C{sub 18} alkyl ligands was studied in reversed-phase liquid chromatography (RPLC) from the viewpoints of two extrathermodynamic relationships: enthalpy-entropy compensation (EEC) and linear free-energy relationship (LFER). First, the values of the surface diffusion coefficient (D{sub s}), normalized by the density of the alkyl ligands, were analyzed with the modified Arrhenius equation, following the four approaches proposed in earlier research. This showed that an actual EEC resulting from substantial physicochemical effects occurs for surface diffusion and suggested a mechanistic similarity of molecular migration bymore » surface diffusion, irrespective of the alkyl chain length. Second, a new model based on EEC was derived to explain the LFER between the logarithms of D{sub s} measured under different RPLC conditions. This showed that the changes of free energy, enthalpy, and entropy of surface diffusion are linearly correlated with the carbon number in the alkyl ligands of the bonded phases and that the contribution of the C{sub 18} ligand to the changes of the thermodynamic parameters corresponds to that of the C{sub 10} ligand. The new LFER model correlates the slope and intercept of the LFER to the compensation temperatures derived from the EEC analyses and to several parameters characterizing the molecular contributions to the changes in enthalpy and entropy. Finally, the new model was used to estimate D{sub s} under various RPLC conditions. The values of D{sub s} that were estimated from only two original experimental D{sub s} data were in agreement with corresponding experimental D{sub s} values, with relative errors of {approx}20%, irrespective of some RPLC conditions.« less

Self-Healing of Unentangled Polymer Networks with Reversible Bonds

PubMed Central

Stukalin, Evgeny B.; Cai, Li-Heng; Kumar, N. Arun; Leibler, Ludwik; Rubinstein, Michael

2013-01-01

Self-healing polymeric materials are systems that after damage can revert to their original state with full or partial recovery of mechanical strength. Using scaling theory we study a simple model of autonomic self-healing of unentangled polymer networks. In this model one of the two end monomers of each polymer chain is fixed in space mimicking dangling chains attachment to a polymer network, while the sticky monomer at the other end of each chain can form pairwise reversible bond with the sticky end of another chain. We study the reaction kinetics of reversible bonds in this simple model and analyze the different stages in the self-repair process. The formation of bridges and the recovery of the material strength across the fractured interface during the healing period occur appreciably faster after shorter waiting time, during which the fractured surfaces are kept apart. We observe the slowest formation of bridges for self-adhesion after bringing into contact two bare surfaces with equilibrium (very low) density of open stickers in comparison with self-healing. The primary role of anomalous diffusion in material self-repair for short waiting times is established, while at long waiting times the recovery of bonds across fractured interface is due to hopping diffusion of stickers between different bonded partners. Acceleration in bridge formation for self-healing compared to self-adhesion is due to excess non-equilibrium concentration of open stickers. Full recovery of reversible bonds across fractured interface (formation of bridges) occurs after appreciably longer time than the equilibration time of the concentration of reversible bonds in the bulk. PMID:24347684

Modification of Surface Density of a Porous Medium

NASA Technical Reports Server (NTRS)

Stackpoole, Margaret M. (Inventor); Espinoza, Christian (Inventor)

2016-01-01

A method for increasing density of a region of a porous, phenolic bonded ("PPB") body adjacent to a selected surface to increase failure tensile strength of the adjacent region and/or to decrease surface recession at elevated temperatures. When the surface-densified PPB body is brought together with a substrate, having a higher failure tensile strength, to form a composite body with a PPB body/substrate interface, the location of tensile failure is moved to a location spaced apart from the interface, the failure tensile strength of the PPB body is increased, and surface recession of the material at elevated temperature is reduced. The method deposits and allows diffusion of a phenolic substance on the selected surface. The PPB body and the substrate may be heated and brought together to form the composite body. The phenolic substance is allowed to diffuse into the PPB body, to volatilize and to cure, to provide a processed body with an increased surface density.

Characteristics and porcelain bond strength of (Ti,Al)N coating on dental alloys.

PubMed

Chung, Kwok-Hung; Duh, Jeng-Gong; Shin, Daehwan; Cagna, David R; Cronin, Robert J

2002-01-01

The effect of a novel titanium-aluminum nitride film, or (Ti,Al)N film, on the bond strength between a dental porcelain and two nickel-based dental alloy substrates was investigated. A thin layer of (Ti,Al)N film was deposited on flat metal samples using a reactive radio-frequency sputtering method. A uniform thickness of porcelain was applied to the film- coated metal samples. Metal-ceramic specimens were subjected to three-point bending, and failure loads were recorded. Bond strengths between the porcelain and (Ti,Al)N-coated metal alloys ranged from 159.0 +/- 11.7 N to 278.0 +/- 12.3 N. These values were significantly greater (p< 0.05) than bond strengths recorded for control samples that did not incorporate the (Ti,Al)N film. An electron probe microanalyzer with a line profile mode was used to characterize the interface between the (Ti,Al)N film and the porcelain. Results of this investigation suggest that the (Ti,Al)N film (1) increases the flexural bond strength between dental porcelain and nickel-based alloy substrates by permitting elemental diffusion, (2) interferes with the surface oxide formation that characteristically originates from the nickel-based metal alloy substrate, and (3) provides an appropriate oxide layer for porcelain application. Copyright 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 516-521, 2002

Investigation of Thermal Interface Materials Using Phase-Sensitive Transient Thermoreflectance Technique: Preprint

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

Feng, X.; King, C.; DeVoto, D.

2014-08-01

With increasing power density in electronics packages/modules, thermal resistances at multiple interfaces are a bottleneck to efficient heat removal from the package. In this work, the performance of thermal interface materials such as grease, thermoplastic adhesives and diffusion-bonded interfaces are characterized using the phase-sensitive transient thermoreflectance technique. A multi-layer heat conduction model was constructed and theoretical solutions were derived to obtain the relation between phase lag and the thermal/physical properties. This technique enables simultaneous extraction of the contact resistance and bulk thermal conductivity of the TIMs. With the measurements, the bulk thermal conductivity of Dow TC-5022 thermal grease (70 tomore » 75 um bondline thickness) was 3 to 5 W/(m-K) and the contact resistance was 5 to 10 mm2-K/W. For the Btech thermoplastic material (45 to 80 μm bondline thickness), the bulk thermal conductivity was 20 to 50 W/(m-K) and the contact resistance was 2 to 5 mm2-K/W. Measurements were also conducted to quantify the thermal performance of diffusion-bonded interface for power electronics applications. Results with the diffusion-bonded sample showed that the interfacial thermal resistance is more than one order of magnitude lower than those of traditional TIMs, suggesting potential pathways to efficient thermal management.« less

Equilibration and analysis of first-principles molecular dynamics simulations of water

NASA Astrophysics Data System (ADS)

Dawson, William; Gygi, François

2018-03-01

First-principles molecular dynamics (FPMD) simulations based on density functional theory are becoming increasingly popular for the description of liquids. In view of the high computational cost of these simulations, the choice of an appropriate equilibration protocol is critical. We assess two methods of estimation of equilibration times using a large dataset of first-principles molecular dynamics simulations of water. The Gelman-Rubin potential scale reduction factor [A. Gelman and D. B. Rubin, Stat. Sci. 7, 457 (1992)] and the marginal standard error rule heuristic proposed by White [Simulation 69, 323 (1997)] are evaluated on a set of 32 independent 64-molecule simulations of 58 ps each, amounting to a combined cumulative time of 1.85 ns. The availability of multiple independent simulations also allows for an estimation of the variance of averaged quantities, both within MD runs and between runs. We analyze atomic trajectories, focusing on correlations of the Kohn-Sham energy, pair correlation functions, number of hydrogen bonds, and diffusion coefficient. The observed variability across samples provides a measure of the uncertainty associated with these quantities, thus facilitating meaningful comparisons of different approximations used in the simulations. We find that the computed diffusion coefficient and average number of hydrogen bonds are affected by a significant uncertainty in spite of the large size of the dataset used. A comparison with classical simulations using the TIP4P/2005 model confirms that the variability of the diffusivity is also observed after long equilibration times. Complete atomic trajectories and simulation output files are available online for further analysis.

Effects of solvent evaporation on water sorption/solubility and nanoleakage of adhesive systems

PubMed Central

CHIMELI, Talita Baumgratz Cachapuz; D'ALPINO, Paulo Henrique Perlatti; PEREIRA, Patrícia Nóbrega; HILGERT, Leandro Augusto; DI HIPÓLITO, Vinicius; GARCIA, Fernanda Cristina Pimentel

2014-01-01

Objective To evaluate the influence of solvent evaporation in the kinetics of water diffusion (water sorption-WS, solubility-SL, and net water uptake) and nanoleakage of adhesive systems. Material and Methods Disk-shaped specimens (5.0 mm in diameter x 0.8 mm in thickness) were produced (N=48) using the adhesives: Clearfil S3 Bond (CS3)/Kuraray, Clearfil SE Bond - control group (CSE)/Kuraray, Optibond Solo Plus (OS)/Kerr and Scotchbond Universal Adhesive (SBU)/3M ESPE. The solvents were either evaporated for 30 s or not evaporated (N=24/per group), and then photoactivated for 80 s (550 mW/cm2). After desiccation, the specimens were weighed and stored in distilled water (N=12) or mineral oil (N=12) to evaluate the water diffusion over a 7-day period. Net water uptake (%) was also calculated as the sum of WS and SL. Data were submitted to 3-way ANOVA/Tukey's test (α=5%). The nanoleakage expression in three additional specimens per group was also evaluated after ammoniacal silver impregnation after 7 days of water storage under SEM. Results Statistical analysis revealed that only the factor "adhesive" was significant (p<0.05). Solvent evaporation had no influence in the WS and SL of the adhesives. CSE (control) presented significantly lower net uptake (5.4%). The nanoleakage was enhanced by the presence of solvent in the adhesives. Conclusions Although the evaporation has no effect in the kinetics of water diffusion, the nanoleakage expression of the adhesives tested increases when the solvents are not evaporated. PMID:25141201

Equilibration and analysis of first-principles molecular dynamics simulations of water.

PubMed

Dawson, William; Gygi, François

2018-03-28

First-principles molecular dynamics (FPMD) simulations based on density functional theory are becoming increasingly popular for the description of liquids. In view of the high computational cost of these simulations, the choice of an appropriate equilibration protocol is critical. We assess two methods of estimation of equilibration times using a large dataset of first-principles molecular dynamics simulations of water. The Gelman-Rubin potential scale reduction factor [A. Gelman and D. B. Rubin, Stat. Sci. 7, 457 (1992)] and the marginal standard error rule heuristic proposed by White [Simulation 69, 323 (1997)] are evaluated on a set of 32 independent 64-molecule simulations of 58 ps each, amounting to a combined cumulative time of 1.85 ns. The availability of multiple independent simulations also allows for an estimation of the variance of averaged quantities, both within MD runs and between runs. We analyze atomic trajectories, focusing on correlations of the Kohn-Sham energy, pair correlation functions, number of hydrogen bonds, and diffusion coefficient. The observed variability across samples provides a measure of the uncertainty associated with these quantities, thus facilitating meaningful comparisons of different approximations used in the simulations. We find that the computed diffusion coefficient and average number of hydrogen bonds are affected by a significant uncertainty in spite of the large size of the dataset used. A comparison with classical simulations using the TIP4P/2005 model confirms that the variability of the diffusivity is also observed after long equilibration times. Complete atomic trajectories and simulation output files are available online for further analysis.

Diffusion-Welded Microchannel Heat Exchanger for Industrial Processes

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

Piyush Sabharwall; Denis E. Clark; Michael V. Glazoff

The goal of next generation reactors is to increase energy ef?ciency in the production of electricity and provide high-temperature heat for industrial processes. The ef?cient transfer of energy for industrial applications depends on the ability to incorporate effective heat exchangers between the nuclear heat transport system and the industrial process. The need for ef?ciency, compactness, and safety challenge the boundaries of existing heat exchanger technology. Various studies have been performed in attempts to update the secondary heat exchanger that is downstream of the primary heat exchanger, mostly because its performance is strongly tied to the ability to employ more ef?cientmore » industrial processes. Modern compact heat exchangers can provide high compactness, a measure of the ratio of surface area-to-volume of a heat exchange. The microchannel heat exchanger studied here is a plate-type, robust heat exchanger that combines compactness, low pressure drop, high effectiveness, and the ability to operate with a very large pressure differential between hot and cold sides. The plates are etched and thereafter joined by diffusion welding, resulting in extremely strong all-metal heat exchanger cores. After bonding, any number of core blocks can be welded together to provide the required ?ow capacity. This study explores the microchannel heat exchanger and draws conclusions about diffusion welding/bonding for joining heat exchanger plates, with both experimental and computational modeling, along with existing challenges and gaps. Also, presented is a thermal design method for determining overall design speci?cations for a microchannel printed circuit heat exchanger for both supercritical (24 MPa) and subcritical (17 MPa) Rankine power cycles.« less

On the diffusion and self-trapping of surface dimers

NASA Astrophysics Data System (ADS)

Kappus, W.

The theory of elastic interactions between surface atoms which are caused by substrate strains is applied to the interaction of dimers on the (211) surface of tungsten. From the comparison of theoretical and experimental interactions which were derived from the diffusion behaviour of dimers, conclusions are drawn on the nature of the adatom-substrate bond.

On the diffusion and self-trapping of surface dimers

NASA Astrophysics Data System (ADS)

Kappus, W.

1982-03-01

The theory of elastic interactions between surface atoms which are caused by substrate strains is applied to the interaction of dimers on the (211) surface of tungsten. From the comparison of theoretical and experimental interactions which were derived from the diffusion behaviour of dimers, conclusions are drawn on the nature of the adatom-substrate bond.

Increased rate of solvent diffusion in a prototypical supramolecular gel measured on the picosecond timescale.

PubMed

Seydel, Tilo; Edkins, Robert M; Jones, Christopher D; Foster, Jonathan A; Bewley, Robert; Aguilar, Juan A; Edkins, Katharina

2018-06-14

Solvent diffusion in a prototypical supramolecular gel probed by quasi-elastic neutron scattering on the picosecond timescale is faster than that in the respective bulk solvent. This phenomenon is hypothesized to be due to disruption of the hydrogen bonding of the solvent by the large hydrophobic surface of the gel network.

WET EFFLUENT PARALLEL PLATE DIFFUSION DENUDER COUPLED CAPILLARY ION CHROMATOGRAPH FOR THE DETERMINATION OF ATMOSPHERIC TRACE GASES. (R825344)

EPA Science Inventory

We describe an inexpensive, compact parallel plate diffusion denuder coupled capillary IC system for the determination of soluble ionogenic atmospheric trace gases. The active sampling area (0.6×10 cm) of the denuder is formed in a novel manner by thermally bonding silica ge...

Femtosecond dynamics in hydrogen-bonded solvents

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

Castner, E.W. Jr.; Chang, Y.J.

1993-09-01

We present results on the ultrafast dynamics of pure hydrogen-bonding solvents, obtained using femtosecond Fourier-transform optical-heterodyne-detected, Raman-induced Kerr effect spectroscopy. Solvent systems we have studied include the formamides, water, ethylene glycol, and acetic acid. Inertial and diffusive motions are clearly resolved. We comment on the effect that such ultrafast solvent motions have on chemical reactions in solution.

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

NASA Astrophysics Data System (ADS)

Prisk, T. R.; Hoffmann, C.; Kolesnikov, A. I.; Mamontov, E.; Podlesnyak, A. A.; Wang, X.; Kent, P. R. C.; Anovitz, L. M.

2018-05-01

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factor reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10-100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.

Robust Joining and Integration Technologies for Advanced Metallic, Ceramic, and Composite Systems

NASA Technical Reports Server (NTRS)

Singh, M.; Shpargel, Tarah; Morscher, Gregory N.; Halbig, Michael H.; Asthana, Rajiv

2006-01-01

Robust integration and assembly technologies are critical for the successful implementation of advanced metallic, ceramic, carbon-carbon, and ceramic matrix composite components in a wide variety of aerospace, space exploration, and ground based systems. Typically, the operating temperature of these components varies from few hundred to few thousand Kelvin with different working times (few minutes to years). The wide ranging system performance requirements necessitate the use of different integration technologies which includes adhesive bonding, low temperature soldering, active metal brazing, diffusion bonding, ARCJoinT, and ultra high temperature joining technologies. In this presentation, a number of joining examples and test results will be provided related to the adhesive bonding and active metal brazing of titanium to C/C composites, diffusion bonding of silicon carbide to silicon carbide using titanium interlayer, titanium and hastelloy brazing to silicon carbide matrix composites, and ARCJoinT joining of SiC ceramics and SiC matrix composites. Various issues in the joining of metal-ceramic systems including thermal expansion mismatch and resulting residual stresses generated during joining will be discussed. In addition, joint design and testing issues for a wide variety of joints will be presented.

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

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

Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

DOE PAGES

Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.; ...

2018-05-09

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

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

McDaniel, Jesse G.; Yethiraj, Arun

The diffusion of protons in self-assembled systems is potentially important for the design of efficient proton exchange membranes. In this work, we study proton dynamics in a low-water content, lamellar phase of an sodium-carboxylate gemini surfactant/water system using computer simulations. The hopping of protons via the Grotthuss mechanism is explicity allowed through the multi-state empirical valence bond (MS-EVB) method. We find that the hydronium ion is trapped on the hydrophobic side of the surfactant-water interface, and proton diffusion then proceeds by hopping between surface sites. The importance of hydrophobic traps is surprising, because one would expect the hydronium ions tomore » be trapped at the charged head-groups. Finally, the physics illustrated in this system should be relevant to the proton dynamics in other amphiphilic membrane systems, whenever there exists exposed hydrophobic surface regions.« less

Joining of Silicon Carbide-Based Ceramics by Reaction Forming Method

NASA Technical Reports Server (NTRS)

Singh, M.; Kiser, J. D.

1997-01-01

Recently, there has been a surge of interest in the development and testing of silicon-based ceramics and composite components for a number of aerospace and ground based systems. The designs often require fabrication of complex shaped parts which can be quite expensive. One attractive way of achieving this goal is to build up complex shapes by joining together geometrically simple shapes. However, the joints should have good mechanical strength and environmental stability comparable to the bulk materials. These joints should also be able to maintain their structural integrity at high temperatures. In addition, the joining technique should be practical, reliable, and affordable. Thus, joining has been recognized as one of the enabling technologies for the successful utilization of silicon carbide based ceramic components in high temperature applications. Overviews of various joining techniques, i.e., mechanical fastening, adhesive bonding, welding, brazing, and soldering have been provided in recent publications. The majority of the techniques used today are based on the joining of monolithic ceramics with metals either by diffusion bonding, metal brazing, brazing with oxides and oxynitrides, or diffusion welding. These techniques need either very high temperatures for processing or hot pressing (high pressures). The joints produced by these techniques have different thermal expansion coefficients than the ceramic materials, which creates a stress concentration in the joint area. The use temperatures for these joints are around 700 C. Ceramic joint interlayers have been developed as a means of obtaining high temperature joints. These joint interlayers have been produced via pre-ceramic polymers, in-situ displacement reactions, and reaction bonding techniques. Joints produced by the pre-ceramic polymer approach exhibit a large amounts of porosity and poor mechanical properties. On the other hand, hot pressing or high pressures are needed for in-situ displacement reactions and reaction bonding techniques. Due to the equipment required, these techniques are impractical for joining large or complex shaped components.

The coefficient of bond thermal expansion measured by extended x-ray absorption fine structure.

PubMed

Fornasini, P; Grisenti, R

2014-10-28

The bond thermal expansion is in principle different from the lattice expansion and can be measured by correlation sensitive probes such as extended x-ray absorption fine structure (EXAFS) and diffuse scattering. The temperature dependence of the coefficient α(bond)(T) of bond thermal expansion has been obtained from EXAFS for CdTe and for Cu. A coefficient α(tens)(T) of negative expansion due to tension effects has been calculated from the comparison of bond and lattice expansions. Negative lattice expansion is present in temperature intervals where α(bond) prevails over α(tens); this real-space approach is complementary but not equivalent to the Grüneisen theory. The relevance of taking into account the asymmetry of the nearest-neighbours distribution of distances in order to get reliable bond expansion values and the physical meaning of the third cumulant are thoroughly discussed.

Eutectic-based wafer-level-packaging technique for piezoresistive MEMS accelerometers and bond characterization using molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Aono, T.; Kazama, A.; Okada, R.; Iwasaki, T.; Isono, Y.

2018-03-01

We developed a eutectic-based wafer-level-packaging (WLP) technique for piezoresistive micro-electromechanical systems (MEMS) accelerometers on the basis of molecular dynamics analyses and shear tests of WLP accelerometers. The bonding conditions were experimentally and analytically determined to realize a high shear strength without solder material atoms diffusing to adhesion layers. Molecular dynamics (MD) simulations and energy dispersive x-ray (EDX) spectrometry done after the shear tests clarified the eutectic reaction of the solder materials used in this research. Energy relaxation calculations in MD showed that the diffusion of solder material atoms into the adhesive layer was promoted at a higher temperature. Tensile creep MD simulations also suggested that the local potential energy in a solder material model determined the fracture points of the model. These numerical results were supported by the shear tests and EDX analyses for WLP accelerometers. Consequently, a bonding load of 9.8 kN and temperature of 300 °C were found to be rational conditions because the shear strength was sufficient to endure the polishing process after the WLP process and there was little diffusion of solder material atoms to the adhesion layer. Also, eutectic-bonding-based WLP was effective for controlling the attenuation of the accelerometers by determining the thickness of electroplated solder materials that played the role of a cavity between the accelerometers and lids. If the gap distance between the two was less than 6.2 µm, the signal gains for x- and z-axis acceleration were less than 20 dB even at the resonance frequency due to air-damping.

Diffuse scattering measurements of static atomic displacements in crystalline binary solid solutions

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

Ice, G.E.; Sparks, C.J.; Jiang, X.

1997-09-01

Diffuse x-ray scattering from crystalline solid solutions is sensitive to both local chemical order and local bond distances. In short-range ordered alloys, fluctuations of chemistry and bond distances break the long-range symmetry of the crystal within a local region and contribute to the total energy of the alloy. Recent use of tunable synchrotron radiation to change the x-ray scattering contrast between elements has greatly advanced the measurement of bond distances between the three kinds of atom pairs found in crystalline binary alloys. The estimated standard deviation on these recovered static displacements approaches {+-}0.001 {angstrom} (0.0001 nm) which is an ordermore » of magnitude more precise than obtained with EXAFS. In addition, both the radial and tangential displacements can be recovered to five near neighbors and beyond. These static displacement measurements provide new information which challenges the most advanced theoretical models of binary crystalline alloys. 29 refs., 8 figs., 2 tabs.« less

Structure and sorption properties of CNC reinforced PVA films.

PubMed

Popescu, Maria-Cristina

2017-08-01

Bio-nanocomposite films based on cellulose nanocrystals reinforced poly(vinyl alcohol) were obtained by solvent casting method. To assess the structural features of the films, different spectral techniques (FTIR, 2D COS and XRD) have been used. Infrared and 2D correlation spectroscopy evidenced the presence of H-bond interactions between the PVA and CNC, and the variation in the conformational rearrangements, while XRD showed that the crystallite size and the crystallinity degree were affected by the incorporation of CNC. At low content of CNC in the PVA matrix, the crystallinity degree decreased to 29.9%, while at higher CNC content increased to 80.6%, comparing to PVA (35.4%). To evaluate the interaction with water, contact angle measurement, water sorption and NIR spectroscopy were used, respectively. The increase of the CNC content induced a reduction in water sorption ability from 93% for PVA to 75% for PVA/CNC films, indicating the involvement of the hydroxyl groups in new hydrogen bonded interactions. By analyzing the variation of the NIR bands from 1930, 1902 and 1985nm, was observed that the water molecules interact with the polymer matrix through moderate hydrogen bond before diffusing into the free volume of the matrix and form stronger hydrogen bonds. Copyright © 2017 Elsevier B.V. All rights reserved.

Aggregation control of quantum dots through ion-mediated hydrogen bonding shielding.

PubMed

Liu, Jianbo; Yang, Xiaohai; Wang, Kemin; He, Xiaoxiao; Wang, Qing; Huang, Jin; Liu, Yan

2012-06-26

Nanoparticle stabilization against detrimental aggregation is a critical parameter that needs to be well controlled. Herein, we present a facile and rapid ion-mediated dispersing technique that leads to hydrophilic aggregate-free quantum dots (QDs). Because of the shielding of the hydrogen bonds between cysteamine-capped QDs, the presence of F(-) ions disassembled the aggregates of QDs and afforded their high colloidal stability. The F(-) ions also greatly eliminated the nonspecific adsorption of the QDs on glass slides and cells. Unlike the conventional colloidal stabilized method that requires the use of any organic ligand and/or polymer for the passivation of the nanoparticle surface, the proposed approach adopts the small size and large diffusion coefficient of inorganic ions as dispersant, which offers the disaggregation a fast reaction dynamics and negligible influence on their intrinsic surface functional properties. Therefore, the ion-mediated dispersing strategy showed great potential in chemosensing and biomedical applications.

Hydrogen bonded structure, polarity, molecular motion and frequency fluctuations at liquid-vapor interface of a water-methanol mixture: an ab initio molecular dynamics study.

PubMed

Choudhuri, Jyoti Roy; Chandra, Amalendu

2014-10-07

We have performed ab initio molecular dynamics simulations of a liquid-vapor interfacial system consisting of a mixture of water and methanol molecules. Detailed results are obtained for the structural and dynamical properties of the bulk and interfacial regions of the mixture. Among structural properties, we have looked at the inhomogeneous density profiles of water and methanol molecules, hydrogen bond distributions and also the orientational profiles of bulk and interfacial molecules. The methanol molecules are found to have a higher propensity to be at the interface than water molecules. It is found that the interfacial molecules show preference for specific orientations so as to form water-methanol hydrogen bonds at the interface with the hydrophobic methyl group pointing towards the vapor side. It is also found that for both types of molecules, the dipole moment decreases at the interface. It is also found that the local electric field of water influences the dipole moment of methanol molecules. Among the dynamical properties, we have calculated the diffusion, orientational relaxation, hydrogen bond dynamics, and vibrational frequency fluctuations in bulk and interfacial regions. It is found that the diffusion and orientation relaxation of the interfacial molecules are faster than those of the bulk. However, the hydrogen bond lifetimes are longer at the interface which can be correlated with the time scales found from the decay of frequency time correlations. The slower hydrogen bond dynamics for the interfacial molecules with respect to bulk can be attributed to diminished cooperative effects at the interface due to reduced density and number of hydrogen bonds.

Effect of Pd Surface Roughness on the Bonding Process and High Temperature Reliability of Au Ball Bonds

NASA Astrophysics Data System (ADS)

Huang, Y.; Kim, H. J.; McCracken, M.; Viswanathan, G.; Pon, F.; Mayer, M.; Zhou, Y. N.

2011-06-01

A 0.3- μm-thick electrolytic Pd layer was plated on 1 μm of electroless Ni on 1 mm-thick polished and roughened Cu substrates with roughness values ( R a) of 0.08 μm and 0.5 μm, respectively. The rough substrates were produced with sand-blasting. Au wire bonding on the Ni/Pd surface was optimized, and the electrical reliability was investigated under a high temperature storage test (HTST) during 800 h at 250°C by measuring the ball bond contact resistance, R c. The average value of R c of optimized ball bonds on the rough substrate was 1.96 mΩ which was about 40.0% higher than that on the smooth substrate. The initial bondability increased for the rougher surface, so that only half of the original ultrasonic level was required, but the reliability was not affected by surface roughness. For both substrate types, HTST caused bond healing, reducing the average R c by about 21% and 27%, respectively. Au diffusion into the Pd layer was observed in scanning transmission electron microscopy/ energy dispersive spectroscopy (STEM-EDS) line-scan analysis after HTST. It is considered that diffusion of Au or interdiffusion between Au and Pd can provide chemically strong bonding during HTST. This is supported by the R c decrease measured as the aging time increased. Cu migration was indicated in the STEM-EDS analysis, but its effect on reliability can be ignored. Au and Pd tend to form a complete solid solution at the interface and can provide reliable interconnection for high temperature (250°C) applications.

Optimized ultra-thin manganin alloy passivated fine-pitch damascene compatible bump-less Cu-Cu bonding at sub 200 °C for three-dimensional Integration applications

NASA Astrophysics Data System (ADS)

Panigrahi, Asisa Kumar; Hemanth Kumar, C.; Bonam, Satish; Ghosh, Tamal; Rama Krishna Vanjari, Siva; Govind Singh, Shiv

2018-02-01

Enhanced Cu diffusion, Cu surface passivation, and smooth surface at the bonding interface are the key essentials for high quality Cu-Cu bonding. Previously, we have demonstrated optimized 3 nm thin Manganin metal-alloy passivation from oxidation and also helps to reduce the surface roughness to about 0.8 nm which substantially led to high quality Cu-Cu bonding. In this paper, we demonstrated an ultra fine-pitch (<25 µm) Cu-Cu bonding using an optimized Manganin metal-alloy passivation. This engineered surface passivation approach led to high quality bonding at sub 200 °C temperature and 0.4 MPa. Very low specific contact resistance of 1.4 × 10-7 Ω cm2 and the defect free bonded interface is clear indication of high quality bonding for future multilayer integrations. Furthermore, electrical characterization of the bonded structure was performed under various robust conditions as per International Technology Roadmap for Semiconductors (ITRS Roadmap) in order to satisfy the stability of the bonded structure.

Effect of TiO2 nanoparticles incorporation on antibacterial properties and shear bond strength of dental composite used in Orthodontics

PubMed Central

Sodagar, Ahmad; Akhoundi, Mohamad Sadegh Ahmad; Bahador, Abbas; Jalali, Yasamin Farajzadeh; Behzadi, Zahra; Elhaminejad, Farideh; Mirhashemi, Amir Hossein

2017-01-01

ABSTRACT Introduction: Plaque accumulation and bond failure are drawbacks of orthodontic treatment, which requires composite for bonding of brackets. As the antimicrobial properties of TiO2 nanoparticles (NPs) have been proven, the aim of this study was to evaluate the antimicrobial and mechanical properties of composite resins modified by the addition of TiO2 NPs. Methods: Orthodontics composite containing 0%, 1%, 5% and 10% NPs were prepared. 180 composite disks were prepared for elution test, disk agar diffusion test and biofilm inhibition test to collect the counts of microorganisms on three days, measure the inhibition diameter and quantify the viable counts of colonies consequently. For shear bond strength (SBS) test, 48 intact bovine incisors were divided into four groups. Composites containing 0%, 1%, 5% and 10% NPs were used for bonding of bracket. The bracket/tooth SBS was measured by using an universal testing machine. Results: All concentration of TiO2 NPs had a significant effect on creation and extension of inhibition zone. For S. mutans and S. sanguinis, all concentration of TiO2 NPs caused reduction of the colony counts. Composite containing 10% TiO2 NPs had significant effect on reduction of colony counts for S. mutans and S. sanguinis in all three days. The highest mean shear bond strength belonged to the control group, while the lowest value was seen in 10% NPs composite. Conclusions: Incorporating TiO2 nanoparticles into composite resins confer antibacterial properties to adhesives, while the mean shear bond of composite containing 1% and 5% NPs still in an acceptable range. PMID:29160346

Diffusion welded nonconsumable electrode assembly and use thereof for electrolytic production of metals and silicon

DOEpatents

Byrne, Stephen C.; Vasudevan, Asuri K.

1984-01-01

A nonconsumable electrode assembly suitable for use in the production of metal by electrolytic reduction of a metal compound dissolved in a molten salt, the assembly comprising a metal conductor diffusion welded to a portion of a ceramic electrode body having a level of free metal or metal alloy sufficient to effect a metal bond.

American option pricing in Gauss-Markov interest rate models

NASA Astrophysics Data System (ADS)

Galluccio, Stefano

1999-07-01

In the context of Gaussian non-homogeneous interest-rate models, we study the problem of American bond option pricing. In particular, we show how to efficiently compute the exercise boundary in these models in order to decompose the price as a sum of a European option and an American premium. Generalizations to coupon-bearing bonds and jump-diffusion processes for the interest rates are also discussed.

Diffuse Vibrational Signature of a Single Proton Embedded in the Oxalate Scaffold, HO2CCO2(-).

PubMed

Wolke, Conrad T; DeBlase, Andrew F; Leavitt, Christopher M; McCoy, Anne B; Johnson, Mark A

2015-12-31

To understand how the D2d oxalate scaffold (C2O4)(2-) distorts upon capture of a proton, we report the vibrational spectra of the cryogenically cooled HO2CCO2(-) anion and its deuterated isotopologue DO2CCO2(-). The transitions associated with the skeletal vibrations and OH bending modes are sharp and are well described by inclusion of cubic terms in the normal mode expansion of the potential surface through an extended Fermi resonance analysis. The ground state structure features a five-membered ring with an asymmetric intramolecular proton bond. The spectral signatures of the hydrogen stretches, on the contrary, are surprisingly diffuse, and this behavior is not anticipated by the extended Fermi scheme. We trace the diffuse bands to very strong couplings between the high-frequency OH-stretch and the low-frequency COH bends as well as heavy particle skeletal deformations. A simple vibrationally adiabatic model recovers this breadth of oscillator strength as a 0 K analogue of the motional broadening commonly used to explain the diffuse spectra of H-bonded systems at elevated temperatures, but where these displacements arise from the configurations present at the vibrational zero-point level.

Improving proton conduction pathways in di- and triblock copolymer membranes: Branched versus linear side chains

NASA Astrophysics Data System (ADS)

Dorenbos, G.

2017-06-01

Phase separation within a series of polymer membranes in the presence of water is studied by dissipative particle dynamics. Each polymer contains hydrophobic A beads and hydrophilic C beads. Three parent architectures are constructed from a backbone composed of connected hydrophobic A beads to which short ([C]), long ([A3C]), or symmetrically branched A5[AC][AC] side chains spring off. Three di-block copolymer derivatives are constructed by covalently bonding an A30 block to each parent architecture. Also three tri-blocks with A15 blocks attached to both ends of each parent architecture are modeled. Monte Carlo tracer diffusion calculations through the water containing pores for 1226 morphologies reveal that water diffusion for parent architectures is slowest and diffusion through the di-blocks is fastest. Furthermore, diffusion increases with side chain length and is highest for branched side chains. This is explained by the increase of water pore size with , which is the average number of bonds that A beads are separated from a nearest C bead. Optimization of within the amphiphilic parent architecture is expected to be essential in improving proton conduction in polymer electrolyte membranes.

Fabrication and evaluation of advanced titanium structural panels for supersonic cruise aircraft

NASA Technical Reports Server (NTRS)

Payne, L.

1977-01-01

Flightworthy primary structural panels were designed, fabricated, and tested to investigate two advanced fabrication methods for titanium alloys. Skin-stringer panels fabricated using the weldbraze process, and honeycomb-core sandwich panels fabricated using a diffusion bonding process, were designed to replace an existing integrally stiffened shear panel on the upper wing surface of the NASA YF-12 research aircraft. The investigation included ground testing and Mach 3 flight testing of full-scale panels, and laboratory testing of representative structural element specimens. Test results obtained on full-scale panels and structural element specimens indicate that both of the fabrication methods investigated are suitable for primary structural applications on future civil and military supersonic cruise aircraft.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

Diffusion bonding of CMSX-4 to UDIMET 720 using PVD-coated interfaces and HIP

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

Larker, R.; Ockborn, J.; Selling, B.

There is an increasing interest in development of manufacturing methods for Dual Property BLISKs (BLaded dISKs), consisting of creep resistant airfoils and fatigue resistant disks bonded together by a durable joint. Optimum heat treatments are, however, very different for creep resistant single crystal CMSX-4 and fatigue resistant polycrystalline Udimet 720 selected in this study, but fortunately the first aging treatment for CMSX-4 (1140 C, 2-6h, AC) is similar to the partial solution treatment of U 720 HS2 (1115 C, 4h, OQ). Based on this, diffusion bonding was performed by HIP at 1120 C and 200 MPa argon pressure for 4more » h, followed by cooling to 400 C. Subsequently, a shortened Udimet 720 HS2 two-step aging treatment was adopted by heating to 650 C for 6 h followed by cooling to 400 C, heating to 760 C for 2 h, and finally cooling to R.T. under remaining HIP pressure. Plasma etching followed by thin (80 nm) PVD coating with either nickel or titanium were used to clean and protect the polished surfaces before joining. The selection of coatings was governed by the possibility to reduce oxidized nickel by flushing with hydrogen at 330 C during evacuation of the HIP capsules, and by the large solubility of oxygen in titanium. Hot tensile testing was performed at 750 C on both joined and reference materials subjected to the modified heat treatment. Initially solution treated Udimet 720 and CMSX-4 comprised the reference materials. The testing showed that joints with Ni-PV coatings were almost as strong as Udimet 720 (although with very limited elongation), while the joints with Ti-PVD coatings were weaker.« less

The mechanism of proton conduction in phosphoric acid

NASA Astrophysics Data System (ADS)

Vilčiauskas, Linas; Tuckerman, Mark E.; Bester, Gabriel; Paddison, Stephen J.; Kreuer, Klaus-Dieter

2012-06-01

Neat liquid phosphoric acid (H3PO4) has the highest intrinsic proton conductivity of any known substance and is a useful model for understanding proton transport in other phosphate-based systems in biology and clean energy technologies. Here, we present an ab initio molecular dynamics study that reveals, for the first time, the microscopic mechanism of this high proton conductivity. Anomalously fast proton transport in hydrogen-bonded systems involves a structural diffusion mechanism in which intramolecular proton transfer is driven by specific hydrogen bond rearrangements in the surrounding environment. Aqueous media transport excess charge defects through local hydrogen bond rearrangements that drive individual proton transfer reactions. In contrast, strong, polarizable hydrogen bonds in phosphoric acid produce coupled proton motion and a pronounced protic dielectric response of the medium, leading to the formation of extended, polarized hydrogen-bonded chains. The interplay between these chains and a frustrated hydrogen-bond network gives rise to the high proton conductivity.

Molecular Binding Contributes to Concentration Dependent Acrolein Deposition in Rat Upper Airways: CFD and Molecular Dynamics Analyses

PubMed Central

Hu, Qin; Si, Xiuhua April

2018-01-01

Existing in vivo experiments show significantly decreased acrolein uptake in rats with increasing inhaled acrolein concentrations. Considering that high-polarity chemicals are prone to bond with each other, it is hypothesized that molecular binding between acrolein and water will contribute to the experimentally observed deposition decrease by decreasing the effective diffusivity. The objective of this study is to quantify the probability of molecular binding for acrolein, as well as its effects on acrolein deposition, using multiscale simulations. An image-based rat airway geometry was used to predict the transport and deposition of acrolein using the chemical species model. The low Reynolds number turbulence model was used to simulate the airflows. Molecular dynamic (MD) simulations were used to study the molecular binding of acrolein in different media and at different acrolein concentrations. MD results show that significant molecular binding can happen between acrolein and water molecules in human and rat airways. With 72 acrolein embedded in 800 water molecules, about 48% of acrolein compounds contain one hydrogen bond and 10% contain two hydrogen bonds, which agreed favorably with previous MD results. The percentage of hydrogen-bonded acrolein compounds is higher at higher acrolein concentrations or in a medium with higher polarity. Computational dosimetry results show that the size increase caused by the molecular binding reduces the effective diffusivity of acrolein and lowers the chemical deposition onto the airway surfaces. This result is consistent with the experimentally observed deposition decrease at higher concentrations. However, this size increase can only explain part of the concentration-dependent variation of the acrolein uptake and acts as a concurrent mechanism with the uptake-limiting tissue ration rate. Intermolecular interactions and associated variation in diffusivity should be considered in future dosimetry modeling of high-polarity chemicals such as acrolein. PMID:29584651

Modelling and Microstructural Characterization of Sintered Metallic Porous Materials

PubMed Central

Depczynski, Wojciech; Kazala, Robert; Ludwinek, Krzysztof; Jedynak, Katarzyna

2016-01-01

This paper presents selected characteristics of the metallic porous materials produced by the sintering of metal powders. The authors focus on materials produced from the iron powder (Fe) of ASC 100.29 and Distaloy SE. ASC 100.29 is formed by atomization and has a characteristic morphology. It consists of spherical particles of different sizes forming agglomerates. Distaloy SE is also based on the sponge-iron. The porous material is prepared using the patented method of sintering the mixture of iron powder ASC 100.29, Fe(III) oxide, Distaloy SE and Fe(III) oxide in the reducing atmosphere of dissociated ammonia. As a result, the materials with open pores of micrometer sizes are obtained. The pores are formed between iron particles bonded by diffusion bridges. The modelling of porous materials containing diffusion bridges that allows for three-dimensional (3D) imaging is presented. PMID:28773690

Summary of Prior Work on Joining of Oxide Dispersion-Strengthened Alloys

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

Wright, Ian G; Tatlock, Gordon J; Badairy, H.

2009-08-01

There is a range of joining techniques available for use with ODS alloys, but care should be exercised in matching the technique to the final duty requirements of the joint. The goal for joining ODS alloys is a joint with no local disruption of the distribution of the oxide dispersion, and no significant change in the size and orientation of the alloy microstructure. Not surprisingly, the fusion welding processes typically employed with wrought alloys produce the least satisfactory results with ODS alloys, but some versions, such as fusion spot welding, and the laser and electron-beam welding technologies, have demonstrated potentialmore » for producing sound joints. Welds made using solid-state spot welding reportedly have exhibited parent metal properties. Thus, it is possible to employ processes that result in significant disruption of the alloy microstructure, as long as the processing parameters are adjustment to minimize the extent of or influence of the changes in the alloy microstructure. Selection among these joining approaches largely depends on the particular application and component configuration, and an understanding of the relationships among processing, alloy microstructure, and final properties is key. Recent developments have resulted in friction welding evolving to be a prime method for joining ODS sheet products, and variants of brazing/diffusion bonding have shown excellent promise for use with tubes and pipes. The techniques that come closest to the goal defined above involve solid-state diffusion bonding and, in particular, it has been found that secondary recrystallization of joints made by pulsed plasma-assisted diffusion can produce the desired, continuous, large alloy grain structure through the joint. Such joints have exhibited creep rupture failure at >82% of the load needed to fail the monolithic parent alloy at 1000 C.« less

Proline induced disruption of the structure and dynamics of water.

PubMed

Yu, Dehong; Hennig, Marcus; Mole, Richard A; Li, Ji Chen; Wheeler, Cheryl; Strässle, Thierry; Kearley, Gordon J

2013-12-21

We use quasi-elastic neutron scattering spectroscopy to study the diffusive motion of water molecules at ambient temperature as a function of the solute molar fraction of the amino acid, proline. We validate molecular dynamics simulations against experimental quasielastic neutron scattering data and then use the simulations to reveal, and understand, a strong dependence of the translational self-diffusion coefficient of water on the distance to the amino acid molecule. An analysis based on the juxtaposition of water molecules in the simulation shows that the rigidity of proline imposes itself on the local water structure, which disrupts the hydrogen-bond network of water leading to an increase in the mean lifetime of hydrogen bonds. The net effect is some distortion of the proline molecule and a slowing down of the water mobility.

Sprayed skin turbine component

DOEpatents

Allen, David B

2013-06-04

Fabricating a turbine component (50) by casting a core structure (30), forming an array of pits (24) in an outer surface (32) of the core structure, depositing a transient liquid phase (TLP) material (40) on the outer surface of the core structure, the TLP containing a melting-point depressant, depositing a skin (42) on the outer surface of the core structure over the TLP material, and heating the assembly, thus forming both a diffusion bond and a mechanical interlock between the skin and the core structure. The heating diffuses the melting-point depressant away from the interface. Subsurface cooling channels (35) may be formed by forming grooves (34) in the outer surface of the core structure, filling the grooves with a fugitive filler (36), depositing and bonding the skin (42), then removing the fugitive material.

Energetics of a Li Atom adsorbed on B/N doped graphene with monovacancy

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

Rani, Babita, E-mail: babitabaghla15@gmail.com; Department of Physics, Punjabi University, Patiala 147002; Jindal, V.K.

We use density functional theory (DFT) to study the adsorption properties and diffusion of Li atom across B/N-pyridinic graphene. Regardless of the dopant type, B atoms of B-pyridinic graphene lose electron density. On the other hand, N atoms (p-type dopants) have tendency to gain electron density in N-pyridinic graphene. Higher chemical reactivity and electronic conductivity of B/N-pyridinic graphene are responsible for stronger binding of Li with the substrates as compared to pristine graphene. The binding energy of Li with B/N-pyridinic graphene exceeds the cohesive energy of bulk Li, making it energetically unfavourable for Li to form clusters on these substrates.more » Li atom gets better adsorbed on N-pyridinic graphene due to an additional p-p hybridization of the orbitals while Li on B-pyridinic prefers the ionic bonding. Also, significant distortion of N-pyridinic graphene upon Li adsorption is a consequence of the change in bonding mechanism between Li atom and the substrate. Our results show that bonding character and hence binding energies between Li and graphene can be tuned with the help of B/N doping of monovacancy defects. Further, the sites for most stable adsorption are different for the two types of doped and defective graphene, leading to greater Li uptake capacity of B-pyridinic graphene near the defect. In addition, B-pyridinic graphene offering lower diffusion barrier, ensures better Li kinetics. Thus, B-pyridinic graphene presents itself as a better anode material for LIBs as compared to N-pyridinic graphene. - Graphical abstract: Adsorption and diffusion of Li atom across the B/N doped monovacancy graphene is studied using ab-initio DFT calculations. Our results show that bonding mechanism and binding of Li with graphene can be tuned with the help of N/B doping of defects. Also, B-pyridinic graphene presents itself as a better anode material for lithium ion batteries as compared to N-pyridinic graphene. Display Omitted - Highlights: • Density functional theory (DFT) calculations are employed to study the effect of B/N doping of monovacancy graphene on the adsorption and diffusion of Li atom across the sheet using VASP. • Higher chemical reactivity and electronic conductivity of B/N-pyridinic graphene (p-type semiconductors) as compared to pristine graphene lead to stronger binding of Li. It also exceeds the cohesive energy of bulk Li. Thus, uniform distribution of Li atoms is possible on both substrates. • Li gets adsorbed stably at centre of defect in N-pyridinic graphene. B-pyridinic graphene has stable adsorption of Li at hollow site of hexagon, neighboring the defect, having only one boron atom. It leads to maximum Li uptake capacity of B-pyridinic graphene. • Li gets better adsorbed on N-pyridinic graphene due to an additional p-p hybridization of the orbitals. This change in bonding mechanism causes significant distortion of the substrate. On the other hand, Li on B-pyridinic graphene shows ionic bonding character. • B-pyridinic graphene offers lower energy barrier for Li to diffuse across the substrate in comparison to N-pyridinic graphene. Thus, B-pyridinic graphene presents itself as a better anode material for lithium ion batteries due to optimal Li adsorption and better diffusion kinetics.« less

Retention and effective diffusion of model metabolites on porous graphitic carbon.

PubMed

Lunn, Daniel B; Yun, Young J; Jorgenson, James W

2017-12-29

The study of metabolites in biological samples is of high interest for a wide range of biological and pharmaceutical applications. Reversed phase liquid chromatography is a common technique used for the separation of metabolites, but it provides little retention for polar metabolites. An alternative to C18 bonded phases, porous graphitic carbon has the ability to provide significant retention for both non-polar and polar analytes. The goal of this work is to study the retention and effective diffusion properties of porous graphitic carbon, to see if it is suitable for the wide injection bands and long run times associated with long, packed capillary-scale separations. The retention of a set of standard metabolites was studied for both stationary phases over a wide range of mobile phase conditions. This data showed that porous graphitic carbon benefits from significantly increased retention (often >100 fold) under initial gradient conditions for these metabolites, suggesting much improved ability to focus a wide injection band at the column inlet. The effective diffusion properties of these columns were studied using peak-parking experiments with the standard metabolites under a wide range of retention conditions. Under the high retention conditions, which can be associated with retention after injection loading for gradient separations, D eff /D m ∼0.1 for both the C18-bonded and porous graphitic carbon columns. As C18 bonded particles are widely, and successfully utilized for long gradient separations without issue of increasing peak width from longitudinal diffusion, this suggests that porous graphitic carbon should be amenable for long runtime gradient separations as well. Copyright © 2017 Elsevier B.V. All rights reserved.

Minority carrier diffusion and defects in InGaAsN grown by molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Kurtz, Steven R.; Klem, J. F.; Allerman, A. A.; Sieg, R. M.; Seager, C. H.; Jones, E. D.

2002-02-01

To gain insight into the nitrogen-related defects of InGaAsN, nitrogen vibrational mode spectra, Hall mobilities, and minority carrier diffusion lengths are examined for InGaAsN (1.1 eV band gap) grown by molecular beam epitaxy (MBE). Annealing promotes the formation of In-N bonding, and lateral carrier transport is limited by large scale (≫mean free path) material inhomogeneities. Comparing solar cell quantum efficiencies with our earlier results for devices grown by metalorganic chemical vapor deposition (MOCVD), we find significant electron diffusion in the MBE material (reversed from the hole diffusion in MOCVD material), and minority carrier diffusion in InGaAsN cannot be explained by a "universal," nitrogen-related defect.

Analysis of the temporal effects on grating evolution in photopolymer

NASA Astrophysics Data System (ADS)

Kelly, John V.; Gleeson, Michael R.; Close, Ciara E.; O'Neill, Feidhlim T.; Sheridan, John T.; Gallego, Sergi; Neipp, Cristian

2006-04-01

The nonlocal polymerization driven diffusion model is used to describe holographic grating formation in acrylamidebased photopolymer. The free radical chain polymerization process results in polymer being generated nonlocal both in space and time to the point of chain initiation. A Gaussian spatial material response function and an exponential temporal material response function are used to account for these effects. In this paper we firstly examine the nature of the temporal evolution of grating formation for short recording periods. It is shown that in this case, temporal effects become most notable and the inclusion of the nonlocal temporal response function is shown to be necessary to accurately describe the process. In particular, brief post exposure selfamplification of the refractive index modulation is noted. This is attributed to continued chain growth for a brief period after exposure. Following this a slight decay in the grating amplitude also occurs. This we believe is due to the continued diffusion of monomer after exposure. Since the sinusoidal recording pattern generates a monomer concentration gradient during the recording process monomer diffusion occurs both during and after exposure. The evolution of the refractive index modulation is determined by the respective refractive index values of the recording material components. From independent measurements it is noted that the refractive index value of the monomer is slightly less than that of the background material. Therefore as monomer diffuses back into the dark regions, a reduction in overall refractive index modulation occurs. Volume changes occurring within the material also affect the nature of grating evolution. To model these effects we employ a free volume concept. Due to the fact that the covalent single carbon bond in the polymer is up to 50% shorter than the van der Waals bond in the liquid monomer state, free volume is created when monomer is converted to polymer. For each bond conversion we assume a hole is generated which then collapses at some characteristic rate constant. Incorporating each of these effects into our model, the model is then solved using a Finite-Difference Time- Domain method (FDTD). The Lorentz-Lorenz relation is used to determine the overall evolution refractive index modulation and the corresponding diffraction efficiency of the resulting grating is calculated using Rigorous Coupled Wave Analysis (RCWA). Fits are then carried out to experimental data for 1 second exposures. Good quality fits are achieved and material parameters extracted. Monomer diffusion rates are determined to be of the order of D ~ 10 -10 cm 2/s and the time constant of the nonlocal material temporal response function being of the order of τ n ~ 10 -2s. Material shrinkage occurring over these recording periods is also determined.

Pathways for diffusion in the potential energy landscape of the network glass former SiO2

NASA Astrophysics Data System (ADS)

Niblett, S. P.; Biedermann, M.; Wales, D. J.; de Souza, V. K.

2017-10-01

We study the dynamical behaviour of a computer model for viscous silica, the archetypal strong glass former, and compare its diffusion mechanism with earlier studies of a fragile binary Lennard-Jones liquid. Three different methods of analysis are employed. First, the temperature and time scale dependence of the diffusion constant is analysed. Negative correlation of particle displacements influences transport properties in silica as well as in fragile liquids. We suggest that the difference between Arrhenius and super-Arrhenius diffusive behaviour results from competition between the correlation time scale and the caging time scale. Second, we analyse the dynamics using a geometrical definition of cage-breaking transitions that was proposed previously for fragile glass formers. We find that this definition accurately captures the bond rearrangement mechanisms that control transport in open network liquids, and reproduces the diffusion constants accurately at low temperatures. As the same method is applicable to both strong and fragile glass formers, we can compare correlation time scales in these two types of systems. We compare the time spent in chains of correlated cage breaks with the characteristic caging time and find that correlations in the fragile binary Lennard-Jones system persist for an order of magnitude longer than those in the strong silica system. We investigate the origin of the correlation behaviour by sampling the potential energy landscape for silica and comparing it with the binary Lennard-Jones model. We find no qualitative difference between the landscapes, but several metrics suggest that the landscape of the fragile liquid is rougher and more frustrated. Metabasins in silica are smaller than those in binary Lennard-Jones and contain fewer high-barrier processes. This difference probably leads to the observed separation of correlation and caging time scales.

Anisotropic diffusion and capture on surfaces: Time dependent modeling and visualization in 2 dimensions

NASA Astrophysics Data System (ADS)

Yang, Pu

Since the application of nanowires may lead to a new generation of electronic, optoelectronic and magnetic devices, there is much research on understanding the growth mechanism of various "self assembled" nanowires on semiconductor surfaces. The motivation of the present work is to use theoretical modeling to study the conditions required to form and grow elongated islands and nanowires. In this work, a modeling method is developed to study the time-dependent anisotropic diffusion and growth in two dimensions for an array of rectangular islands. This method uses discrete Fast Fourier Transformation (FFT) to solve the time-dependent diffusion equation on the surface. The ad-particles are captured and incorporated to the island edge to simulate island growth. Implemented in MATLABRTM programs, this model produces expected faceted shapes; the calculation runs very fast on a common personal computer. Time-dependent island growth and the evolving diffusion field have been visualized using simple MATLABRTM functions and can be made into MATLABRTM movies. This modeling method is applied to simulate elongated island and nanowire growth by incorporating anisotropic bonding at the island edge. When there is a full sink in one direction and partial sink in the other direction at the island edge, the model results in the growth of an elongated island with an aspect ratio that stabilizes after it reaches a certain value. This result agrees with experimental data on "endotaxial" nanowire growth. For the island edge with a full sink in one direction and no sink in the other direction, the island grows in length with constant width, which is comparable to experimental data on Bi nanoline and rare-earth metal nanowire growth.

Boron nitride nanotube as a delivery system for platinum drugs: Drug encapsulation and diffusion coefficient prediction.

PubMed

Khatti, Zahra; Hashemianzadeh, Seyed Majid

2016-06-10

Molecular dynamics (MD) simulation has been applied to investigate a drug delivery system based on boron nitride nanotubes, particularly the delivery of platinum-based anticancer drugs. For this propose, the behavior of carboplatin drugs inserted in boron nitride nanotubes (BNNT) as a carrier was studied. The diffusion rate of water molecules and carboplatin was investigated inside functionalized and pristine boron nitride nanotubes. The penetration rate of water and drug in functionalized BNNT was higher than that in pristine BNNT due to favorable water-mediated hydrogen bonding in hydroxyl edge-functionalized BNNT. Additionally, the encapsulation of multiple carboplatin drugs inside functionalized boron nitride nanotubes with one to five drug molecules confined inside the nanotube cavity was examined. At high drug loading, the hydrogen bond formation between adjacent drugs and the non-bonded van der Waals interaction between carboplatin and functionalized BNNT inner surface were found to be influential in drug displacement within the functionalized BNNT cavity for higher drug-loading capacity. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular Dynamic Simulation of Space and Earth-Grown Crystal Structures of Thermostable T1 Lipase Geobacillus zalihae Revealed a Better Structure.

PubMed

Ishak, Siti Nor Hasmah; Aris, Sayangku Nor Ariati Mohamad; Halim, Khairul Bariyyah Abd; Ali, Mohd Shukuri Mohamad; Leow, Thean Chor; Kamarudin, Nor Hafizah Ahmad; Masomian, Malihe; Rahman, Raja Noor Zaliha Raja Abd

2017-09-25

Less sedimentation and convection in a microgravity environment has become a well-suited condition for growing high quality protein crystals. Thermostable T1 lipase derived from bacterium Geobacillus zalihae has been crystallized using the counter diffusion method under space and earth conditions. Preliminary study using YASARA molecular modeling structure program for both structures showed differences in number of hydrogen bond, ionic interaction, and conformation. The space-grown crystal structure contains more hydrogen bonds as compared with the earth-grown crystal structure. A molecular dynamics simulation study was used to provide insight on the fluctuations and conformational changes of both T1 lipase structures. The analysis of root mean square deviation (RMSD), radius of gyration, and root mean square fluctuation (RMSF) showed that space-grown structure is more stable than the earth-grown structure. Space-structure also showed more hydrogen bonds and ion interactions compared to the earth-grown structure. Further analysis also revealed that the space-grown structure has long-lived interactions, hence it is considered as the more stable structure. This study provides the conformational dynamics of T1 lipase crystal structure grown in space and earth condition.

Structure, energetics and vibrational spectra of dimers, trimers, and tetramers of HX (X = Cl, Br, I)

NASA Astrophysics Data System (ADS)

Latajka, Zdzislaw; Scheiner, Steve

1997-03-01

The title complexes are studied by correlated ab initio methods using a pseudopotential double-ζ basis set, augmented by diffuse sp and two sets of polarization functions. The binding energies of the complexes decrease in the order HCl > HBr > HI. In the mixed HX…HX' dimers, the nature of the proton-donor molecule is more important than is the proton-acceptor with respect to the strength of the interaction. Only one minimum is found on the potential energy surface of the trimers and tetramers, which corresponds to the C nh cyclic structure. Enlargement of the complex leads to progressively greater individual H-bond energy and HX bond stretch, coupled with reduced intermolecular separation and smaller nonlinearity of each H-bond. Electron correlation makes a larger contribution as the atomic number of X increases. The highest degree of cooperativity is noted for oligomers of HCl and HBr, as compared to HI. The nonadditivity is dominated by terms present at the SCF level. The vibrational frequencies exhibit trends that generally parallel the energetics and geometry patterns, particularly the red shifts of the HX stretches and the intermolecular modes.

Nitrogen vacancy, self-interstitial diffusion, and Frenkel-pair formation/dissociation in B 1 TiN studied by ab initio and classical molecular dynamics with optimized potentials

NASA Astrophysics Data System (ADS)

Sangiovanni, D. G.; Alling, B.; Steneteg, P.; Hultman, L.; Abrikosov, I. A.

2015-02-01

We use ab initio and classical molecular dynamics (AIMD and CMD) based on the modified embedded-atom method (MEAM) potential to simulate diffusion of N vacancy and N self-interstitial point defects in B 1 TiN. TiN MEAM parameters are optimized to obtain CMD nitrogen point-defect jump rates in agreement with AIMD predictions, as well as an excellent description of Ti Nx(˜0.7

Thermally assisted peeling of an elastic strip in adhesion with a substrate via molecular bonds

NASA Astrophysics Data System (ADS)

Qian, Jin; Lin, Ji; Xu, Guang-Kui; Lin, Yuan; Gao, Huajian

A statistical model is proposed to describe the peeling of an elastic strip in adhesion with a flat substrate via an array of non-covalent molecular bonds. Under an imposed tensile peeling force, the interfacial bonds undergo diffusion-type transition in their bonding state, a process governed by a set of probabilistic equations coupled to the stretching, bending and shearing of the elastic strip. Because of the low characteristic energy scale associated with molecular bonding, thermal excitations are found to play an important role in assisting the escape of individual molecular bonds from their bonding energy well, leading to propagation of the peeling front well below the threshold peel-off force predicted by the classical theories. Our study establishes a link between the deformation of the strip and the spatiotemporal evolution of interfacial bonds, and delineates how factors like the peeling force, bending rigidity of the strip and binding energy of bonds influence the resultant peeling velocity and dimensions of the process zone. In terms of the apparent adhesion strength and dissipated energy, the bond-mediated interface is found to resist peeling in a strongly rate-dependent manner.

In-vitro transdentinal diffusion of monomers from adhesives.

PubMed

Putzeys, Eveline; Duca, Radu Corneliu; Coppens, Lieve; Vanoirbeek, Jeroen; Godderis, Lode; Van Meerbeek, Bart; Van Landuyt, Kirsten L

2018-06-01

Biocompatibility of adhesives is important since adhesives may be applied on dentin near the pulp. Accurate knowledge of the quantity of monomers reaching the pulp is important to determine potential side effects. The aim of this study was to assess the transdentinal diffusion of residual monomers from dental adhesive systems using an in-vitro pulp chamber model. Dentin disks with a thickness of 300 µm were produced from human third molars. These disks were fixed between two open-ended glass tubes, representing an in-vitro pulp chamber. The etch-and-rinse adhesive OptiBond FL and the self-etch adhesive Clearfil SE Bond were applied to the dentin side of the disks, while on in the pulpal side, the glass tube was filled with 600 µL water. The transdentinal diffusion of different monomers was quantified using ultra-performance liquid chromatography-tandem mass spectrometry. The monomers HEMA, CQ, BisGMA, GPDM, 10-MDP and UDMA eluted from the dental materials and were able to diffuse through the dentin disks to a certain extent. Compounds with a lower molecular weight (uncured group: HEMA 7850 nmol and CQ 78.2 nmol) were more likely to elute and diffuse compared to monomers with a higher molecular weight (uncured group: BisGMA 0.42 nmol). When the adhesives were left uncured, diffusion was up to 10 times higher compared to the cured conditions. This in-vitro research resulted in the quantification of various monomers able to diffuse through dentin and therefore contributes to a more detailed understanding about the potential exposure of the dental pulp to monomers from dental adhesives. Biocompatibility of adhesives is important since adhesives may be applied on dentin near the pulp, where tubular density and diameter are greatest. Copyright © 2018. Published by Elsevier Ltd.

Hydrogen loss and its improved retention in hydrogen plasma treated a-SiNx:H films: ERDA study with 100 MeV Ag7+ ions

NASA Astrophysics Data System (ADS)

Bommali, R. K.; Ghosh, S.; Khan, S. A.; Srivastava, P.

2018-05-01

Hydrogen loss from a-SiNx:H films under irradiation with 100 MeV Ag7+ ions using elastic recoil detection analysis (ERDA) experiment is reported. The results are explained under the basic assumptions of the molecular recombination model. The ERDA hydrogen concentration profiles are composed of two distinct hydrogen desorption processes, limited by rapid molecular diffusion in the initial stages of irradiation, and as the fluence progresses a slow process limited by diffusion of atomic hydrogen takes over. Which of the aforesaid processes dominates, is determined by the continuously evolving Hydrogen concentration within the films. The first process dominates when the H content is high, and as the H concentration falls below a certain threshold (Hcritical) the irradiation generated H radicals have to diffuse through larger distances before recombining to form H2, thereby significantly bringing down the hydrogen evolution rate. The ERDA measurements were also carried out for films treated with low temperature (300 °C) hydrogen plasma annealing (HPA). The HPA treated films show a clear increase in Hcritical value, thus indicating an improved diffusion of atomic hydrogen, resulting from healing of weak bonds and passivation of dangling bonds. Further, upon HPA films show a significantly higher H concentration relative to the as-deposited films, at advanced fluences. These results indicate the potential of HPA towards improved H retention in a-SiNx:H films. The study distinguishes clearly the presence of two diffusion processes in a-SiNx:H whose diffusion rates differ by an order of magnitude, with atomic hydrogen not being able to diffuse further beyond ∼ 1 nm from the point of its creation.

Elevated temperature properties of boron/aluminum composites

NASA Technical Reports Server (NTRS)

Sullivan, P. G.

1978-01-01

The high temperature properties of boron/aluminum composites, fabricated by an air diffusion bonding technique utilizing vacuum-bonded monolayer tape are reported. Seventeen different combinations of matrix alloy, reinforcement diameter, reinforcement volume percent, angle-ply and matrix enhancement (i.e. titanium cladding and interleaves) were fabricated, inspected, and tested. It is shown that good to excellent mechanical properties could be obtained for air-bonded boron/aluminum composites and that these properties did not decrease significantly up to a test temperature of at least 260 C. Composites made with 8 mil B/W fiber show a much greater longitudinal strength dependence on volume percent fiber than composites made with 5.6 mil fiber. The addition of titanium caused difficulties in composite bonding and yielded composites with reduced strength.

The Use Of Fluorescence Quenching To Measure Oxygen Concentration

NASA Astrophysics Data System (ADS)

Cox, M. E.; Dunn, B.

1986-01-01

The method of fluorescence quenching is used to measure the concentration of molecular oxygen. The method is rapid, reversible, and does not consume oxygen. The method may provide the basis for a unique biomedical sensor. The key to developing such a device lies in the choice of a fluorophor/polymer composite matrix having the desired optical and transport properties. Experimental results will be presented for certain parameters essential for assessing device development. The properties of interest include the kinetics of fluorescence quenching, the biomolecular rate constants, the temperature dependence of oxygen solubility and diffusivity in the composite matrix, and the oxygen diffusion coefficient. Poly(dimethyl siloxane) [PDMS] was chosen as the polymer host because it is biocompatible, hydrophobic, has a high diffusivity for the simple gases, and is easily bonded to fused silica. 9,10-diphenyl anthracene [9,10-D] was selected since it is readily soluble in a number of organic solvents, has an excitation spectrum in the near UV, an emission spectrum in the visible, a long fluorescence lifetime, and a high quantum yield. When incorporated into PDMS, the optical spectra of 9,10-D does not alter appreciably. The response time of the device is determined by the solution/diffusion kinetics of oxygen in PDMS. The solubility of oxygen in PDMS decreases with increasing temperature and an enthalpy of solution of off = -3.0 kcal/mole. (1) The diffusion of oxyzen in PDMS is found to obey an Arrhenius relation over the temperature range of 5'C to 450C with D = Do exp (-ED/RT) (2) where Do = 0.115 cm2/s (3) and ED = 4.77 kcal/mole. (4) Results of these studies indicate that an appropriate device, based on a fluorophor/polymer composite, for the measurement of oxygen concentration should be sensitive over those ranges which are important for physiological monitoring.

Self-generated Local Heating Induced Nanojoining for Room Temperature Pressureless Flexible Electronic Packaging

PubMed Central

Peng, Peng; Hu, Anming; Gerlich, Adrian P.; Liu, Yangai; Zhou, Y. Norman

2015-01-01

Metallic bonding at an interface is determined by the application of heat and/or pressure. The means by which these are applied are the most critical for joining nanoscale structures. The present study considers the feasibility of room-temperature pressureless joining of copper wires using water-based silver nanowire paste. A novel mechanism of self-generated local heating within the silver nanowire paste and copper substrate system promotes the joining of silver-to-silver and silver-to-copper without any external energy input. The localized heat energy was delivered in-situ to the interfaces to promote atomic diffusion and metallic bond formation with the bulk component temperature stays near room-temperature. This local heating effect has been detected experimentally and confirmed by calculation. The joints formed at room-temperature without pressure achieve a tensile strength of 5.7 MPa and exhibit ultra-low resistivity in the range of 101.3 nOhm·m. The good conductivity of the joint is attributed to the removal of organic compounds in the paste and metallic bonding of silver-to-copper and silver-to-silver. The water-based silver nanowire paste filler material is successfully applied to various flexible substrates for room temperature bonding. The use of chemically generated local heating may become a potential method for energy in-situ delivery at micro/nanoscale. PMID:25788019

Molecular Dynamics Simulations for Loading-Dependent Diffusion of CO2, SO2, CH4, and Their Binary Mixtures in ZIF-10: The Role of Hydrogen Bond.

PubMed

Li, Li; Yang, Deshuai; Fisher, Trevor R; Qiao, Qi; Yang, Zhen; Hu, Na; Chen, Xiangshu; Huang, Liangliang

2017-10-24

The loading-dependent diffusion behavior of CH 4 , CO 2 , SO 2 , and their binary mixtures in ZIF-10 has been investigated in detail by using classical molecular dynamics simulations. Our simulation results demonstrate that the self-diffusion coefficient D i of CH 4 molecules decreases sharply and monotonically with the loading while those of both CO 2 and SO 2 molecules initially display a slight increase at low uptakes and follow a slow decrease at high uptakes. Accordingly, the interaction energies between CH 4 molecules and ZIF-10 remain nearly constant regardless of the loading due to the absence of hydrogen bonds (HBs), while the interaction energies between CO 2 (or SO 2 ) and ZIF-10 decease rapidly with the loading, especially at small amounts of gas molecules. Such different loading-dependent diffusion and interaction mechanisms can be attributed to the relevant HB behavior between gas molecules and ZIF-10. At low loadings, both the number and strength of HBs between CO 2 (or SO 2 ) molecules and ZIF-10 decrease obviously as the loading increases, which is responsible for the slight increase of their diffusion coefficients. However, at high loadings, their HB strength increases with the loading. Similar loading-dependent phenomena of diffusion, interaction, and HB behavior can be observed for CH 4, CO 2 , and SO 2 binary mixtures in ZIF-10, only associated with some HB competition between CO 2 and SO 2 molecules in the case of the CO 2 /SO 2 mixture.

Shearography for Non-Destructive Evaluation with Applications to BAT Mask Tile Adhesive Bonding and Specular Surface Honeycomb Panels

NASA Technical Reports Server (NTRS)

Lysak, Daniel B.

2003-01-01

In this report we examine the applicability of shearography techniques for nondestructive inspection and evaluation in two unique application areas. In the first application, shearography is used to evaluate the quality of adhesive bonds holding lead tiles to the BAT gamma ray mask for the NASA Swift program. By exciting the mask with a vibration, the more poorly bonded tiles can be distinguished by their greater displacement response, which is readily identifiable in the shearography image. A quantitative analysis is presented that compares the shearography results with a destructive pull test measuring the force at bond failure. Generally speaking, the results show good agreement. Further investigation would be useful to optimize certain test parameters such as vibration frequency and amplitude. The second application is to evaluate the bonding between the skin and core of a honeycomb structure with a specular (mirror-like) surface. In standard shearography techniques, the object under test must have a diffuse surface to generate the speckle patterns in laser light, which are then sheared. A novel configuration using the specular surface as a mirror to image speckles from a diffuser is presented, opening up the use of shearography to a new class of objects that could not have been examined with the traditional approach. This new technique readily identifies large scale bond failures in the panel, demonstrating the validity of this approach. For the particular panel examined here, some scaling issues should be examined further to resolve the measurement scale down to the very small size of the core cells. In addition, further development should be undertaken to determine the general applicability of the new approach and to establish a firm quantitative foundation.

Comparison of the antibacterial activity of different self-etching primers and adhesives.

PubMed

Korkmaz, Yonca; Ozalp, Meral; Attar, Nuray

2008-11-01

The aim of this study was to evaluate the antibacterial effects of different one-step and two-step self-etching primer/adhesives on Streptococcus mutans (S. mutans), Lactobacillus casei (L. casei), and Lactobacillus acidophilus (L. acidophilus). The antibacterial effects of Clearfil Protect Bond Primer and Bonding agent; AdheSE Primer and Bonding agent; Adper Prompt L-Pop; Futurabond NR; Clearfil Tri S Bond; and Cervitec (positive control, 1% chlorhexidine varnish) were tested against standard strains of S. mutans, L. Casei, and L. acidophilus using the disk diffusion method. Standard filter paper disks (n=5) impregnated with 20 microL of each material were prepared. After incubation at 37 masculineC for 48 hours in a 5-10% CO2 atmosphere, the diameter of inhibition zones were measured in millimeters. Data were analyzed using one way analysis of variance (ANOVA) and multivariate analysis of variance (MANOVA). Duncan's Multiple Range Test was used for pairwise comparison. The size of inhibition zones produced by primer/adhesives varied among the brands. AdheSE Primer: S. mutans (20.6+/-1.51); L. casei (14.8+/-1.78); L. acidophilus (11.4+/-0.54). Adper Prompt L-Pop: S. mutans (19.6+/-1.51); L. casei (13.8+/-1.64); L. acidophilus (13.8+/-1.09). Cervitec: S. mutans (23+/-0.00); L. casei (27+/-0.70); L. acidophilus (22.4+/-0.54). Clearfil Protect Bond Primer: S. mutans (17+/-0.00); L. casei (17.6+/-0.54); L. acidophilus (22.4+/-0.54). Futurabond NR was found effective only against S. mutans (14.6+/-1.67). Of all the materials tested, AdheSE Bonding agent, Clearfil Protect Bond Bonding agent, and Clearfil Tri S Bond exhibited no inhibition zone (-) for all bacteria tested. Among the adhesives tested Clearafil Protect Bond Primer based upon monomer methacryloyloxydodecylpyridiniium bromide (MDPB) was found to be the most potent material against L. acidophilus and L. casei. AdheSE Primer and Adper Prompt L-Pop are highly effective against S. mutans. Compared with other adhesive systems, Clearfil Protect Bond Primer (containing MDPB) showed a high antibacterial effect against all microorganizms tested. Two-step, self-etching primer/adhesive system Clearfil Protect Bond might be a suitable choice under minimally invasive restorations. The recently developed one-step, self-etching system Clearfil Tri S Bond showed no antibacterial effect against microorgazims tested.

JACKETING URANIUM

DOEpatents

Saller, H.A.; Keeler, J.R.

1959-07-14

The bonding to uranium of sheathing of iron or cobalt, or nickel, or alloys thereof is described. The bonding is accomplished by electro-depositing both surfaces to be joined with a coating of silver and amalgamating or alloying the silver layer with mercury or indium. Then the silver alloy is homogenized by exerting pressure on an assembly of the uranium core and the metal jacket, reducing the area of assembly and heating the assembly to homogenize by diffusion.

Structure and Bonding in Noncrystalline Solids Abstracts

DTIC Science & Technology

1983-06-02

displacement cascades are unlikely. Related damage studies as diffuse X- ray scattering, magnetic susceptibility and positron - annihilation lifetime...the positron annihilation lifetime data; diffuse X-ray scattering studies give evidence for "amorphized" clusters in neutron but not in elec-ron...feldspar glasses and glasses in the system CaO- MgO -SiO 2 . These results indicate that the nearest-neighbor and next- nearest-neighbor environments are very

Trends in Effective Diffusion Coefficients for Ion-exchange Strengthening of Soda Lime Silicate Glasses

NASA Astrophysics Data System (ADS)

Karlsson, Stefan; Wondraczek, Lothar; Ali, Sharafat; Jonson, Bo

2017-04-01

Monovalent cations enable efficient ion exchange processes due to their high mobility in silicate glasses. Numerous properties can be modified in this way, e.g., mechanical, optical, electrical or chemical performance. In particular, alkali cation exchange has received significant attention, primarily with respect to introducing compressive stress into the surface region of a glass, which increases mechanical durability. However, most of the present applications rely on specifically tailored matrix compositions in which the cation mobility is enhanced. This largely excludes the major area of soda lime silicates (SLS) such as are commodity in almost all large-scale applications of glasses. Basic understanding of the relations between structural parameters and the effective diffusion coefficients may help to improve ion-exchanged SLS glass products, on the one hand in terms of obtainable strength and on the other in terms of cost. In the present paper, we discuss the trends in the effective diffusion coefficients when exchanging Na+ for various monovalent cations (K+, Cu+, Ag+, Rb+ and Cs+) by drawing relations to physico-chemical properties. Correlations of effective diffusion coefficients were found for the bond dissociation energy and the electronic cation polarizability, indicating that localization and rupture of bonds are of importance for the ion exchange rate.

Strain effect on the adsorption, diffusion, and molecular dissociation of hydrogen on Mg (0001) surface

NASA Astrophysics Data System (ADS)

Lei, Huaping; Wang, Caizhuang; Yao, Yongxin; Wang, Yangang; Hupalo, Myron; McDougall, Dan; Tringides, Michael; Ho, Kaiming

2013-12-01

The adsorption, diffusion, and molecular dissociation of hydrogen on the biaxially strained Mg (0001) surface have been systematically investigated by the first principle calculations based on density functional theory. When the strain changes from the compressive to tensile state, the adsorption energy of H atom linearly increases while its diffusion barrier linearly decreases oppositely. The dissociation barrier of H2 molecule linearly reduces in the tensile strain region. Through the chemical bonding analysis including the charge density difference, the projected density of states and the Mulliken population, the mechanism of the strain effect on the adsorption of H atom and the dissociation of H2 molecule has been elucidated by an s-p charge transfer model. With the reduction of the orbital overlap between the surface Mg atoms upon the lattice expansion, the charge transfers from p to s states of Mg atoms, which enhances the hybridization of H s and Mg s orbitals. Therefore, the bonding interaction of H with Mg surface is strengthened and then the atomic diffusion and molecular dissociation barriers of hydrogen decrease accordingly. Our works will be helpful to understand and to estimate the influence of the lattice deformation on the performance of Mg-containing hydrogen storage materials.

Proton Diffusion through Bilayer Pores

DOE PAGES

McDaniel, Jesse G.; Yethiraj, Arun

2017-09-26

The transport of protons through channels in complex environments is important in biology and materials science. In this work, we use multistate empirical valence bond simulations to study proton transport within a well-defined bilayer pore in a lamellar L β phase lyotropic liquid crystal (LLC). The LLC is formed from the self-assembly of dicarboxylate gemini surfactants in water, and a bilayer-spanning pore of radius of approximately 3–5 Å results from the uneven partitioning of surfactants between the two leaflets of the lamella. Local proton diffusion within the pore is significantly faster than diffusion at the bilayer surface, which is duemore » to the greater hydrophobicity of the surfactant/water interface within the pore. Proton diffusion proceeds by surface transport along exposed hydrophobic pockets at the surfactant/water interface and depends on the continuity of hydronium–water hydrogen bond networks. At the bilayer surface, there is a reduced fraction of the “Zundel” intermediates that are central to the Grotthuss transport mechanism, whereas the fraction of these species within the bilayer pore is similar to that in bulk water. Our results demonstrate that the chemical nature of the confining interface, in addition to confinement length scale, is an important determiner of local proton transport in nanoconfined aqueous environments.« less

Fabrication and evaluation of enhanced diffusion bonded titanium honeycomb core sandwich panels with titanium aluminide face sheets

NASA Technical Reports Server (NTRS)

Hoffmann, E. K.; Bird, R. K.; Bales, T. T.

1989-01-01

A joining process was developed for fabricating lightweight, high temperature sandwich panels for aerospace applications using Ti-14Al-21Nb face sheets and Ti-3Al-2.5V honeycomb core. The process, termed Enhanced Diffusion Bonding (EDB), relies on the formation of a eutectic liquid through solid-state diffusion at elevated temperatures and isothermal solidification to produce joints in thin-gage titanium and titanium aluminide structural components. A technique employing a maskant on the honeycomb core was developed which permitted electroplating a controlled amount of EDB material only on the edges of the honeycomb core in order to minimize the structural weight and metallurgical interaction effects. Metallurgical analyses were conducted to determine the interaction effects between the EDB materials and the constituents of the sandwich structure following EDB processing. The initial mechanical evaluation was conducted with butt joint specimens tested at temperatures from 1400 - 1700 F. Further mechanical evaluation was conducted with EDB sandwich specimens using flatwise tension tests at temperatures from 70 - 1100 F and edgewise compression tests at ambient temperature.

In-Field Diffuse Ultraviolet Spectroscopy and Imaging of the Stardust Sample Return Capsule

NASA Technical Reports Server (NTRS)

Pugel, D. Elizabeth; Stackpoole, Mairead; McNamara, Karen; Schwartz, C.; Warren, J.; Kontinos, Dean

2008-01-01

In-field diffuse Ultraviolet (UV) spectroscopy and imaging systems were developed for the purposes of evaluating the surface chemical composition of spacecraft thermal control coatings and materials. The investigation of these systems and the compilation of an associated UV reflectance and luminescence database were conducted using the Stardust Sample Return Capsule (SRC), located at the Johnson Space Center. Spectral responses of the surfaces of the Stardust forebody and aftbody in both reflectance and fluorescence modes were examined post-flight. In this paper, we report on two primary findings of in-field diffuse UV spectroscopy and imaging: (1) deduction of the thermal history of thermal control coatings of the forebody and (2) bond line variations in the aftbody. In the forebody, the thermal history of thermal control coatings may be deduced from the presence of particular semiconducting defect states associated with ZnO, a common emissivity constituent in thermal control coatings. A spatial dependence of this history was mapped for these regions. In the aftbody, luminescing defect states, associated with Si and SiO2 color centers were found along regions of bond variability.

Very Hard Corrosion-Resistant Roll-Bonded Cr Coating on Mild Steel in Presence of Graphite

NASA Astrophysics Data System (ADS)

Kumar, Pankaj; Khara, S.; Shekhar, S.; Mondal, K.

2017-12-01

The present work discusses the development of very hard Cr and Cr-carbide coating by roll bonding of Cr powder on a mild steel followed by annealing at 800, 1000, 1100 and 1200 °C with and without the presence of graphite powder packing in argon environment. In addition, the effect of a roll skin pass of 5% prior to the application of coating was studied. The presence of graphite allows diffusion of both carbon and Cr in the mild steel substrate, leading to the formation of Cr-carbide on the outer surface, making the surface very hard (VHN 1800). Depending on the annealing temperature and processing condition, diffusion layer thickness of Cr is found to be in the range of 10-250 μm with Cr content of 12.5-15 wt.% across the diffusion layer. Excellent stable passivity of the coated surface is observed in 0.2 N H2SO4, which is comparable to a highly passivating 304 stainless steel, and very low corrosion rate of the coating is observed as compared to the substrate mild steel.

Development of impact resistant boron/aluminum composites for turbojet engine fan blades

NASA Technical Reports Server (NTRS)

Melnyk, P.; Toth, I. J.

1975-01-01

Composite fabrication was performed by vacuum press diffusion bonding by both the foil-filament array and preconsolidated monotape methods. The effect of matrix material, fiber diameter, matrix enhancement, fiber volume reinforcement, test temperature, angle-plying, notch, impact orientation, processing variables and fabrication methods on tensile strength and Charpy impact resistance are evaluated. Root attachment concepts, were evaluated by room and elevated temperature tensile testing, as well as by pendulum-Izod and ballistic impact testing. Composite resistance to foreign object damage was also evaluated by ballistic impacting of panels using projectiles of gelatin, RTV rubber and steel at various velocities, and impingement angles. A significant improvement in the pendulum impact resistance of B-Al composites was achieved.

Development of High Temperature Dissimilar Joint Technology for Fission Surface Power Systems

NASA Technical Reports Server (NTRS)

Locci, Ivan E.; Bowman, Cheryl L.; Gabb, Timothy P.

2009-01-01

NASA is developing fission surface power (FSP) system technology as a potential option for use on the surface of the moon or Mars. The goal is to design a robust system that takes full advantage of existing materials data bases. One of the key components of the power conversion system is the hot-side Heat Exchanger (HX). One possible design for this heat exchanger requires a joint of the dissimilar metals 316L stainless steel and Inconel 718, which must sustain extended operation at high temperatures. This study compares two joining techniques, brazing and diffusion bonding, in the context of forming the requisite stainless steel to superalloy joint. The microstructures produced by brazing and diffusion bonding, the effect of brazing cycle on the mechanical tensile properties of the alloys, and the strength of several brazed joints will be discussed.

Rhenium Mechanical Properties and Joining Technology

NASA Technical Reports Server (NTRS)

Reed, Brian D.; Biaglow, James A.

1996-01-01

Iridium-coated rhenium (Ir/Re) provides thermal margin for high performance and long life radiation cooled rockets. Two issues that have arisen in the development of flight Ir/Re engines are the sparsity of rhenium (Re) mechanical property data (particularly at high temperatures) required for engineering design, and the inability to directly electron beam weld Re chambers to C103 nozzle skirts. To address these issues, a Re mechanical property database is being established and techniques for creating Re/C103 transition joints are being investigated. This paper discusses the tensile testing results of powder metallurgy Re samples at temperatures from 1370 to 2090 C. Also discussed is the evaluation of Re/C103 transition pieces joined by both, explosive and diffusion bonding. Finally, the evaluation of full size Re transition pieces, joined by inertia welding, as well as explosive and diffusion bonding, is detailed.

Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

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

Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V., E-mail: aneimark@rutgers.edu

2016-01-07

Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. Themore » DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.« less

pH-dependence of single-protein adsorption and diffusion at a liquid chromatographic interface.

PubMed

Kisley, Lydia; Poongavanam, Mohan-Vivekanandan; Kourentzi, Katerina; Willson, Richard C; Landes, Christy F

2016-02-01

pH is a common mobile phase variable used to control protein separations due to the tunable nature of amino acid and adsorbent charge. Like other column variables such as column density and ligand loading density, pH is usually optimized empirically. Single-molecule spectroscopy extracts molecular-scale data to provide a framework for mechanistic optimization of pH. The adsorption and diffusion of a model globular protein, α-lactalbumin, was studied by single-molecule microscopy at a silica-aqueous interface analogous to aqueous normal phase and hydrophilic interaction chromatography and capillary electrophoresis interfaces at varied pH. Electrostatic repulsion resulting in free diffusion was observed at pH above the isoelectric point of the protein. In contrast, at low pH strong adsorption and surface diffusion with either no (D ∼ 0.01 μm(2) /s) or translational (D ∼ 0.3 μm(2) /s) motion was observed where the protein likely interacted with the surface through electrostatic, hydrophobic, and hydrogen bonding forces. The fraction of proteins immobilized could be increased by lowering the pH. These results show that retention of proteins at the silica interface cannot be viewed solely as an adsorption/desorption process and that the type of surface diffusion, which ultimately leads to ensemble chromatographic separations, can be controlled by tuning long-range electrostatic and short-range hydrophobic and hydrogen bonding forces with pH. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold atoms and dimers on amorphous SiO(2): calculation of optical properties and cavity ringdown spectroscopy measurements.

PubMed

Del Vitto, Annalisa; Pacchioni, Gianfranco; Lim, Kok Hwa; Rösch, Notker; Antonietti, Jean-Marie; Michalski, Marcin; Heiz, Ulrich; Jones, Harold

2005-10-27

We report on the optical absorption spectra of gold atoms and dimers deposited on amorphous silica in size-selected fashion. Experimental spectra were obtained by cavity ringdown spectroscopy. Issues on soft-landing, fragmentation, and thermal diffusion are discussed on the basis of the experimental results. In parallel, cluster and periodic supercell density functional theory (DFT) calculations were performed to model atoms and dimers trapped on various defect sites of amorphous silica. Optically allowed electronic transitions were calculated, and comparisons with the experimental spectra show that silicon dangling bonds [[triple bond]Si(.-)], nonbridging oxygen [[triple bond]Si-O(.-)], and the silanolate group [[triple bond]Si-O(-)] act as trapping centers for the gold particles. The results are not only important for understanding the chemical bonding of atoms and clusters on oxide surfaces, but they will also be of fundamental interest for photochemical studies of size-selected clusters on surfaces.

Low-temperature direct copper-to-copper bonding enabled by creep on (111) surfaces of nanotwinned Cu

PubMed Central

Liu, Chien-Min; Lin, Han-Wen; Huang, Yi-Sa; Chu, Yi-Cheng; Chen, Chih; Lyu, Dian-Rong; Chen, Kuan-Neng; Tu, King-Ning

2015-01-01

Direct Cu-to-Cu bonding was achieved at temperatures of 150–250 °C using a compressive stress of 100 psi (0.69 MPa) held for 10–60 min at 10−3 torr. The key controlling parameter for direct bonding is rapid surface diffusion on (111) surface of Cu. Instead of using (111) oriented single crystal of Cu, oriented (111) texture of extremely high degree, exceeding 90%, was fabricated using the oriented nano-twin Cu. The bonded interface between two (111) surfaces forms a twist-type grain boundary. If the grain boundary has a low angle, it has a hexagonal network of screw dislocations. Such network image was obtained by plan-view transmission electron microscopy. A simple kinetic model of surface creep is presented; and the calculated and measured time of bonding is in reasonable agreement. PMID:25962757

Reduction-oxidation Enabled Glass-ceramics to Stainless Steel Bonding Part II interfacial bonding analysis

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

Dai, Steve Xunhu

2015-09-01

Among glass-ceramic compositions modified with a variety of oxidants (AgO, FeO, NiO, PbO, SnO, CuO, CoO, MoO 3 and WO 3) only CuO and CoO doped glass-ceramics showed existence of bonding oxides through reduction-oxidation (redox) at the GC-SS interface. The CuO-modified glass-ceramics demonstrate the formation of a continuous layer of strong bonding Cr 2O 3 at the interface in low partial oxygen (PO 2) atmosphere. However, in a local reducing atmosphere, the CuO is preferentially reduced at the surface of glass-ceramic rather than the GC-SS interface for redox. The CoO-modified glass-ceramics demonstrate improved GC-SS bonding. But the low mobility ofmore » Co ++ ions in the GC limited the amount of CoO that can diffuse to and participate in redox at the interface.« less

Antibacterial activity and dentin bonding ability of combined use of Clearfil SE Protect and sodium hypochlorite.

PubMed

Muratovska, Ilijana; Kitagawa, Haruaki; Hirose, Nanako; Kitagawa, Ranna; Imazato, Satoshi

2018-02-08

The aim of this study was to evaluate the antibacterial activity and dentin bonding ability of a commercial self-etch adhesive Clearfil SE Protect (Kuraray Noritake Dental, Tokyo, Japan) in combination with sodium hypochlorite (NaOCl). Agar disc diffusion tests and measurement of minimum inhibitory/bactericidal concentrations (MIC/MBC) against Streptococcus mutans were performed to evaluate antibacterial effects. The mixture solution of 5.25% NaOCl and the primer of Clearfil SE Protect demonstrated less antibacterial activity than primer only. In microtensile bond strength tests using non-carious human molars, pretreatment with 5.25% NaOCl aqueous solution had no influence on the bond strength of Clearfil SE Protect. These results indicate that pretreatment with NaOCl does not influence the bonding ability of Clearfil SE Protect, while their combined use does not enhance cavity disinfecting effects.

Cytotoxicity of Light-Cured Dental Materials according to Different Sample Preparation Methods

PubMed Central

Lee, Myung-Jin; Kim, Mi-Joo; Kwon, Jae-Sung; Lee, Sang-Bae; Kim, Kwang-Mahn

2017-01-01

Dental light-cured resins can undergo different degrees of polymerization when applied in vivo. When polymerization is incomplete, toxic monomers may be released into the oral cavity. The present study assessed the cytotoxicity of different materials, using sample preparation methods that mirror clinical conditions. Composite and bonding resins were used and divided into four groups according to sample preparation method: uncured; directly cured samples, which were cured after being placed on solidified agar; post-cured samples were polymerized before being placed on agar; and “removed unreacted layer” samples had their oxygen-inhibition layer removed after polymerization. Cytotoxicity was evaluated using an agar diffusion test, MTT assay, and confocal microscopy. Uncured samples were the most cytotoxic, while removed unreacted layer samples were the least cytotoxic (p < 0.05). In the MTT assay, cell viability increased significantly in every group as the concentration of the extracts decreased (p < 0.05). Extracts from post-cured and removed unreacted layer samples of bonding resin were less toxic than post-cured and removed unreacted layer samples of composite resin. Removal of the oxygen-inhibition layer resulted in the lowest cytotoxicity. Clinicians should remove unreacted monomers on the resin surface immediately after restoring teeth with light-curing resin to improve the restoration biocompatibility. PMID:28772647

Effect of Isothermal Hold on the Microstructural Evolution of the Stainless Steel 304L/Zircaloy-4 Interface

NASA Astrophysics Data System (ADS)

Lebaili, A.; Taouinet, M.; Nibou, D.; Lebaili, S.; Hodaj, F.

2017-07-01

The transition from solid-state bonding of the stainless steel 304L/Zircaloy-4 diffusion couple to a partial liquid-phase bonding is important for the bonding process at temperatures ranging from 950 to 1050 °C. In this study, the temperature at which a melting process occurs at the interface after 45 min of isothermal holdings is determined experimentally. This melting process leads to a drastic change in the thickness of the reaction products zone (RPZ) as well as on its microstructure. Diffusion couples were characterized by SEM-EDS, and quantitative chemical analyses of different phases are performed by EPMA. The RPZ consists of three layers: the (α-Fe-Cr) phase layer and two layers consisting of Zr(Fe,Cr)2 (ɛ), Zr2(Fe,Ni) and (α-Zr) phases. The thickness of these layers strongly depends on the holding temperature. The analysis allowed the description of the physicochemical phenomena occurring during isothermal holding as well as during cooling. The solidification paths are determined at 1000, 1020 and 1050 °C. Hardness tests are performed on the bonded samples in order to qualify the mechanical properties of different phases of the RPZ. This study leads to a better understanding of the complex phenomena intervening in the joining process which is very useful for applications in industrial scale.

Deer mouse hemoglobin exhibits a lowered oxygen affinity owing to mobility of the E helix.

PubMed

Inoguchi, Noriko; Oshlo, Jake R; Natarajan, Chandrasekhar; Weber, Roy E; Fago, Angela; Storz, Jay F; Moriyama, Hideaki

2013-04-01

The deer mouse, Peromyscus maniculatus, exhibits altitude-associated variation in hemoglobin oxygen affinity. To examine the structural basis of this functional variation, the structure of the hemoglobin was solved. Recombinant hemoglobin was expressed in Escherichia coli and was purified by ion-exchange chromatography. Recombinant hemoglobin was crystallized by the hanging-drop vapor-diffusion method using polyethylene glycol as a precipitant. The obtained orthorhombic crystal contained two subunits in the asymmetric unit. The refined structure was interpreted as the aquo-met form. Structural comparisons were performed among hemoglobins from deer mouse, house mouse and human. In contrast to human hemoglobin, deer mouse hemoglobin lacks the hydrogen bond between α1Trp14 in the A helix and α1Thr67 in the E helix owing to the Thr67Ala substitution. In addition, deer mouse hemoglobin has a unique hydrogen bond at the α1β1 interface between residues α1Cys34 and β1Ser128.

Deer mouse hemoglobin exhibits a lowered oxygen affinity owing to mobility of the E helix

PubMed Central

Inoguchi, Noriko; Oshlo, Jake R.; Natarajan, Chandrasekhar; Weber, Roy E.; Fago, Angela; Storz, Jay F.; Moriyama, Hideaki

2013-01-01

The deer mouse, Peromyscus maniculatus, exhibits altitude-associated variation in hemoglobin oxygen affinity. To examine the structural basis of this functional variation, the structure of the hemoglobin was solved. Recombinant hemoglobin was expressed in Escherichia coli and was purified by ion-exchange chromatography. Recombinant hemoglobin was crystallized by the hanging-drop vapor-diffusion method using polyethylene glycol as a precipitant. The obtained orthorhombic crystal contained two subunits in the asymmetric unit. The refined structure was interpreted as the aquo-met form. Structural comparisons were performed among hemoglobins from deer mouse, house mouse and human. In contrast to human hemoglobin, deer mouse hemoglobin lacks the hydrogen bond between α1Trp14 in the A helix and α1Thr67 in the E helix owing to the Thr67Ala substitution. In addition, deer mouse hemoglobin has a unique hydrogen bond at the α1β1 interface between residues α1Cys34 and β1Ser128. PMID:23545644

Fabrication of gas turbine water-cooled composite nozzle and bucket hardware employing plasma spray process

DOEpatents

Schilke, Peter W.; Muth, Myron C.; Schilling, William F.; Rairden, III, John R.

1983-01-01

In the method for fabrication of water-cooled composite nozzle and bucket hardware for high temperature gas turbines, a high thermal conductivity copper alloy is applied, employing a high velocity/low pressure (HV/LP) plasma arc spraying process, to an assembly comprising a structural framework of copper alloy or a nickel-based super alloy, or combination of the two, and overlying cooling tubes. The copper alloy is plamsa sprayed to a coating thickness sufficient to completely cover the cooling tubes, and to allow for machining back of the copper alloy to create a smooth surface having a thickness of from 0.010 inch (0.254 mm) to 0.150 inch (3.18 mm) or more. The layer of copper applied by the plasma spraying has no continuous porosity, and advantageously may readily be employed to sustain a pressure differential during hot isostatic pressing (HIP) bonding of the overall structure to enhance bonding by solid state diffusion between the component parts of the structure.

A systemic investigation of hydrogen peroxide clusters (H2O2)n (n = 1-6) and liquid-state hydrogen peroxide: based on atom-bond electronegativity equalization method fused into molecular mechanics and molecular dynamics.

PubMed

Yu, Chun-Yang; Yang, Zhong-Zhi

2011-03-31

Hydrogen peroxide (HP) clusters (H(2)O(2))(n) (n = 1-6) and liquid-state HP have been systemically investigated by the newly constructed ABEEM/MM fluctuating charge model. Because of the explicit description of charge distribution and special treatment of the hydrogen-bond interaction region, the ABEEM/MM potential model gives reasonable properties of HP clusters, including geometries, interaction energies, and dipole moments, when comparing with the present ab initio results. Meanwhile, the average dipole moment, static dielectric constant, heats of vaporization, radial distribution function, and diffusion constant for the dynamic properties of liquid HP at 273 K and 1 atm are fairly consistent with the available experimental data. To the best of our knowledge, this is the first theoretical investigation of condensed HP. The properties of HP monomer are studied in detail involving the structure, torsion potentials, molecular orbital analysis, charge distribution, dipole moment, and vibrational frequency.

The acousto-ultrasonic approach

NASA Technical Reports Server (NTRS)

Vary, Alex

1987-01-01

The nature and underlying rationale of the acousto-ultrasonic approach is reviewed, needed advanced signal analysis and evaluation methods suggested, and application potentials discussed. Acousto-ultrasonics is an NDE technique combining aspects of acoustic emission methodology with ultrasonic simulation of stress waves. This approach uses analysis of simulated stress waves for detecting and mapping variations of mechanical properties. Unlike most NDE, acousto-ultrasonics is less concerned with flaw detection than with the assessment of the collective effects of various flaws and material anomalies. Acousto-ultrasonics has been applied chiefly to laminated and filament-wound fiber reinforced composites. It has been used to assess the significant strength and toughness reducing effects that can be wrought by combinations of essentially minor flaws and diffuse flaw populations. Acousto-ultrasonics assesses integrated defect states and the resultant variations in properties such as tensile, shear, and flexural strengths and fracture resistance. Matrix cure state, porosity, fiber orientation, fiber volume fraction, fiber-matrix bonding, and interlaminar bond quality are underlying factors.

Characteristics of copper-clad aluminum rods prepared by horizontal continuous casting

NASA Astrophysics Data System (ADS)

Zhang, Yubo; Fu, Ying; Jie, Jinchuan; Wu, Li; Svynarenko, Kateryna; Guo, Qingtao; Li, Tingju; Wang, Tongmin

2017-11-01

An innovative horizontal continuous casting method was developed and successfully used to prepare copper-clad aluminum (CCA) rods with a diameter of 85 mm and a sheath thickness of 16 mm. The solidification structure and element distribution near the interface of the CCA ingots were investigated by means of a scanning electron microscope, an energy dispersive spectrometer, and an electron probe X-ray microanalyzer. The results showed that the proposed process can lead to a good metallurgical bond between Cu and Al. The interface between Cu and Al was a multilayered structure with a thickness of 200 μm, consisting of Cu9Al4, CuAl2, α-Al/CuAl2 eutectic, and α-Al + α-Al/CuAl2 eutectic layers from the Cu side to the Al side. The mean tensile-shear strength of the CCA sample was 45 MPa, which fulfills the requirements for the further extrusion process. The bonding and diffusion mechanisms are also discussed in this paper.

Coiled Tube Gas Heaters For Nuclear Gas-Brayton Power Conversion

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

Peterson, Per F.

This project developed an alternative design for heat exchangers for application to heating supercritical carbon dioxide (S-CO 2) or air for power conversion. We have identified an annular coiled tube bundle configuration–where hot sodium enters tubes from multiple vertical inlet manifold pipes, flows in a spiral pattern radially inward and downward, and then exits into an equal number of vertical outlet manifold pipes–as a potentially attractive option. The S-CO 2 gas or air flows radially outward through the tube bundle. Coiled tube gas heaters (CTGHs) are expected to have excellent thermal shock, long-term thermal creep, in-service inspection, and reparability characteristics,more » compared to alternative options. CTGHs have significant commonality with modern nuclear steam generators. Extensive experience exists with the design, manufacture, operation, in-service inspection and maintenance of nuclear steam generators. The U.S. Nuclear Regulatory Commission also has extensive experience with regulatory guidance documented in NUREG 0800. CTGHs leverage this experience and manufacturing capability. The most important difference between steam generators and gas-Brayton cycles such as the S-CO 2 cycle is that the heat exchangers must operate with counter flow with high effectiveness to minimize the pinch-point temperature difference between the hot liquid coolant and the heated gas. S-CO 2-cycle gas heaters also operate at sufficiently elevated temperatures that time dependent creep is important and allowable stresses are relatively low. Designing heat exchangers to operate in this regime requires configurations that minimize stresses and stress concentrations. The cylindrical tubes and cylindrical manifold pipes used in CTGHs are particularly effective geometries. The first major goal of this research project was to develop and experimentally validate a detailed, 3-D multi-phase (gas-solid-liquid) heat transport model for CTGHs, using methods similar to earlier UCB multi-scale models for PCHEs, which will enable optimization of CTGH designs with respect to the number of manifold pipes, S-CO 2 and sodium circulating power, and other design parameters. CTGHs are relatively novel because the tubes loaded in compression as well as the manifold pipes which form the tube sheets. The second major goal of the experimental and modeling effort was to optimize the assembly and heat treatment of the tube-to-tubesheet joints, using a novel tapered joint configuration, and to develop diffusion-bonded joints with high shear strength and creep resistance, as has been done in other applications for tapered plugs. The project would also conduct creep testing of these tubesheet joints in pressurized furnaces under prototypical conditions of stress and temperature, however this was not feasible due to numerous hinderances. Detailed microstructural investigations was conducted on the diffusion bond interface, while the bond strength was evaluated by tensile testing. The mechanical testing quantified the overall strength of the bond and measured the pull out force as well as long term behavior, which complemented the microstructural analysis and gave a complete understanding of the diffusion bond.« less

Non-hoop winding effect on bonding temperature of laser assisted tape winding process

NASA Astrophysics Data System (ADS)

Zaami, Amin; Baran, Ismet; Akkerman, Remko

2018-05-01

One of the advanced methods for production of thermoplastic composite methods is laser assisted tape winding (LATW). Predicting the temperature in LATW process is very important since the temperature at nip-point (bonding line through width) plays a pivotal role in a proper bonding and hence the mechanical performance. Despite the hoop-winding where the nip-point is the straight line, non-hoop winding includes a curved nip-point line. Hence, the non-hoop winding causes somewhat a different power input through laser-rays and-reflections and consequently generates unknown complex temperature profile on the curved nip-point line. Investigating the temperature at the nip-point line is the point of interest in this study. In order to understand this effect, a numerical model is proposed to capture the effect of laser-rays and their reflections on the nip-point temperature. To this end, a 3D optical model considering the objects in LATW process is considered. Then, the power distribution (absorption and reflection) from the optical analysis is used as an input (heat flux distribution) for the thermal analysis. The thermal analysis employs a fully-implicit advection-diffusion model to calculate the temperature on the surfaces. The results are examined to demonstrate the effect of winding direction on the curved nip-point line (tape width) which has not been considered in literature up to now. Furthermore, the results can be used for designing a better and more efficient setup in the LATW process.

Diffusion quantum Monte Carlo and density functional calculations of the structural stability of bilayer arsenene

NASA Astrophysics Data System (ADS)

Kadioglu, Yelda; Santana, Juan A.; Özaydin, H. Duygu; Ersan, Fatih; Aktürk, O. Üzengi; Aktürk, Ethem; Reboredo, Fernando A.

2018-06-01

We have studied the structural stability of monolayer and bilayer arsenene (As) in the buckled (b) and washboard (w) phases with diffusion quantum Monte Carlo (DMC) and density functional theory (DFT) calculations. DMC yields cohesive energies of 2.826(2) eV/atom for monolayer b-As and 2.792(3) eV/atom for w-As. In the case of bilayer As, DMC and DFT predict that AA-stacking is the more stable form of b-As, while AB is the most stable form of w-As. The DMC layer-layer binding energies for b-As-AA and w-As-AB are 30(1) and 53(1) meV/atom, respectively. The interlayer separations were estimated with DMC at 3.521(1) Å for b-As-AA and 3.145(1) Å for w-As-AB. A comparison of DMC and DFT results shows that the van der Waals density functional method yields energetic properties of arsenene close to DMC, while the DFT + D3 method closely reproduced the geometric properties from DMC. The electronic properties of monolayer and bilayer arsenene were explored with various DFT methods. The bandgap values vary significantly with the DFT method, but the results are generally qualitatively consistent. We expect the present work to be useful for future experiments attempting to prepare multilayer arsenene and for further development of DFT methods for weakly bonded systems.

Liquid li structure and dynamics: A comparison between OFDFT and second nearest-neighbor embedded-atom method

DOE PAGES

Chen, Mohan; Vella, Joseph R.; Panagiotopoulos, Athanassios Z.; ...

2015-04-08

The structure and dynamics of liquid lithium are studied using two simulation methods: orbital-free (OF) first-principles molecular dynamics (MD), which employs OF density functional theory (DFT), and classical MD utilizing a second nearest-neighbor embedded-atom method potential. The properties we studied include the dynamic structure factor, the self-diffusion coefficient, the dispersion relation, the viscosity, and the bond angle distribution function. Our simulation results were compared to available experimental data when possible. Each method has distinct advantages and disadvantages. For example, OFDFT gives better agreement with experimental dynamic structure factors, yet is more computationally demanding than classical simulations. Classical simulations can accessmore » a broader temperature range and longer time scales. The combination of first-principles and classical simulations is a powerful tool for studying properties of liquid lithium.« less

Why do proton conducting polybenzimidazole phosphoric acid membranes perform well in high-temperature PEM fuel cells?

PubMed

Melchior, Jan-Patrick; Majer, Günter; Kreuer, Klaus-Dieter

2016-12-21

Transport properties and hydration behavior of phosphoric acid/(benz)imidazole mixtures are investigated by diverse NMR techniques, thermogravimetric analysis (TGA) and conductivity measurements. The monomeric systems can serve as models for phosphoric acid/poly-benzimidazole membranes which are known for their exceptional performance in high temperature PEM fuel cells. 1 H- and 31 P-NMR data show benzimidazole acting as a strong Brønsted base with respect to neat phosphoric acid. Since benzimidazole's nitrogens are fully protonated with a low rate for proton exchange with phosphate species, proton diffusion and conduction processes must take place within the hydrogen bond network of phosphoric acid only. The proton exchange dynamics between phosphate and benzimidazole species pass through the intermediate exchange regime (with respect to NMR line separations) with exchange times being close to typical diffusion times chosen in PFG-NMR diffusion measurements (ms regime). The resulting effects, as described by the Kärger equation, are included into the evaluation of PFG-NMR data for obtaining precise proton diffusion coefficients. The highly reduced proton diffusion coefficient within the phosphoric acid part of the model systems compared to neat phosphoric acid is suggested to be the immediate consequence of proton subtraction from phosphoric acid. This reduces hydrogen bond network frustration (imbalance of the number of proton donors and acceptors) and therefore also the rate of structural proton diffusion, phosphoric acid's acidity and hygroscopicity. Reduced water uptake, shown by TGA, goes along with reduced electroosmotic water drag which is suggested to be the reason for PBI-phosphoric acid membranes performing better in fuel cells than other phosphoric-acid-containing electrolytes with higher protonic conductivity.

Effects of thermal cycling on graphie-fiber-reinforced 6061 aluminum

NASA Technical Reports Server (NTRS)

Dries, G. A.; Tompkins, S. S.

1986-01-01

Graphite-reinforced aluminum alloy metal-matrix composites are among materials being considered for structural components in dimensionally stable space structures. This application requires materials with low values of thermal expansions and high specific stiffnesses. They must remain stable during exposures to the space environment for periods extending to 20 years. The effects of thermal cycling on the thermal expansion behavior and mechanical properties of Thornel P100 graphite 6061 aluminum composites, as fabricated and after thermal processing to eliminate thermal strain hysteresis, have been investigated. Two groups of composites were studied: one was fabricated by hot roll bonding and the other by diffusion bonding. Processing significantly reduced strain hysteresis during thermal cycling in both groups and improved the ultimate tensile strength and modulus in the diffusion-bonded composites. Thermal cycling stabilized the as-fabricated composites by reducing the residual fabrication stress and increased the matrix strength by metallurgical aging. Thermal expansion behavior of both groups after processing was insensitive to thermal cycling. Data scatter was too large to determine effects of thermal cycling on the mechanical properties. The primary effects of processing and thermal cycling can be attributed to changes in the metallurgical condition and stress state of the matrix.

Coupled diffusion in lipid bilayers upon close approach

DOE PAGES

Pronk, Sander; Lindahl, Erik; Kasson, Peter M.

2014-12-23

Biomembrane interfaces create regions of slowed water dynamics in their vicinity. When two lipid bilayers come together, this effect is further accentuated, and the associated slowdown can affect the dynamics of larger-scale processes such as membrane fusion. We have used molecular dynamics simulations to examine how lipid and water dynamics are affected as two lipid bilayers approach each other. These two interacting fluid systems, lipid and water, both slow and become coupled when the lipid membranes are separated by a thin water layer. We show in particular that the water dynamics become glassy, and diffusion of lipids in the apposedmore » leaflets becomes coupled across the water layer, while the “outer” leaflets remain unaffected. This dynamic coupling between bilayers appears mediated by lipid–water–lipid hydrogen bonding, as it occurs at bilayer separations where water–lipid hydrogen bonds become more common than water–water hydrogen bonds. We further show that such coupling occurs in simulations of vesicle–vesicle fusion prior to the fusion event itself. As a result, such altered dynamics at membrane–membrane interfaces may both stabilize the interfacial contact and slow fusion stalk formation within the interface region.« less

Intraparticle diffusion limitations in the hydrogenation of monounsaturated edible oils and their fatty acid methyl esters

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

Jonker, G.H.; Veldsink, J.W.; Beenackers, A.A.C.M.

1998-12-01

Intraparticle diffusion limitation in the hydrogenation and isomerization of fatty acid methyl esters (FAMEs) and edible oils (triacylglycerol, TAG) in porous nickel catalyst was investigated both under reactive and under inert conditions. Under reactive conditions, the diffusion coefficients were determined from the best fits of the model simulations applying the intrinsic reacting kinetics of monounsaturated FAME hydrogenation to experiments under diffusion limited conditions. Due to the absence of reaction (hydrogenation of double bonds), the obtained effective H{sub z} diffusion coefficient (D{sub e}) with the HPLC technique is volume averaged and thereby determined by the larger intercrystalline pores (<30% of themore » total pore volume) only. Moreover, D{sub e} measured under reaction conditions reflected the influence of the micropores, resulting in a 10-fold lower value.« less

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

Surodin, S. I., E-mail: surodin.bsn@mail.ru; Nikolitchev, D. E.; Kryukov, R. N.

The concentration profiles of species in silicon subjected to gallium and nitrogen co-implantation and subsequent annealing have been investigated by the method of X-ray photoelectron spectroscopy combined with the layer-by-layer ion etching of the implanted layer. It is shown that practically entire implanted gallium undergoes out-diffusion, but the preliminary implantation of nitrogen for the synthesis of a barrier SiN{sub x} layer makes it possible to avoid the essential loss of gallium. In this case, about 14 % of implanted gallium bond to nitrogen. The obtained data are discussed from the viewpoint of the possibility of ion synthesis of GaN inclusionsmore » in silicon matrix.« less

How multiple social networks affect user awareness: The information diffusion process in multiplex networks

NASA Astrophysics Data System (ADS)

Li, Weihua; Tang, Shaoting; Fang, Wenyi; Guo, Quantong; Zhang, Xiao; Zheng, Zhiming

2015-10-01

The information diffusion process in single complex networks has been extensively studied, especially for modeling the spreading activities in online social networks. However, individuals usually use multiple social networks at the same time, and can share the information they have learned from one social network to another. This phenomenon gives rise to a new diffusion process on multiplex networks with more than one network layer. In this paper we account for this multiplex network spreading by proposing a model of information diffusion in two-layer multiplex networks. We develop a theoretical framework using bond percolation and cascading failure to describe the intralayer and interlayer diffusion. This allows us to obtain analytical solutions for the fraction of informed individuals as a function of transmissibility T and the interlayer transmission rate θ . Simulation results show that interaction between layers can greatly enhance the information diffusion process. And explosive diffusion can occur even if the transmissibility of the focal layer is under the critical threshold, due to interlayer transmission.

Diffusion coefficients of Mg isotopes in enstatite and forsterite melts calculated by first-principles molecular dynamic simulations

NASA Astrophysics Data System (ADS)

Huang, F.; Qi, Y.; Liu, X.; He, L.

2016-12-01

Stable isotopes can be fractionated by kinetic chemical diffusion because diffusion coefficients (D) of isotopes are mass-dependent. Diffusive isotopic fractionation recorded in rocks and minerals provide unique temporal constrains on geological processes. The mass dependence of D can be described in the form of Di/Dj= (mj/mi)β, where m denotes masses of isotope i and j, and β is an emperical parameter used to quantify the diffusive transport of isotopes [1]. β values can be estimated by experimental calibration and observation of natural samples, which are still rarely reported because it is challenging to precisely quantify the boundary conditions of diffusion processes [2,3,4]. Recent advances in computation technique provide a new way to theoretically calculate β values. For instance, classical molecular dynamics with empirical potential have been used to simulate interactions between atoms and estimate β of Mg isotopes in MgSiO3 melt [3]. Here, to further consider the effect of bonding and electron properties on β values, we apply first-principles Born-Oppenheimer Molecular Dynamics and pseudo-isotope methods (assuming mj/mi = 1/24, 1/4, 2, and 5) to estimate β for MgSiO3 and Mg2SiO4 melts. Our calculation shows that β of Mg isotopes with pseudo-mass ratios are consistent, indicating the reliability of the pseudo-isotope method. For MgSiO3 melt, β is 0.18 at 4000K and 0 GPa, higher than the value calculatedusing molecular dynamics simulations (0.135) [3]. For Mg2SiO4 melt at 0 GPa, β values are: 0.23 ± 0.04 at 2300K, 0.24 ± 0.07 at 3000K, and 0.24 ± 0.01 at 4000K. Notably, β of MgSiO3 and Mg2SiO4 melts are significantly higher than the value determined by diffusion experiments (0.05) [2]. These results indicate that β values are not sensitive to temperature, but dependent on melt composition.

Elasticity and critical bending moment of model colloidal aggregates.

PubMed

Pantina, John P; Furst, Eric M

2005-04-08

The bending mechanics of singly bonded colloidal aggregates are measured using laser tweezers. We find that the colloidal bonds are capable of supporting significant torques, providing a direct measurement of the tangential interactions between particles. A critical bending moment marks the limit of linear bending elasticity, past which small-scale rearrangements occur. These mechanical properties underlie the rheology and dynamics of colloidal gels formed by diffusion-limited cluster aggregation, and give critical insight into the contact interactions between Brownian particles.

Nature of electron trap states under inversion at In0.53Ga0.47As/Al2O3 interfaces

NASA Astrophysics Data System (ADS)

Colleoni, Davide; Pourtois, Geoffrey; Pasquarello, Alfredo

2017-03-01

In and Ga impurities substitutional to Al in the oxide layer resulting from diffusion out of the substrate are identified as candidates for electron traps under inversion at In0.53Ga0.47As/Al2O3 interfaces. Through density-functional calculations, these defects are found to be thermodynamically stable in amorphous Al2O3 and to be able to capture two electrons in a dangling bond upon breaking bonds with neighboring O atoms. Through a band alignment based on hybrid functional calculations, it is inferred that the corresponding defect levels lie at ˜1 eV above the conduction band minimum of In0.53Ga0.47As, in agreement with measured defect densities. These results support the technological importance of avoiding cation diffusion into the oxide layer.

The crack problem in bonded nonhomogeneous materials

NASA Technical Reports Server (NTRS)

Erdogan, Fazil; Kaya, A. C.; Joseph, P. F.

1988-01-01

The plane elasticity problem for two bonded half planes containing a crack perpendicular to the interface was considered. The effect of very steep variations in the material properties near the diffusion plane on the singular behavior of the stresses and stress intensity factors were studied. The two materials were thus, assumed to have the shear moduli mu(o) and mu(o) exp (Beta x), x=0 being the diffusion plane. Of particular interest was the examination of the nature of stress singularity near a crack tip terminating at the interface where the shear modulus has a discontinuous derivative. The results show that, unlike the crack problem in piecewise homogeneous materials for which the singularity is of the form r/alpha, 0 less than alpha less than 1, in this problem the stresses have a standard square-root singularity regardless of the location of the crack tip. The nonhomogeneity constant Beta has, however, considerable influence on the stress intensity factors.

The crack problem in bonded nonhomogeneous materials

NASA Technical Reports Server (NTRS)

Erdogan, F.; Joseph, P. F.; Kaya, A. C.

1991-01-01

The plane elasticity problem for two bonded half planes containing a crack perpendicular to the interface was considered. The effect of very steep variations in the material properties near the diffusion plane on the singular behavior of the stresses and stress intensity factors were studied. The two materials were thus, assumed to have the shear moduli mu(o) and mu(o) exp (Beta x), x=0 being the diffusion plane. Of particular interest was the examination of the nature of stress singularity near a crack tip termination at the interface where the shear modulus has a discontinuous derivative. The results show that, unlike the crack problem in piecewise homogeneous materials for which the singularity is of the form r/alpha, 0 less than alpha less than 1, in this problem the stresses have a standard square-root singularity regardless of the location of the crack tip. The nonhomogeneity constant Beta has, however, considerable influence on the stress intensity factors.

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

Yoo, Hyun Deog; Liang, Yanliang; Dong, Hui

Magnesium rechargeable batteries potentially offer high-energy density, safety, and low cost due to the ability to employ divalent, dendrite-free, and earth-abundant magnesium metal anode. Despite recent progress, further development remains stagnated mainly due to the sluggish scission of magnesium-chloride bond and slow diffusion of divalent magnesium cations in cathodes. Here in this paper we report a battery chemistry that utilizes magnesium monochloride cations in expanded titanium disulfide. Combined theoretical modeling, spectroscopic analysis, and electrochemical study reveal fast diffusion kinetics of magnesium monochloride cations without scission of magnesium-chloride bond. The battery demonstrates the reversible intercalation of 1 and 1.7 magnesium monochloridemore » cations per titanium at 25 and 60 °C, respectively, corresponding to up to 400 mAh g -1 capacity based on the mass of titanium disulfide. The large capacity accompanies with excellent rate and cycling performances even at room temperature, opening up possibilities for a variety of effective intercalation hosts for multivalent-ion batteries.« less

Hydrogen bond dynamics in bulk alcohols.

PubMed

Shinokita, Keisuke; Cunha, Ana V; Jansen, Thomas L C; Pshenichnikov, Maxim S

2015-06-07

Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics-quantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquid--alcohols--has attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve the interplay of hydrophobic and hydrophilic groups.

Identifying Mechanisms of Interfacial Dynamics Using Single-Molecule Tracking

PubMed Central

Kastantin, Mark; Walder, Robert; Schwartz, Daniel K.

2012-01-01

The “soft” (i.e. non-covalent) interactions between molecules and surfaces are complex and highly-varied (e.g. hydrophobic, hydrogen bonding, ionic) often leading to heterogeneous interfacial behavior. Heterogeneity can arise either from spatial variation of the surface/interface itself or from molecular configurations (i.e. conformation, orientation, aggregation state, etc.). By observing adsorption, diffusion, and desorption of individual fluorescent molecules, single-molecule tracking can characterize these types of heterogeneous interfacial behavior in ways that are inaccessible to traditional ensemble-averaged methods. Moreover, the fluorescence intensity or emission wavelength (in resonance energy transfer experiments) can be used to simultaneously track molecular configuration and directly relate this to the resulting interfacial mobility or affinity. In this feature article, we review recent advances involving the use of single-molecule tracking to characterize heterogeneous molecule-surface interactions including: multiple modes of diffusion and desorption associated with both internal and external molecular configuration, Arrhenius activated interfacial transport, spatially dependent interactions, and many more. PMID:22716995

Computational Study of Quasi-2D Liquid State in Free Standing Platinum, Silver, Gold, and Copper Monolayers.

PubMed

Yang, Li-Ming; Ganz, Ariel B; Dornfeld, Matthew; Ganz, Eric

2016-12-01

Recently, freestanding atomically thick Fe metal patches up to 10 atoms wide have been fabricated experimentally in tiny pores in graphene. This concept can be extended conceptually to extended freestanding monolayers. We have therefore performed ab initio molecular dynamics simulations to evaluate the early melting stages of platinum, silver, gold, and copper freestanding metal monolayers. Our calculations show that all four freestanding monolayers will form quasi-2D liquid layers with significant out-of-plane motion and diffusion in the plane. Remarkably, we observe a 4% reduction in the Pt most likely bond length as the system enters the liquid state at 2400 K (and a lower effective spring constant), compared to the system at 1200 and 1800 K. We attribute this to the reduced average number of bonds per atom in the Pt liquid state. We used the highly accurate and reliable Density Functional Theory (DFT-D) method that includes dispersion corrections. These liquid states are found at temperatures of 2400 K, 1050 K, 1600 K, and 1400 K for platinum, silver, gold, and copper respectively. The pair correlation function drops in the liquid state, while the bond orientation order parameter is reduced to a lesser degree. Movies of the simulations can be viewed online (see Supplementary Material).

Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [ Co ( terpy ) 2 ] 2 +

DOE PAGES

Biasin, Elisa; van Driel, Tim Brandt; Kjær, Kasper S.; ...

2016-06-30

Here, we study the structural dynamics of photoexcited [Co(terpy) 2] 2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of themore » high spin state is established on a single-picosecond time scale and that this state has a lifetime of ~7 ps.« less

Bifunctional catalytic electrode

NASA Technical Reports Server (NTRS)

Cisar, Alan (Inventor); Murphy, Oliver J. (Inventor); Clarke, Eric (Inventor)

2005-01-01

The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

Design studies of Laminar Flow Control (LFC) wing concepts using superplastics forming and diffusion bonding (SPF/DB)

NASA Technical Reports Server (NTRS)

Wilson, V. E.

1980-01-01

Alternate concepts and design approaches were developed for suction panels and techniques were defined for integrating these panel designs into a complete LFC 200R wing. The design concepts and approaches were analyzed to assure that they would meet the strength, stability, and internal volume requirements. Cost and weight comparisions of the concepts were also made. Problems of integrating the concepts into a complete aircraft system were addressed. Methods for making splices both chordwise and spanwise, fuel light joints, and internal duct installations were developed. Manufacturing problems such as slot aligment, tapered slot spacing, production methods, and repair techniques were addressed. An assessment of the program was used to developed recommendations for additional research in the development of SPF/DB for LFC structure.

Describing Temperature-Dependent Self-Diffusion Coefficients and Fluidity of 1- and 3-Alcohols with the Compensated Arrhenius Formalism.

PubMed

Fleshman, Allison M; Forsythe, Grant E; Petrowsky, Matt; Frech, Roger

2016-09-22

The location of the hydroxyl group in monohydroxy alcohols greatly affects the temperature dependence of the liquid structure due to hydrogen bonding. Temperature-dependent self-diffusion coefficients, fluidity (the inverse of viscosity), dielectric constant, and density have been measured for several 1-alcohols and 3-alcohols with varying alkyl chain lengths. The data are modeled using the compensated Arrhenius formalism (CAF). The CAF follows a modified transition state theory using an Arrhenius-like expression to describe the transport property, which consists of a Boltzmann factor containing an energy of activation, Ea, and an exponential prefactor containing the temperature-dependent solution dielectric constant, εs(T). Both 1- and 3-alcohols show the Ea of diffusion coefficients (approximately 43 kJ mol(-1)) is higher than the Ea of fluidity (approximately 35 kJ mol(-1)). The temperature dependence of the exponential prefactor in these associated liquids is explained using the dielectric constant and the Kirkwood-Frölich correlation factor, gk. It is argued that the dielectric constant must be used to account for the additional temperature dependence due to variations in the liquid structure (e.g., hydrogen bonding) for the CAF to accurately model the transport property.

Diffusion and Binding of Laponite Clay Nanoparticles into Collagen Fibers for the Formation of Leather Matrix.

PubMed

Shi, Jiabo; Wang, Chunhua; Ngai, To; Lin, Wei

2018-06-13

Understanding accessibility and interactions of clay nanoparticles with collagen fibers is an important fundamental issue for the conversion of collagen to leather matrix. In this study, we have investigated the diffusion and binding of Laponite into the collagen fiber network. Our results indicate that the diffusion behaviors of Laponite into the collagen exhibit the Langmuir adsorption, verifying its affinity for collagen. The introduction of Laponite leads to a shift in the isoelectric point of collagen from ∼6.8 to ∼4.5, indicating the ionic bonding between the positively charged amino groups of the collagen and negatively charged Laponite under the tanning conditions. Fluorescence microscopy, atomic force microscopy, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and wide-angle X-ray diffraction analyses reveal that Laponite nanoparticles can penetrate into collagen microstructure and evenly distributed onto collagen fibrils, not altering native D-periodic banding patterns of collagen fibrils. Attenuated total reflectance-Fourier transform infrared and Raman spectroscopy detections further demonstrate the presence of noncovalent interactions, namely, ionic and hydrogen bonding, between Laponite and collagen. These findings provide a theoretical basis for the use of Laponite as an emerging tanning agent in leather manufacture.

Molecular and ionic diffusion in aqueous - deep eutectic solvent mixtures: probing inter-molecular interactions using PFG NMR.

PubMed

D'Agostino, Carmine; Gladden, Lynn F; Mantle, Mick D; Abbott, Andrew P; Ahmed, Essa I; Al-Murshedi, Azhar Y M; Harris, Robert C

2015-06-21

Pulsed field gradient (PFG) NMR has been used to probe self-diffusion of molecular and ionic species in aqueous mixtures of choline chloride (ChCl) based deep eutectic solvents (DESs), in order to elucidate the effect of water on motion and inter-molecular interactions between the different species in the mixtures, namely the Ch(+) cation and hydrogen bond donor (HBD). The results reveal an interesting and complex behaviour of such mixtures at a molecular level. In general, it is observed that the hydroxyl protons ((1)H) of Ch(+) and the hydrogen bond donor have diffusion coefficients significantly different from those measured for their parent molecules when water is added. This indicates a clear and significant change in inter-molecular interactions. In aqueous Ethaline, the hydroxyl species of Ch(+) and HBD show a stronger interaction with water as water is added to the system. In the case of Glyceline, water has little effect on both hydroxyl proton diffusion of Ch(+) and HBD. In Reline, it is likely that water allows the formation of small amounts of ammonium hydroxide. The most surprising observation is from the self-diffusion of water, which is considerably higher that expected from a homogeneous liquid. This leads to the conclusion that Reline and Glyceline form mixtures that are inhomogeneous at a microscopic level despite the hydrophilicity of the salt and HBD. This work shows that PFG NMR is a powerful tool to elucidate both molecular dynamics and inter-molecular interactions in complex liquid mixtures, such as the aqueous DES mixtures.

Impact of physicochemical properties of porous silica materials conjugated with dexamethasone via pH-responsive hydrazone bond on drug loading and release behavior

NASA Astrophysics Data System (ADS)

Numpilai, Thanapha; Witoon, Thongthai; Chareonpanich, Metta; Limtrakul, Jumras

2017-02-01

The conjugation of dexamethasone (DEX) onto modified-porous silica materials via a pH-responsive hydrazone bond has been reported to be highly efficient method to specifically deliver the DEX to diseased sites. However, the influence of physicochemical properties of porous silica materials has not yet been fully understood. In this paper, the impact of pore sizes, particle sizes and silanol contents on surface functionalization, drug loading and release behavior of porous silica materials conjugated with dexamethasone via pH-responsive hydrazone bond was investigated. The grafting density was found to relate to the number of silanol groups on the surface of porous silica materials. The particle size and macropores of the porous silica materials played an vital role on the drug loading and release behavior. Although the porous silica materials with larger particle sizes possessed a lower grafting density, a larger amount of drug loading could be achieved. Moreover, the porous silica materials with larger particle sizes showed a slower release rate of DEX due to a longer distance for cleaved DEX diffusion out of pores. DEX release rate exhibited pH-dependent, sustained release. At pH 4.5, the amount of DEX release within 10 days could be controlled in the range of 12.74-36.41%, depending on the host material. Meanwhile, less than 1.5% of DEX was released from each of type of the porous silica materials at pH 7.4. The results of silica dissolution suggested that the degradation of silica matrix did not significantly affect the release rate of DEX. In addition, the kinetic modeling studies revealed that the DEX releases followed Korsmeyer-Peppas model with a release exponent (n) ranged from 0.3 to 0.47, indicating a diffusion-controlled release mechanism.

Lubricating Properties of Some Bonded Fluoride and Oxide Coatings for Temperature to 1500 F

NASA Technical Reports Server (NTRS)

Sliney, Harold E.

1960-01-01

The lubricating properties of some experimental ceramic coatings, diffusion-bonded fluoride coatings, and ceramic-bonded fluoride coatings were determined. The experiments were conducted in an air atmosphere at a sliding velocity of 430 feet per minute and at temperatures from 75 to 1500 F. Several ceramic coatings provided substantial reductions in friction coefficient and rider wear (compared with the unlubricated metals). For example, a cobaltous oxide (CoO) base coating gave friction coefficients of 0.24 to 0.36 within the temperature range of 75 to 1400 F; serious galling and welding of the metal surfaces were prevented. The friction coefficients were higher than the arbitrary maximum (0.2) usually considered for effective boundary lubrication. However, when a moderately high friction coefficient can be tolerated, this type of coating may be a useful antiwear composition. Diffusion-bonded calcium fluoride (CaF2) on Haynes Stellite 21 and on Inconel X gave friction coefficients of 0.1 to 0.2 at 1500 F. Endurance life was dependent on the thermal history of the coating; life improved with increased exposure time at elevated temperatures prior to running. Promising results were obtained with ceramic-bonded CaF2 on Inconel X. Effective lubrication and good adherence were obtained with a 3 to 1 ratio of CaF2 to ceramic. A very thin sintered and burnished film of CaF2 applied to the surface of this coating further improved lubrication, particularly above 1350 F. The friction coefficient was 0.2 at 500 F and decreased with increasing temperature to 0.06-at 1500 F. It was 0.25 at 75 F and 0.22 at 250 F.

Metallization for Yb14MnSb11-Based Thermoelectric Materials

NASA Technical Reports Server (NTRS)

Firdosy, Samad; Li, Billy Chun-Yip; Ravi, Vilupanur; Sakamoto, Jeffrey; Caillat, Thierry; Ewell, Richard C.; Brandon, Erik J.

2011-01-01

Thermoelectric materials provide a means for converting heat into electrical power using a fully solid-state device. Power-generating devices (which include individual couples as well as multicouple modules) require the use of ntype and p-type thermoelectric materials, typically comprising highly doped narrow band-gap semiconductors which are connected to a heat collector and electrodes. To achieve greater device efficiency and greater specific power will require using new thermoelectric materials, in more complex combinations. One such material is the p-type compound semiconductor Yb14MnSb11 (YMS), which has been demonstrated to have one of the highest ZT values at 1,000 C, the desired operational temperature of many space-based radioisotope thermoelectric generators (RTGs). Despite the favorable attributes of the bulk YMS material, it must ultimately be incorporated into a power-generating device using a suitable joining technology. Typically, processes such as diffusion bonding and/or brazing are used to join thermoelectric materials to the heat collector and electrodes, with the goal of providing a stable, ohmic contact with high thermal conductivity at the required operating temperature. Since YMS is an inorganic compound featuring chemical bonds with a mixture of covalent and ionic character, simple metallurgical diffusion bonding is difficult to implement. Furthermore, the Sb within YMS readily reacts with most metals to form antimonide compounds with a wide range of stoichiometries. Although choosing metals that react to form high-melting-point antimonides could be employed to form a stable reaction bond, it is difficult to limit the reactivity of Sb in YMS such that the electrode is not completely consumed at an operating temperature of 1,000 C. Previous attempts to form suitable metallization layers resulted in poor bonding, complete consumption of the metallization layer or fracture within the YMS thermoelement (or leg).

Modeling material interfaces with hybrid adhesion method

DOE PAGES

Brown, Nicholas Taylor; Qu, Jianmin; Martinez, Enrique

2017-01-27

A molecular dynamics simulation approach is presented to approximate layered material structures using discrete interatomic potentials through classical mechanics and the underlying principles of quantum mechanics. This method isolates the energetic contributions of the system into two pure material layers and an interfacial region used to simulate the adhesive properties of the diffused interface. The strength relationship of the adhesion contribution is calculated through small-scale separation calculations and applied to the molecular surfaces through an inter-layer bond criterion. By segregating the contributions into three regions and accounting for the interfacial excess energies through the adhesive surface bonds, it is possiblemore » to model each material with an independent potential while maintaining an acceptable level of accuracy in the calculation of mechanical properties. This method is intended for the atomistic study of the delamination mechanics, typically observed in thin-film applications. Therefore, the work presented in this paper focuses on mechanical tensile behaviors, with observations in the elastic modulus and the delamination failure mode. To introduce the hybrid adhesion method, we apply the approach to an ideal bulk copper sample, where an interface is created by disassociating the force potential in the middle of the structure. Various mechanical behaviors are compared to a standard EAM control model to demonstrate the adequacy of this approach in a simple setting. In addition, we demonstrate the robustness of this approach by applying it on (1) a Cu-Cu 2O interface with interactions between two atom types, and (2) an Al-Cu interface with two dissimilar FCC lattices. These additional examples are verified against EAM and COMB control models to demonstrate the accurate simulation of failure through delamination, and the formation and propagation of dislocations under loads. Finally, the results conclude that by modeling the energy contributions of an interface using hybrid adhesion bonds, we can provide an accurate approximation method for studies of large-scale mechanical properties, as well as the representation of various delamination phenomena at the atomic scale.« less

Insight into the molecular mechanism of water evaporation via the finite temperature string method.

PubMed

Musolino, Nicholas; Trout, Bernhardt L

2013-04-07

The process of water's evaporation at its liquid/air interface has proven challenging to study experimentally and, because it constitutes a rare event on molecular time scales, presents a challenge for computer simulations as well. In this work, we simulated water's evaporation using the classical extended simple point charge model water model, and identified a minimum free energy path for this process in terms of 10 descriptive order parameters. The measured free energy change was 7.4 kcal/mol at 298 K, in reasonable agreement with the experimental value of 6.3 kcal/mol, and the mean first-passage time was 1375 ns for a single molecule, corresponding to an evaporation coefficient of 0.25. In the observed minimum free energy process, the water molecule diffuses to the surface, and tends to rotate so that its dipole and one O-H bond are oriented outward as it crosses the Gibbs dividing surface. As the water molecule moves further outward through the interfacial region, its local density is higher than the time-averaged density, indicating a local solvation shell that protrudes from the interface. The water molecule loses donor and acceptor hydrogen bonds, and then, with its dipole nearly normal to the interface, stops donating its remaining hydrogen bond. At that point, when the final, accepted hydrogen bond is broken, the water molecule is free. We also analyzed which order parameters are most important in the process and in reactive trajectories, and found that the relative orientation of water molecules near the evaporating molecule, and the number of accepted hydrogen bonds, were important variables in reactive trajectories and in kinetic descriptions of the process.

High-temperature dynamic behavior in bulk liquid water: A molecular dynamics simulation study using the OPC and TIP4P-Ew potentials

NASA Astrophysics Data System (ADS)

Gabrieli, Andrea; Sant, Marco; Izadi, Saeed; Shabane, Parviz Seifpanahi; Onufriev, Alexey V.; Suffritti, Giuseppe B.

2018-02-01

Classical molecular dynamics simulations were performed to study the high-temperature (above 300 K) dynamic behavior of bulk water, specifically the behavior of the diffusion coefficient, hydrogen bond, and nearest-neighbor lifetimes. Two water potentials were compared: the recently proposed "globally optimal" point charge (OPC) model and the well-known TIP4P-Ew model. By considering the Arrhenius plots of the computed inverse diffusion coefficient and rotational relaxation constants, a crossover from Vogel-Fulcher-Tammann behavior to a linear trend with increasing temperature was detected at T* ≈ 309 and T* ≈ 285 K for the OPC and TIP4P-Ew models, respectively. Experimentally, the crossover point was previously observed at T* ± 315-5 K. We also verified that for the coefficient of thermal expansion α P ( T, P), the isobaric α P ( T) curves cross at about the same T* as in the experiment. The lifetimes of water hydrogen bonds and of the nearest neighbors were evaluated and were found to cross near T*, where the lifetimes are about 1 ps. For T < T*, hydrogen bonds persist longer than nearest neighbors, suggesting that the hydrogen bonding network dominates the water structure at T < T*, whereas for T > T*, water behaves more like a simple liquid. The fact that T* falls within the biologically relevant temperature range is a strong motivation for further analysis of the phenomenon and its possible consequences for biomolecular systems.

Mechanisms for Flow-Enhanced Cell Adhesion

PubMed Central

Zhu, Cheng; Yago, Tadayuki; Lou, Jizhong; Zarnitsyna, Veronika I.; McEver, Rodger P.

2009-01-01

Cell adhesion is mediated by specific receptor—ligand bonds. In several biological systems, increasing flow has been observed to enhance cell adhesion despite the increasing dislodging fluid shear forces. Flow-enhanced cell adhesion includes several aspects: flow augments the initial tethering of flowing cells to a stationary surface, slows the velocity and increases the regularity of rolling cells, and increases the number of rollingly adherent cells. Mechanisms for this intriguing phenomenon may include transport-dependent acceleration of bond formation and force-dependent deceleration of bond dissociation. The former includes three distinct transport modes: sliding of cell bottom on the surface, Brownian motion of the cell, and rotational diffusion of the interacting molecules. The latter involves a recently demonstrated counterintuitive behavior called catch bonds where force prolongs rather than shortens the lifetimes of receptor—ligand bonds. In this article, we summarize our recently published data that used dimensional analysis and mutational analysis to elucidate the above mechanisms for flow-enhanced leukocyte adhesion mediated by L-selectinligand interactions. PMID:18299992

Microstructure and hydrogen bonding in water-acetonitrile mixtures.

PubMed

Mountain, Raymond D

2010-12-16

The connection of hydrogen bonding between water and acetonitrile in determining the microheterogeneity of the liquid mixture is examined using NPT molecular dynamics simulations. Mixtures for six, rigid, three-site models for acetonitrile and one water model (SPC/E) were simulated to determine the amount of water-acetonitrile hydrogen bonding. Only one of the six acetonitrile models (TraPPE-UA) was able to reproduce both the liquid density and the experimental estimates of hydrogen bonding derived from Raman scattering of the CN stretch band or from NMR quadrupole relaxation measurements. A simple modification of the acetonitrile model parameters for the models that provided poor estimates produced hydrogen-bonding results consistent with experiments for two of the models. Of these, only one of the modified models also accurately determined the density of the mixtures. The self-diffusion coefficient of liquid acetonitrile provided a final winnowing of the modified model and the successful, unmodified model. The unmodified model is provisionally recommended for simulations of water-acetonitrile mixtures.

The hydroxyl species and acid sites on diatomite surface: a combined IR and Raman study

NASA Astrophysics Data System (ADS)

Yuan, P.; Wu, D. Q.; He, H. P.; Lin, Z. Y.

2004-04-01

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), Raman spectroscopy of adsorbed pyridine molecules (Py-Raman) and in situ Py-IR have been used to investigate the hydroxyl species and acid sites on diatomite surfaces. The Lewis (L) and Brønsted (B) acid sites, and various hydroxyl species, including isolated hydroxyl groups, H-bonded hydroxyl groups and physically adsorbed water, are identified. The L acid sites in diatomite samples are resulted from the clay impurities, and the B acid sites are resulted from some moderate strength H-bonded hydroxyl groups. At room temperature, both of the isolated and H-bonded silanols associate with the physically adsorbed water by hydrogen bond. After calcination treatment, physically adsorbed water will be desorbed from the silanols, and the silanols will condense with the increase of temperature. Generally, the H-bonded silanols condense more easily than the isolated ones. The properties of surface hydroxyl species of diatomaceous silica are more similar to precipitated silica rather than fumed silica.

Enhanced bonding property of cold-sprayed Zn-Al coating on interstitial-free steel substrate with a nanostructured surface layer

NASA Astrophysics Data System (ADS)

Liang, Y. L.; Wang, Z. B.; Zhang, J.; Zhang, J. B.; Lu, K.

2016-11-01

By means of surface mechanical attrition treatment (SMAT), a gradient nanostructured surface layer was fabricated on a hot-rolled interstitial-free steel plate. A Zn-Al coating was subsequently deposited on the SMAT sample by using cold spray process. The bonding property of the coating on the SMAT substrate was compared with that on the coarse-grained (CG) sample. Stud-pull tests showed that the bonding strength in the as-sprayed SMAT sample is ∼30% higher than that in the as-sprayed CG sample. No further improvement in bonding strength was achieved in the coated SMAT sample after annealing at 400 °C, mostly due to the formation of cracks and intermetallic compounds at the coating/substrate interface in an earlier stage (<30 min) and in a final stage (>90 min), respectively. The enhanced bonding property of the Zn-Al coating on the SMAT sample might be related with the promoted atomic diffusion and hardness in the nanostructured surface layer.

Thermodynamic properties and diffusion of water + methane binary mixtures

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

Shvab, I.; Sadus, Richard J., E-mail: rsadus@swin.edu.au

2014-03-14

Thermodynamic and diffusion properties of water + methane mixtures in a single liquid phase are studied using NVT molecular dynamics. An extensive comparison is reported for the thermal pressure coefficient, compressibilities, expansion coefficients, heat capacities, Joule-Thomson coefficient, zero frequency speed of sound, and diffusion coefficient at methane concentrations up to 15% in the temperature range of 298–650 K. The simulations reveal a complex concentration dependence of the thermodynamic properties of water + methane mixtures. The compressibilities, heat capacities, and diffusion coefficients decrease with increasing methane concentration, whereas values of the thermal expansion coefficients and speed of sound increase. Increasing methanemore » concentration considerably retards the self-diffusion of both water and methane in the mixture. These effects are caused by changes in hydrogen bond network, solvation shell structure, and dynamics of water molecules induced by the solvation of methane at constant volume conditions.« less

Anomalous cation diffusion in salt-doped confined bilayer ice.

PubMed

Qiu, Hu; Xue, Minmin; Shen, Chun; Guo, Wanlin

2018-05-17

The diffusive dynamics of aqueous electrolyte solutions in nanoconfined spaces has attracted considerable attention due to their potential applications in desalination, biosensors and supercapacitors. Here we show by molecular dynamics simulations that lithium and sodium ions diffuse at a rate at least an order of magnitude higher than that of water molecules when the ions are trapped in an ice bilayer confined between two parallel plates. This novel picture is in sharp contrast to the prevailing view that the diffusion rate of ions is comparable to or even lower than that of water in both bulk and confined solutions. The predicted high ion mobility stems from frequent lateral hopping of ions along the coordination sites inside the hydrogen-bonding network connecting the two water layers of the ice bilayer. This anomalous diffusion should provide new insights into the physics of confined aqueous electrolytes.

Adsorption of oxygen on low-index surfaces of the TiAl{sub 3} alloy

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

Latyshev, A. M.; Bakulin, A. V.; Kulkova, S. E., E-mail: kulkova@ms.tsc.ru

Method of the projector augmented waves in the plane-wave basis within the generalized-gradient approximation for the exchange-correlation functional has been used to study oxygen adsorption on (001), (100), and (110) low-index surfaces of the TiAl{sub 3} alloy. It has been established that the sites that are most energetically preferred for the adsorption of oxygen are hollow (H) positions on the (001) surface and bridge (B) positions on the (110) and (100) surfaces. Structural and electronic factors that define their energy preference have been discussed. Changes in the atomic and electronic structure of subsurface layers that occur as the oxygen concentrationmore » increases to three monolayers have been analyzed. It has been shown that the formation of chemical bonds of oxygen with both components of the alloy leads to the appearance of states that are split-off from the bottoms of their valence bands, which is accompanied by the formation of a forbidden gap at the Fermi level and by a weakening of the Ti–Al metallic bonds in the alloy. On the Al-terminated (001) and (110) surfaces, the oxidation of aluminum dominates over that of titanium. On the whole, the binding energy of oxygen on the low-index surfaces with a mixed termination is higher than that at the aluminum-terminated surface. The calculation of the diffusion of oxygen in the TiAl{sub 3} alloy has shown that the lowest barriers correspond to the diffusion between tetrahedral positions in the (001) plane; the diffusion of oxygen in the [001] direction occurs through octahedral and tetrahedral positions. An increase in the concentration of aluminum in the alloy favors a reduction in the height of the energy barriers as compared to the corresponding barriers in the γ-TiAl alloy.« less

Molecular Dynamics Study of the Solution Structure, Clustering, and Diffusion of Four Aqueous Alkanolamines.

PubMed

Melnikov, Sergey M; Stein, Matthias

2018-03-15

CO 2 sequestration from anthropogenic resources is a challenge to the design of environmental processes at a large scale. Reversible chemical absorption by amine-based solvents is one of the most efficient methods of CO 2 removal. Molecular simulation techniques are very useful tools to investigate CO 2 binding by aqueous alkanolamine molecules for further technological application. In the present work, we have performed detailed atomistic molecular dynamics simulations of aqueous solutions of three prototype amines: monoethanolamine (MEA) as a standard, 3-aminopropanol (MPA), 2-methylaminoethanol (MMEA), and 4-diethylamino-2-butanol (DEAB) as potential novel CO 2 absorptive solvents. Solvent densities, radial distribution functions, cluster size distributions, hydrogen-bonding statistics, and diffusion coefficients for a full range of mixture compositions have been obtained. The solvent densities and diffusion coefficients from simulations are in good agreement with those in the experiment. In aqueous solution, MEA, MPA, and MMEA molecules prefer to be fully solvated by water molecules, whereas DEAB molecules tend to self-aggregate. In a range from 30/70-50/50 (w/w) alkanolamine/water mixtures, they form a bicontinuous phase (both alkanolamine and water are organized in two mutually percolating clusters). Among the studied aqueous alkanolamine solutions, the diffusion coefficients decrease in the following order MEA > MPA = MMEA > DEAB. With an increase of water content, the diffusion coefficients increase for all studied alkanolamines. The presented results are a first step for process-scale simulation and provide important qualitative and quantitative information for the design and engineering of efficient new CO 2 removal processes.

Acetone-Assisted Oxygen Vacancy Diffusion on TiO2(110)

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

Xia, Yaobiao; Zhang, Bo; Ye, Jingyun

2012-10-18

We have studied the dynamic relationship between acetone and bridge-bonded oxygen (Ob) vacancy (VO) defect sites on the TiO2(110)-1 × 1 surface using scanning tunneling microscopy (STM) and density function theory (DFT) calculations. We report an adsorbate-assisted VO diffusion mechanism. The STM images taken at 300 K show that acetone preferably adsorbs on the VO site and is mobile. The sequential isothermal STM images directly show that the mobile acetone effectively migrates the position of VO by a combination of two acetone diffusion channels: one is the diffusion along the Ob row and moving as an alkyl group, which healsmore » the initial VO; another is the diffusion from the Ob row to the fivecoordinated Ti4+ row and then moving along the Ti4+ row as an acetone, which leaves a VO behind. The calculated acetone diffusion barriers for the two channels are comparable and agree with experimental results.« less

Vacuum ultraviolet photolysis of hydrogenated amorphous carbons. III. Diffusion of photo-produced H2 as a function of temperature

NASA Astrophysics Data System (ADS)

Martín-Doménech, R.; Dartois, E.; Muñoz Caro, G. M.

2016-06-01

Context. Hydrogenated amorphous carbon (a-C:H) has been proposed as one of the carbonaceous solids detected in the interstellar medium. Energetic processing of the a-C:H particles leads to the dissociation of the C-H bonds and the formation of hydrogen molecules and small hydrocarbons. Photo-produced H2 molecules in the bulk of the dust particles can diffuse out to the gas phase and contribute to the total H2 abundance. Aims: We have simulated this process in the laboratory with plasma-produced a-C:H and a-C:D analogs under astrophysically relevant conditions to investigate the dependence of the diffusion as a function of temperature. Methods: Experimental simulations were performed in a high-vacuum chamber, with complementary experiments carried out in an ultra-high-vacuum chamber. Plasma-produced a-C:H and a-C:D analogs were UV-irradiated using a microwave-discharged hydrogen flow lamp. Molecules diffusing to the gas-phase were detected by a quadrupole mass spectrometer, providing a measurement of the outgoing H2 or D2 flux. By comparing the experimental measurements with the expected flux from a one-dimensional diffusion model, a diffusion coefficient D could be derived for experiments carried out at different temperatures. Results: Dependence on the diffusion coefficient D with the temperature followed an Arrhenius-type equation. The activation energy for the diffusion process was estimated (ED(H2) = 1660 ± 110 K, ED(D2) = 2090 ± 90 K), as well as the pre-exponential factor (D0(H2) = 0.0007 cm2 s-1, D0(D2) = 0.0045 cm2 s-1). Conclusions: The strong decrease of the diffusion coefficient at low dust particle temperatures exponentially increases the diffusion times in astrophysical environments. Therefore, transient dust heating by cosmic rays needs to be invoked for the release of the photo-produced H2 molecules in cold photon-dominated regions, where destruction of the aliphatic component in hydrogenated amorphous carbons most probably takes place.

Mo/Ti Diffusion Bonding for Making Thermoelectric Devices

NASA Technical Reports Server (NTRS)

Sakamoto, Jeffrey; Kisor, Adam; Caillat, Thierry; Lara, Liana; Ravi, Vilupanur; Firdosy, Samad; Fleuiral, Jean-Pierre

2007-01-01

An all-solid-state diffusion bonding process that exploits the eutectoid reaction between molybdenum and titanium has been developed for use in fabricating thermoelectric devices based on skutterudite compounds. In essence, the process is one of heating a flat piece of pure titanium in contact with a flat piece of pure molybdenum to a temperature of about 700 C while pushing the pieces together with a slight pressure [a few psi (of the order of 10 kPa)]. The process exploits the energy of mixing of these two metals to form a strong bond between them. These two metals were selected partly because the bonds formed between them are free of brittle intermetallic phases and are mechanically and chemically stable at high temperatures. The process is a solution of the problem of bonding hot-side metallic interconnections (denoted hot shoes in thermoelectric jargon) to titanium-terminated skutterudite n and p legs during the course of fabrication of a unicouple, which is the basic unit cell of a thermoelectric device (see figure). The hot-side operating temperature required for a skutterudite thermoelectric device is 700 C. This temperature precludes the use of brazing to attach the hot shoe; because brazing compounds melt at lower temperatures, the hot shoe would become detached during operation. Moreover, the decomposition temperature of one of the skutterudite compounds is 762 C; this places an upper limit on the temperature used in bonding the hot shoe. Molybdenum was selected as the interconnection metal because the eutectoid reaction between it and the titanium at the ends of the p and n legs has characteristics that are well suited for this application. In addition to being suitable for use in the present bonding process, molybdenum has high electrical and thermal conductivity and excellent thermal stability - characteristics that are desired for hot shoes of thermoelectric devices. The process takes advantage of the chemical potential energy of mixing between molybdenum and titanium. These metals have a strong affinity for each other. They are almost completely soluble in each other and remain in the solid state at temperatures above the eutectoid temperature of 695 C. As a result, bonds formed by interdiffusion of molybdenum and titanium are mechanically stable at and well above the original bonding temperature of about 700 C. Inasmuch as the bonds are made at approximately the operating temperature, thermomechanical stresses associated with differences in thermal expansion are minimized.

Application of vacuum stability test to determine thermal decomposition kinetics of nitramines bonded by polyurethane matrix

NASA Astrophysics Data System (ADS)

Elbeih, Ahmed; Abd-Elghany, Mohamed; Elshenawy, Tamer

2017-03-01

Vacuum stability test (VST) is mainly used to study compatibility and stability of energetic materials. In this work, VST has been investigated to study thermal decomposition kinetics of four cyclic nitramines, 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-HNIW, CL-20), bonded by polyurethane matrix based on hydroxyl terminated polybutadiene (HTPB). Model fitting and model free (isoconversional) methods have been applied to determine the decomposition kinetics from VST results. For comparison, the decomposition kinetics were determined isothermally by ignition delay technique and non-isothermally by Advanced Kinetics and Technology Solution (AKTS) software. The activation energies for thermolysis obtained by isoconversional method based on VST technique of RDX/HTPB, HMX/HTPB, BCHMX/HTPB and CL20/HTPB were 157.1, 203.1, 190.0 and 176.8 kJ mol-1 respectively. Model fitting method proved that the mechanism of thermal decomposition of BCHMX/HTPB is controlled by the nucleation model while all the other studied PBXs are controlled by the diffusion models. A linear relationship between the ignition temperatures and the activation energies was observed. BCHMX/HTPB is interesting new PBX in the research stage.

Theoretical study of the BeLi, BeNa, MgLi, MgNa, and AlBe molecules and their negative ions

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry

1992-01-01

The alkaline earth-alkali diatomics are found to have weak bonds, because the diffuse alkali valence s orbitals cannot form a bond of sufficient strength to pay the promotion energy of the alkaline-earth atoms. This leads to van der Waals bonding in the neutrals as well as the negative ions. In fact, the negative ions have larger binding energies than the neutrals as a result of the much larger polarizability of the negative ion. The binding energy of AlBe is significantly larger than the Be-alkali molecules, due to a covalent contribution to the bonding. The binding energy in AlBe(-) is considerably larger than AlBe; the binding energy of the X 3Sigma(-) state of AlBe(-) is computed to be 1.36 eV, as compared with 0.57 eV for the X 2Pi state of AlBe.

The electronegativity equalization method fused with molecular mechanics: a fluctuating charge and flexible body potential function for [Emim][Gly] ionic liquids.

PubMed

Wu, Yang; Li, Yao; Hu, Na; Hong, Mei

2014-02-14

Recently, experimental and theoretical studies on amino acid ionic liquid (AAIL) systems have attracted much attention. A transferable intermolecular potential approach that includes fluctuating charges and a flexible body based on a combination of the electronegativity equalization method and molecular mechanics (EEM/MM), and its application to an AAIL system containing 1-ethyl-3-methylimidazolium ([Emim](+)) and glycine ([Gly](-)) are explored and tested in this study. A consistent integration of EEM with MM requires the input of the EEM charges of all atoms into the MM intermolecular electrostatic interaction term. Compared with ionic liquid (IL) force fields, the EEM/MM model has an outstanding feature: the EEM/MM model not only presents the electrostatic interaction of atoms and their changes in response to different ambient environments but also introduces "the H-bond interaction region" in which a new parameter kHB(RHB) is used to describe the electrostatic interaction of hydrogen atoms in [Emim](+) and oxygen atoms in [Gly](-), which can form hydrogen bonds. The EEM/MM model gives quite accurate predictions for gas-phase state properties of [Emim](+), [Gly](-), and ion pairs, such as optimized geometries, dipole moments, vibrational frequencies, and cluster interaction energies. Due to its explicit description of charges and hydrogen bonds, the EEM/MM model also performs well for the liquid-phase properties of [Emim][Gly] under ambient conditions. The calculated properties, such as density, heat of vaporization, the self-diffusion coefficient, and ionic conductivity, are fairly consistent with available experimental results.

Microstructure and Properties of 5083 Al/1060 Al/AZ31 Composite Plate Fabricated by Explosive Welding

NASA Astrophysics Data System (ADS)

Yang, Suyuan; Bao, Jiawei

2018-03-01

A 5083 Al/1060 Al/AZ31 composite plate was fabricated by explosive welding. The microstructure and properties of the composite plate were investigated after explosive welding. The results showed that all bonding interfaces were wavy interfaces. With an increasing distance from the detonation point, the wavelength and the amplitude also increased. The EDS results indicated that a 5-μm diffusion layer was observed at the 1060 Al/AZ31 layer, including the Mg2Al3 phase. Adiabatic shear bands and twin structures were observed in AZ31. The shear bond strength of the 5083 Al/1060 Al interface was 60 MPa, and the shear bond strength of the 1060 Al/AZ31 interface was 84 MPa.

Experimental and theoretical evaluation on the microenvironmental effect of dimethyl sulfoxide on adrenaline in acid aqueous solution

NASA Astrophysics Data System (ADS)

Yu, Zhang-Yu; Liu, Tao; Guo, Dao-Jun; Liu, Yong-Jun; Liu, Cheng-Bu

2010-12-01

The microenvironmental effect of dimethyl sulfoxide (DMSO) on adrenaline was studied by several approaches including the cyclic voltammetry (CV) of adrenaline at a platinum electrode in acid aqueous solution, the chemical shift of 1H nuclear magnetic resonance ( 1H NMR) of adrenaline, and the change of diffusion coefficient of adrenaline. The experimental results demonstrated that DMSO has significant microenvironmental effect on adrenaline, which was confirmed by the density functional theory (DFT) study on the hydrogen bond (H-bond) complexes of adrenaline with water and DMSO.

Screening possible solid electrolytes by calculating the conduction pathways using Bond Valence method

NASA Astrophysics Data System (ADS)

Gao, Jian; Chu, Geng; He, Meng; Zhang, Shu; Xiao, RuiJuan; Li, Hong; Chen, LiQuan

2014-08-01

Inorganic solid electrolytes have distinguished advantages in terms of safety and stability, and are promising to substitute for conventional organic liquid electrolytes. However, low ionic conductivity of typical candidates is the key problem. As connective diffusion path is the prerequisite for high performance, we screen for possible solid electrolytes from the 2004 International Centre for Diffraction Data (ICDD) database by calculating conduction pathways using Bond Valence (BV) method. There are 109846 inorganic crystals in the 2004 ICDD database, and 5295 of them contain lithium. Except for those with toxic, radioactive, rare, or variable valence elements, 1380 materials are candidates for solid electrolytes. The rationality of the BV method is approved by comparing the existing solid electrolytes' conduction pathways we had calculated with those from experiments or first principle calculations. The implication for doping and substitution, two important ways to improve the conductivity, is also discussed. Among them Li2CO3 is selected for a detailed comparison, and the pathway is reproduced well with that based on the density functional studies. To reveal the correlation between connectivity of pathways and conductivity, α/ γ-LiAlO2 and Li2CO3 are investigated by the impedance spectrum as an example, and many experimental and theoretical studies are in process to indicate the relationship between property and structure. The BV method can calculate one material within a few minutes, providing an efficient way to lock onto targets from abundant data, and to investigate the structure-property relationship systematically.

Dispersion Relations for Proton Relaxation in Solid Dielectrics

NASA Astrophysics Data System (ADS)

Kalytka, V. A.; Korovkin, M. V.

2017-04-01

Frequency-temperature spectra of the complex permittivity are studied for proton semiconductors and dielectrics using the methods of a quasi-classical kinetic theory of dielectric relaxation (the Boltzmann kinetic theory) in the linear approximation with respect to the polarizing field in the radio frequency range at temperatures T = 50-450 K. The effect of the quantum transitions of protons on the Debye dispersion relations is taken into account for crystals with hydrogen bonds (HBC) at low temperatures (50-100 K). The diffusion coefficients and the mobilities under electrical transfer of protons in the HBCs are constructed at high temperatures (100-350 K) in a non-linear approximation with respect to the polarizing field.

Method of transferring strained semiconductor structure

DOEpatents

Nastasi, Michael A [Santa Fe, NM; Shao, Lin [College Station, TX

2009-12-29

The transfer of strained semiconductor layers from one substrate to another substrate involves depositing a multilayer structure on a substrate having surface contaminants. An interface that includes the contaminants is formed in between the deposited layer and the substrate. Hydrogen atoms are introduced into the structure and allowed to diffuse to the interface. Afterward, the deposited multilayer structure is bonded to a second substrate and is separated away at the interface, which results in transferring a multilayer structure from one substrate to the other substrate. The multilayer structure includes at least one strained semiconductor layer and at least one strain-induced seed layer. The strain-induced seed layer can be optionally etched away after the layer transfer.

Microscale Waste Heat Driven Cooling System

DTIC Science & Technology

2012-05-02

Concept Slow, expensive, one‐at‐a‐time process Nickel  Brazing  Lower Cost Method Can  braze  50 – 200 in single furnace run (vs 1 – 2 using Diffusion  Bonding...Potential Use of Continuous Belt‐Type Furnace Nickel  Brazing  Technical Issues  Micro channel size reduction and/or blockage Amount of Alloy...Pressure Tightness vs. Channel Blockage Alloy Application:  Spray, Plating, Foil Furnace  Temperature  and Heat/Cool Rates Sustainable Products for a

ms 2: A molecular simulation tool for thermodynamic properties, release 3.0

NASA Astrophysics Data System (ADS)

Rutkai, Gábor; Köster, Andreas; Guevara-Carrion, Gabriela; Janzen, Tatjana; Schappals, Michael; Glass, Colin W.; Bernreuther, Martin; Wafai, Amer; Stephan, Simon; Kohns, Maximilian; Reiser, Steffen; Deublein, Stephan; Horsch, Martin; Hasse, Hans; Vrabec, Jadran

2017-12-01

A new version release (3.0) of the molecular simulation tool ms 2 (Deublein et al., 2011; Glass et al. 2014) is presented. Version 3.0 of ms 2 features two additional ensembles, i.e. microcanonical (NVE) and isobaric-isoenthalpic (NpH), various Helmholtz energy derivatives in the NVE ensemble, thermodynamic integration as a method for calculating the chemical potential, the osmotic pressure for calculating the activity of solvents, the six Maxwell-Stefan diffusion coefficients of quaternary mixtures, statistics for sampling hydrogen bonds, smooth-particle mesh Ewald summation as well as the ability to carry out molecular dynamics runs for an arbitrary number of state points in a single program execution.

HIGH-ENERGY ELECTRON IRRADIATION OF INTERSTELLAR CARBONACEOUS DUST ANALOGS: COSMIC-RAY EFFECTS ON THE CARRIERS OF THE 3.4 μ m ABSORPTION BAND

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

Maté, Belén; Molpeceres, Germán; Jiménez-Redondo, Miguel

2016-11-01

The effects of cosmic rays on the carriers of the interstellar 3.4 μ m absorption band have been investigated in the laboratory. This band is attributed to stretching vibrations of CH{sub 3} and CH{sub 2} in carbonaceous dust. It is widely observed in the diffuse interstellar medium, but disappears in dense clouds. Destruction of CH{sub 3} and CH{sub 2} by cosmic rays could become relevant in dense clouds, shielded from the external ultraviolet field. For the simulations, samples of hydrogenated amorphous carbon (a-C:H) have been irradiated with 5 keV electrons. The decay of the band intensity versus electron fluence reflectsmore » a-C:H dehydrogenation, which is well described by a model assuming that H{sub 2} molecules, formed by the recombination of H atoms liberated through CH bond breaking, diffuse out of the sample. The CH bond destruction rates derived from the present experiments are in good accordance with those from previous ion irradiation experiments of HAC. The experimental simplicity of electron bombardment has allowed the use of higher-energy doses than in the ion experiments. The effects of cosmic rays on the aliphatic components of cosmic dust are found to be small. The estimated cosmic-ray destruction times for the 3.4 μ m band carriers lie in the 10{sup 8} yr range and cannot account for the disappearance of this band in dense clouds, which have characteristic lifetimes of 3 × 10{sup 7} yr. The results invite a more detailed investigation of the mechanisms of CH bond formation and breaking in the intermediate region between diffuse and dense clouds.« less

X-ray spectromicroscopic investigation of natural organochlorine distribution in weathering plant material

NASA Astrophysics Data System (ADS)

Leri, Alessandra C.; Marcus, Matthew A.; Myneni, Satish C. B.

2007-12-01

Natural organochlorine (Cl org) is ubiquitous in soil humus, but the distribution and cycling of different Cl species during the humification of plant material is poorly understood. Our X-ray spectromicroscopic studies indicate that the distributions of Cl org and inorganic Cl -(Cl inorg) in oak leaf material vary dramatically with decay stage, with the most striking changes occurring at the onset of weathering. In healthy or senescent leaves harvested from trees, Cl inorg occurs in sparsely distributed, highly localized "hotspots" associated with trichomes as well as in diffuse concentration throughout the leaf tissue. The Cl inorg associated with trichomes exists either in H-bonded form or in a solid salt matrix, while the Cl inorg in diffuse areas of lower Cl concentration appears exclusively in H-bonded form. Most solid phase Cl inorg leaches from the leaf tissue during early weathering stages, whereas the H-bonded Cl inorg appears to leach away slowly as degradation progresses, persisting through advanced weathering stages. In unweathered leaves, aromatic and aliphatic Cl org were found in rare but concentrated hotspots. In weathered leaves, by contrast, aromatic Cl org hotspots are prevalent, often coinciding with areas of elevated Fe or Mn concentration. Aromatic Cl org is highly soluble in leaves at early weathering stages and insoluble at more advanced stages. These results, combined with optical microscopy, suggest that fungi play a role in the production of aromatic Cl org in weathering leaf material. Aliphatic Cl org occurs in concentrated hotspots in weathered leaves as well as in diffuse areas of low Cl concentration. The distribution and speciation of Cl in weathering oak leaves depicted by this spectromicroscopic study provides new insight into the formation and cycling of Cl org during the decay of natural organic matter.

Derivative effect of laser cladding on interface stability of YSZ@Ni coating on GH4169 alloy: An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Zheng, Haizhong; Li, Bingtian; Tan, Yong; Li, Guifa; Shu, Xiaoyong; Peng, Ping

2018-01-01

Yttria-stabilized zirconia YSZ@Ni core-shell nanoparticles were used to prepare a thermal barrier coating (TBC) on a GH4169 alloy by laser cladding. Microstructural analysis showed that the TBC was composed of two parts: a ceramic and a bonding layer. In places where the ZrO2/Al2O3 eutectic structure was present in the ceramic layer, the Ni atoms diffused into the bonding layer, as confirmed by energy-dispersive X-ray spectroscopy (EDS). The derivative effect of laser cladding results in the original YSZ@Ni core-shell nanoparticles being translated into the Al2O3 crystal, activating the YSZ. The mechanism of ceramic/metal interface cohesion was studied in depth via first-principles and molecular dynamics simulation. The results show that the trend in the diffusion coefficients of Ni, Fe, Al, and Ti is DNi > DFe > DTi > DAl in the melting or solidification process of the material. The enthalpy of formation for Al2O3 is less than that of TiO2, resulting in a thermally grown oxide (TGO) Al2O3 phase transformation. With regard to the electronic structure, the trend in Mulliken population is QO-Ni > QZr-O > QO-Al. Although the bonding is slightly weakened between ZrO2/Al2O3 (QZr-O = 0.158 < QO-Ni = 0.220) compared to that in ZrO2/Ni, TGO Al2O3 can improve the oxidation resistance of the metal matrix. Thus, by comparing the connective and diffusive processes, our findings lay the groundwork for detailed and comprehensive studies of the laser cladding process for the production of composite materials.

Alumina-Forming MAX Phases in Turbine Material Systems

NASA Technical Reports Server (NTRS)

Smialek, James L.; Harder, Bryan J.; Garg, Arnita; Nesbitt, James A.

2015-01-01

Coatings for high temperature turbine components are based on low conductivity YSZ thermal barriers and protective NiAl, NiCoCrAlY bond coats. Good oxidation hot corrosion resistance, intermediate CTE, and strain tolerance of Ti2AlC and Cr2AlC MAX phases are thus of special interest. Their alumina scale growth follows a cubic law in accord with FeCrAlY alloys, with oxygen grain boundary diffusivity: Dgb 1.8 x 10-10 exp(-375 kJmole) m3s. Protective cubic kinetics are also found in high pressure burner rig (6 atm., 25 ms) and TGA tests of MAXthal 211Ti2AlC. The initial portion (0.1 hr) is dominated by fast TiO2 growth (with little evidence of scale volatility in high pressure water vapor, as found for SiO2 scales). Bulk Ti2AlC and Cr2AlC substrates show promise as potential bond coats for YSZ TBCs in 1000-1200 C furnace life (500 h) tests. Cr2AlC is proving to be very resistant to 700-900 C Na2SO4 hot corrosion and is of interest for disk alloys. Preliminary diffusion bonded Cr2AlC-superalloy hybrid couples have survived 1000 hr interrupted furnace tests at 800C with no indication of cracking or debonding. Diffusion zones of -NiAl+Cr7C3 were produced in these above 1000 C, but did not grow to any great extent after 1000 hr at 800 C. Processing as coatings presents challenges, however the basic properties of MAX phases provide novel opportunities for high temperature turbine components.

Iridium Interfacial Stack - IrIS

NASA Technical Reports Server (NTRS)

Spry, David

2012-01-01

Iridium Interfacial Stack (IrIS) is the sputter deposition of high-purity tantalum silicide (TaSi2-400 nm)/platinum (Pt-200 nm)/iridium (Ir-200 nm)/platinum (Pt-200 nm) in an ultra-high vacuum system followed by a 600 C anneal in nitrogen for 30 minutes. IrIS simultaneously acts as both a bond metal and a diffusion barrier. This bondable metallization that also acts as a diffusion barrier can prevent oxygen from air and gold from the wire-bond from infiltrating silicon carbide (SiC) monolithically integrated circuits (ICs) operating above 500 C in air for over 1,000 hours. This TaSi2/Pt/Ir/Pt metallization is easily bonded for electrical connection to off-chip circuitry and does not require extra anneals or masking steps. There are two ways that IrIS can be used in SiC ICs for applications above 500 C: it can be put directly on a SiC ohmic contact metal, such as Ti, or be used as a bond metal residing on top of an interconnect metal. For simplicity, only the use as a bond metal is discussed. The layer thickness ratio of TaSi2 to the first Pt layer deposited thereon should be 2:1. This will allow Si from the TaSi2 to react with the Pt to form Pt2Si during the 600 C anneal carried out after all layers have been deposited. The Ir layer does not readily form a silicide at 600 C, and thereby prevents the Si from migrating into the top-most Pt layer during future anneals and high-temperature IC operation. The second (i.e., top-most) deposited Pt layer needs to be about 200 nm to enable easy wire bonding. The thickness of 200 nm for Ir was chosen for initial experiments; further optimization of the Ir layer thickness may be possible via further experimentation. Ir itself is not easily wire-bonded because of its hardness and much higher melting point than Pt. Below the iridium layer, the TaSi2 and Pt react and form desired Pt2Si during the post-deposition anneal while above the iridium layer remains pure Pt as desired to facilitate easy and strong wire-bonding to the SiC chip circuitry.

Effect of V2O5 on SrO-ZnO-B2O3-SiO2 glass-ceramics for high temperature sealant application

NASA Astrophysics Data System (ADS)

Tiwari, Babita; Bhatacharya, S.; Dixit, A.; Gadkari, S. C.; Kothiyal, G. P.

2012-06-01

Glasses in the SrO-ZnO-B2O3-SiO2 (SZBS) system with and without V2O5 were prepared by melt-quench method and transformed into glass-ceramics by controlled crystallization. Investigated glasses and glass-ceramics have thermal expansion coefficients (TEC) in the range of 95-120 × 10-7/°C (30-600 °C), which match closely with TEC of other components of solid oxide fuel cell (SOFC). Study of thermo-physical properties of SZBS glasses revealed the network modifying effect of V2O5. Addition of V2O5 increases the TEC and decreases the viscosity of the glass which is beneficial for making seal with Crofer-22-APU. Microstructural investigations have shown good bonding of SZBS glasses with Crofer-22-APU. Elemental line scans indicate that inter-diffusion of Fe, Cr and Si across interface, which is thought to be responsible for good bonding with Crofer-22-APU.

The failure analysis and lifetime prediction for the solder joint of the magnetic head

NASA Astrophysics Data System (ADS)

Xiao, Xianghui; Peng, Minfang; Cardoso, Jaime S.; Tang, Rongjun; Zhou, YingLiang

2015-02-01

Micro-solder joint (MSJ) lifetime prediction methodology and failure analysis (FA) are to assess reliability by fatigue model with a series of theoretical calculations, numerical simulation and experimental method. Due to shortened time of solder joints on high-temperature, high-frequency sampling error that is not allowed in productions may exist in various models, including round-off error. Combining intermetallic compound (IMC) growth theory and the FA technology for the magnetic head in actual production, this thesis puts forward a new growth model to predict life expectancy for solder joint of the magnetic head. And the impact of IMC, generating from interface reaction between slider (magnetic head, usually be called slider) and bonding pad, on mechanical performance during aging process is analyzed in it. By further researching on FA of solder ball bonding, thesis chooses AuSn4 growth model that affects least to solder joint mechanical property to indicate that the IMC methodology is suitable to forecast the solder lifetime. And the diffusion constant under work condition 60 °C is 0.015354; the solder lifetime t is 14.46 years.

International space research perspectives of commercialization for German industry

NASA Technical Reports Server (NTRS)

Jordan, H. L.

1985-01-01

A brief overview of space flight activities is presented. West German contributions to satellite mapping, communication satellites, navigation, Spacelab, diffusion under weightlessness, crystal growth in space, metal bonding, and biochemistry are described. The future of the research in the space station is analyzed.

Langevin Equation for DNA Dynamics

NASA Astrophysics Data System (ADS)

Grych, David; Copperman, Jeremy; Guenza, Marina

Under physiological conditions, DNA oligomers can contain well-ordered helical regions and also flexible single-stranded regions. We describe the site-specific motion of DNA with a modified Rouse-Zimm Langevin equation formalism that describes DNA as a coarse-grained polymeric chain with global structure and local flexibility. The approach has successfully described the protein dynamics in solution and has been extended to nucleic acids. Our approach provides diffusive mode analytical solutions for the dynamics of global rotational diffusion and internal motion. The internal DNA dynamics present a rich energy landscape that accounts for an interior where hydrogen bonds and base-stacking determine structure and experience limited solvent exposure. We have implemented several models incorporating different coarse-grained sites with anisotropic rotation, energy barrier crossing, and local friction coefficients that include a unique internal viscosity and our models reproduce dynamics predicted by atomistic simulations. The models reproduce bond autocorrelation along the sequence as compared to that directly calculated from atomistic molecular dynamics simulations. The Langevin equation approach captures the essence of DNA dynamics without a cumbersome atomistic representation.

A preliminary report on the effect of elevated temperature exposure on the mechanical properties of titanium-alloy honeycomb-core sandwich panels.

NASA Technical Reports Server (NTRS)

Bales, T. T.; Cain, R. L.

1971-01-01

A study has been initiated to determine the effects of elevated-temperature exposure on the room-temperature mechanical properties of titanium honeycomb-core sandwich panels fabricated by brazing or spot diffusion bonding. Only flatwise tensile properties following exposure have been determined to date. Preliminary results indicate very little change in the flatwise tensile strength of sandwich panels fabricated by spot diffusion bonding following exposures of 10,000 hr at 600 and 800 F and 1000 hr at 1000 F. Titanium panels fabricated by using a Ti-Zr-Be braze alloy are susceptible to oxidation at elevated temperature and experience flatwise tensile strength degradation after continuous exposures of 7500 hr at 600 F, 1000 hr at 800 F, and less than 100 hr at 1000 F. It is possible that the exposure life of the brazed panels may be substantially increased if the panel edges are sealed to prevent oxidation of the braze alloy.

Fast kinetics of magnesium monochloride cations in interlayer-expanded titanium disulfide for magnesium rechargeable batteries

DOE PAGES

Yoo, Hyun Deog; Liang, Yanliang; Dong, Hui; ...

2017-08-24

Magnesium rechargeable batteries potentially offer high-energy density, safety, and low cost due to the ability to employ divalent, dendrite-free, and earth-abundant magnesium metal anode. Despite recent progress, further development remains stagnated mainly due to the sluggish scission of magnesium-chloride bond and slow diffusion of divalent magnesium cations in cathodes. Here in this paper we report a battery chemistry that utilizes magnesium monochloride cations in expanded titanium disulfide. Combined theoretical modeling, spectroscopic analysis, and electrochemical study reveal fast diffusion kinetics of magnesium monochloride cations without scission of magnesium-chloride bond. The battery demonstrates the reversible intercalation of 1 and 1.7 magnesium monochloridemore » cations per titanium at 25 and 60 °C, respectively, corresponding to up to 400 mAh g -1 capacity based on the mass of titanium disulfide. The large capacity accompanies with excellent rate and cycling performances even at room temperature, opening up possibilities for a variety of effective intercalation hosts for multivalent-ion batteries.« less

Free Energy Landscape of Cellulose as a Driving Factor in the Mobility of Adsorbed Water.

PubMed

Kulasinski, Karol

2017-06-06

The diffusion coefficient of water adsorbed in hydrophilic porous materials, such as noncrystalline cellulose, depends on water activity. Faster diffusion at higher water concentrations is observed in experimental and modeling studies. In this paper, two asymptotic water concentrations, near-vacuum and fully saturated, are investigated at the surface of crystalline cellulose with molecular dynamics simulations. An increasing water concentration leads to significant changes in the free energy landscape due to perturbation of local electrostatic potential. Smoothening of strong energy minima, corresponding to sorption sites, and formation of layered structure facilitates water transport in the vicinity of cellulose. The determined transition probabilities and hydrogen bond stability reflect the changes in the energy landscape. As a result of a concentration increase, the emerging basins of attraction and spreading out of those existing in the diluted state lead to an increase in water entropy. Thermal fluctuations of cellulose are demonstrated to rearrange the landscape in the diluted limit, increase adsorbed water entropy, and decrease the water-cellulose H-bond lifetime.

Evaluation of superplastic forming and co-diffusion bonding of Ti-6Al-4V titanium alloy expanded sandwich structures

NASA Technical Reports Server (NTRS)

Arvin, G. H.; Israeli, L.; Stolpestad, J. H.; Stacher, G. W.

1981-01-01

The application of the superplastic forming/diffusion bonding (SPF/DB) process to supersonic cruise research is investigated. The capability of an SPF/DB titanium structure to meet the structural requirements of the inner wing area of the NASA arrow-wing advanced supersonic transport design is evaluated. Selection of structural concepts and their optimization for minimum weight, SPF/DB process optimization, fabrication of representative specimens, and specimen testing and evaluation are described. The structural area used includes both upper and lower wing panels, where the upper wing panel is used for static compression strength evaluation and the lower panel, in tension, is used for fracture mechanics evaluations. The individual test specimens, cut from six large panels, consist of 39 static specimens, 10 fracture mechanics specimens, and one each full size panel for compression stability and fracture mechanics testing. Tests are performed at temperatures of -54 C (-65 F), room temperature, and 260 C (500 F).

Utilisation of steel furnace slag coarse aggregate in a low calcium fly ash geopolymer concrete

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

Khan, M. S.H.,; Castel, Arnaud; Akbarnezhad, A.

This paper evaluates the performance of steel furnace slag (SFS) coarse aggregate in blended slag and low calcium fly ash geopolymer concrete (GPC). The geopolymer binder is composed of 90% of low calcium fly ash and 10% of ground granulated blast furnace slag (GGBFS). Mechanical and physical properties, shrinkage, and detailed microstructure analysis were carried out. The results showed that geopolymer concrete with SFS aggregate offered higher compressive strength, surface resistivity and pulse velocity than that of GPC with traditional aggregate. The shrinkage results showed no expansion or swelling due to delayed calcium oxide (CaO) hydration after 320 days. Nomore » traditional porous interfacial transition zone (ITZ) was detected using scanning electron microscopy, indicating a better bond between SFS aggregate and geopolymer matrix. Energy dispersive spectroscopy results further revealed calcium (Ca) diffusion at the vicinity of ITZ. Raman spectroscopy results showed no new crystalline phase formed due to Ca diffusion. X-ray fluorescence result showed Mg diffusion from SFS aggregate towards geopolymer matrix. The incorporation of Ca and Mg into the geopolymer structure and better bond between SFS aggregate and geopolymer matrix are the most likely reasons for the higher compressive strength observed in GPC with SFS aggregate.« less

Structure of thin diamond films: A 1H and 13C nuclear-magnetic-resonance study

NASA Astrophysics Data System (ADS)

Pruski, M.; Lang, D. P.; Hwang, Son-Jong; Jia, H.; Shinar, J.

1994-04-01

The 1H and 13C nuclear magnetic resonance (NMR) of thin diamond films deposited from naturally abundant (1.1 at. %) as well as 50% and 100% 13enriched CH4 heavily diluted in H2 is described and discussed. Less than 0.6 at. % of hydrogen is found in the films which contain crystallites up to ~15 μm across. The 1H NMR consists of a broad 50-65-kHz-wide Gaussian line attributed to H atoms bonded to carbon and covering the crystallite surfaces. A narrow Lorentzian line was only occasionally observed and is found not to be intrinsic to the diamond structure. The 13C NMR demonstrates that >99.5% of the C atoms reside in a quaternary diamondlike configuration. 1-13C cross-polarization measurement indicates that, at the very least, the majority of 13C nuclei cross polarized by 1H, i.e., within three bond distances from a 1H at a crystallite surface, reside in sp3 diamondlike coordinated sites. The 13C relaxation rates of the films are four orders of magnitude faster than that of natural diamond and believed to be due to 13C spin diffusion to paramagnetic centers, presumably carbon dangling bonds. Analysis of the measured relaxation rates indicates that within the 13C spin-diffusion length of √DTc1 ~0.05 μm, these centers are uniformly distributed in the diamond crystallites. The possibility that the dangling bonds are located at internal nanovoid surfaces is discussed.

Ion mobility and clustering of sodium hydroxybenzoates in aqueous solutions: a molecular dynamics simulation study.

PubMed

Gujt, Jure; Podlipnik, Črtomir; Bešter-Rogač, Marija; Spohr, Eckhard

2014-09-28

The relative position of the hydroxylic and the carboxylic group in the isomeric hydroxybenzoate (HB) anions is known to have a large impact on transport properties of this species. It also influences crucially the self-organisation of cationic surfactants. In this article a systematic investigation of aqueous solutions of the ortho, meta, and para isomers of the HB anion is presented. Molecular dynamics simulations of all three HB isomers were conducted for two different concentrations at 298.15 K and using two separate water models. From the resulting trajectories we calculated the self-diffusion coefficient of each isomer. According to the calculated self-diffusion coefficients, isomers were ranked in the order o-HB > m-HB > p-HB at both concentrations for both the used SPC and SPC/E water models, which agrees very well with the experiment. The structural analysis revealed that at lower concentration, where the tendency for dimerisation or cluster formation is low, hydrogen bonding with water determines the mobility of the HB anion. o-HB forms the least hydrogen bonds and is therefore the most mobile, and p-HB, which forms the most hydrogen bonds with water, is the least mobile isomer. At higher concentration the formation of clusters also needs to be considered. The ortho isomer predominantly forms dimers with 2 hydrogen bonds per dimer between one OH and one carboxylate group of each anion. m-HB mostly forms clusters of sizes around 5 and p-HB forms clusters of sizes even larger than 10, which can be either rings or chains.

Reversed nanoscale Kirkendall effect in Au–InAs hybrid nanoparticles

DOE PAGES

Liu, Jing; Amit, Yorai; Li, Yuanyuan; ...

2016-10-10

Metal–semiconductor hybrid nanoparticles (NPs) offer interesting synergistic properties, leading to unique behaviors that have already been exploited in photocatalysis, electrical, and optoelectronic applications. A fundamental aspect in the synthesis of metal–semiconductor hybrid NPs is the possible diffusion of the metal species through the semiconductor lattice. The importance of understanding and controlling the co-diffusion of different constituents is demonstrated in the synthesis of various hollow-structured NPs via the Kirkendall effect. Here, we used a postsynthesis room-temperature reaction between AuCl 3 and InAs nanocrystals (NCs) to form metal–semiconductor core–shell hybrid NPs through the “reversed Kirkendall effect”. In the presented system, the diffusionmore » rate of the inward diffusing species (Au) is faster than that of the outward diffusing species (InAs), which results in the formation of a crystalline metallic Au core surrounded by an amorphous, oxidized InAs shell containing nanoscale voids. We used time-resolved X-ray absorption fine-structure (XAFS) spectroscopy to monitor the diffusion process and found that both the size of the Au core and the extent of the disorder of the InAs shell depend strongly on the Au-to-NC ratio. We have determined, based on multielement fit analysis, that Au diffuses into the NC via the kick-out mechanism, substituting for In host atoms; this compromises the structural stability of the lattice and triggers the formation of In–O bonds. These bonds were used as markers to follow the diffusion process and indicate the extent of degradation of the NC lattice. Time-resolved X-ray diffraction (XRD) was used to measure the changes in the crystal structures of InAs and the nanoscale Au phases. By combining the results of XAFS, XRD, and electron microscopy, we correlated the changes in the local structure around Au, As, and In atoms and the changes in the overall InAs crystal structure. This correlative analysis revealed a co-dependence of different structural consequences when introducing Au into the InAs NCs. As a result this study of diffusion effects in nanocrystals has relevance to powerful concepts in solid-state nanochemistry related to processes of cation exchange, doping reactions, and diffusion mechanisms.« less

Reversed Nanoscale Kirkendall Effect in Au–InAs Hybrid Nanoparticles

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

Liu, Jing; Amit, Yorai; Li, Yuanyuan

2016-11-08

Metal–semiconductor hybrid nanoparticles (NPs) offer interesting synergistic properties, leading to unique behaviors that have already been exploited in photocatalysis, electrical, and optoelectronic applications. A fundamental aspect in the synthesis of metal–semiconductor hybrid NPs is the possible diffusion of the metal species through the semiconductor lattice. The importance of understanding and controlling the co-diffusion of different constituents is demonstrated in the synthesis of various hollow-structured NPs via the Kirkendall effect. Here, we used a postsynthesis room-temperature reaction between AuCl 3 and InAs nanocrystals (NCs) to form metal–semiconductor core–shell hybrid NPs through the “reversed Kirkendall effect”. In the presented system, the diffusionmore » rate of the inward diffusing species (Au) is faster than that of the outward diffusing species (InAs), which results in the formation of a crystalline metallic Au core surrounded by an amorphous, oxidized InAs shell containing nanoscale voids. We used time-resolved X-ray absorption fine-structure (XAFS) spectroscopy to monitor the diffusion process and found that both the size of the Au core and the extent of the disorder of the InAs shell depend strongly on the Au-to-NC ratio. We have determined, based on multielement fit analysis, that Au diffuses into the NC via the kick-out mechanism, substituting for In host atoms; this compromises the structural stability of the lattice and triggers the formation of In–O bonds. These bonds were used as markers to follow the diffusion process and indicate the extent of degradation of the NC lattice. Time-resolved X-ray diffraction (XRD) was used to measure the changes in the crystal structures of InAs and the nanoscale Au phases. By combining the results of XAFS, XRD, and electron microscopy, we correlated the changes in the local structure around Au, As, and In atoms and the changes in the overall InAs crystal structure. This correlative analysis revealed a co-dependence of different structural consequences when introducing Au into the InAs NCs. Therefore, this study of diffusion effects in nanocrystals has relevance to powerful concepts in solid-state nanochemistry related to processes of cation exchange, doping reactions, and diffusion mechanisms.« less

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Stinson, Craig A.; Zhang, Wenpeng; Xia, Yu

2017-12-01

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS.

Nanolubrication: patterned lubricating films using ultraviolet (UV) irradiation on hard disks.

PubMed

Zhang, J; Hsu, S M; Liew, Y F

2007-01-01

Nanolubrication is emerging to be the key technical barrier in many devices. One of the key attributes for successful device lubrication is self-sustainability using only several molecular layers. For single molecular species lubrication, one desires bonding strength and molecular mobility to repair the contact by diffusing back to the contact. One way to achieve this is the use of mask to shield the surface with a patterned surface texture, put a monolayer on the surface and induce bonding. Then re-deposit mobile molecules on the surface to bring the thickness back to the desired thickness. This paper describes the use of long wavelength UV irradiation (320-390 nm) to induce bonding of a perfluoropolyether (PFPE) on CN(x) disks for magnetic hard disk application. This allows the use of irradiation to control the degree of bonding on CN(x) coatings. The effect of induced bonding based on this wavelength was studied by comparing 100% mobile PFPE, 100% bonded PFPE, and a mixture of mobile and bonded PFPE in a series of laboratory tests. Using a lateral force microscope, a diamond-tipped atomic force microscope, and a ball-on-inclined plane apparatus, the friction and wear characteristics of these three cases were obtained. Results suggested that the mixed PFPE has the highest shear rupture strength.

Method to improve commercial bonded SOI material

DOEpatents

Maris, Humphrey John; Sadana, Devendra Kumar

2000-07-11

A method of improving the bonding characteristics of a previously bonded silicon on insulator (SOI) structure is provided. The improvement in the bonding characteristics is achieved in the present invention by, optionally, forming an oxide cap layer on the silicon surface of the bonded SOI structure and then annealing either the uncapped or oxide capped structure in a slightly oxidizing ambient at temperatures greater than 1200.degree. C. Also provided herein is a method for detecting the bonding characteristics of previously bonded SOI structures. According to this aspect of the present invention, a pico-second laser pulse technique is employed to determine the bonding imperfections of previously bonded SOI structures.

Viscous friction of hydrogen-bonded matter

NASA Astrophysics Data System (ADS)

Erbas, Aykut; Horinek, Dominik; Netz, Roland R.

2012-02-01

Amontons' law successfully describes friction between macroscopic solid bodies for a wide range of velocities and normal forces. For the diffusion and forced sliding of adhering or entangled macromolecules, proteins and biological complexes, temperature effects are invariably important and a similarly successful friction law at biological length and velocity scales is missing. Hydrogen bonds are key to the specific binding of bio-matter. Here we show that friction between hydrogen-bonded matter obeys in the biologically relevant low-velocity viscous regime a simple equations: the friction force is proportional to the number of hydrogen bonds, the sliding velocity, and a friction coefficient γHB. This law is deduced from atomistic molecular dynamics simulations for short peptide chains that are laterally pulled over hydroxylated substrates in the presence of water and holds for widely different peptides, surface polarities and applied normal forces. The value of γHB is extrapolated from simulations at sliding velocities in the range from v=10-2 m/s to 100 m/s by mapping on a simple stochastic model and turns out to be of the order of γHB˜10-8 kg/s. 3 hydrogen bonds act collectively.

Diffusion of hydrous species in model basaltic melt

NASA Astrophysics Data System (ADS)

Zhang, Li; Guo, Xuan; Wang, Qinxia; Ding, Jiale; Ni, Huaiwei

2017-10-01

Water diffusion in Fe-free model basaltic melt with up to 2 wt% H2O was investigated at 1658-1846 K and 1 GPa in piston-cylinder apparatus using both hydration and diffusion couple techniques. Diffusion profiles measured by FTIR are consistent with a model in which both molecular H2O (H2Om) and hydroxyl (OH) contribute to water diffusion. OH diffusivity is roughly 13% of H2Om diffusivity, showing little dependence on temperature or water concentration. Water diffusion is dominated by the motion of OH until total H2O (H2Ot) concentration reaches 1 wt%. The dependence of apparent H2Ot diffusivity on H2Ot concentration appears to be overestimated by a previous study on MORB melt, but H2Ot diffusivity at 1 wt% H2Ot in basaltic melt is still greater than those in rhyolitic to andesitic melts. The appreciable contribution of OH to water diffusion in basaltic melt can be explained by enhanced mobility of OH, probably associated with the development of free hydroxyl bonded with network-modifying cations, as well as higher OH concentration. Calculation based on the Nernst-Einstein equation demonstrates that OH may serve as an effective charge carrier in hydrous basaltic melt, which could partly account for the previously observed strong influence of water on electrical conductivity of basaltic melt.

Refractive-Index-Based Screening of Membrane-Protein-Mediated Transfer across Biological Membranes

PubMed Central

Brändén, Magnus; Tabaei, Seyed R.; Fischer, Gerhard; Neutze, Richard; Höök, Fredrik

2010-01-01

Abstract Numerous membrane-transport proteins are major drug targets, and therefore a key ingredient in pharmaceutical development is the availability of reliable, efficient tools for membrane transport characterization and inhibition. Here, we present the use of evanescent-wave sensing for screening of membrane-protein-mediated transport across lipid bilayer membranes. This method is based on a direct recording of the temporal variations in the refractive index that occur upon a transfer-dependent change in the solute concentration inside liposomes associated to a surface plasmon resonance (SPR) active sensor surface. The applicability of the method is demonstrated by a functional study of the aquaglyceroporin PfAQP from the malaria parasite Plasmodium falciparum. Assays of the temperature dependence of facilitated diffusion of sugar alcohols on a single set of PfAQP-reconstituted liposomes reveal that the activation energies for facilitated diffusion of xylitol and sorbitol are the same as that previously measured for glycerol transport in the aquaglyceroporin of Escherichia coli (5 kcal/mole). These findings indicate that the aquaglyceroporin selectivity filter does not discriminate sugar alcohols based on their length, and that the extra energy cost of dehydration of larger sugar alcohols, upon entering the pore, is compensated for by additional hydrogen-bond interactions within the aquaglyceroporin pore. PMID:20655840

Refractive-index-based screening of membrane-protein-mediated transfer across biological membranes.

PubMed

Brändén, Magnus; Tabaei, Seyed R; Fischer, Gerhard; Neutze, Richard; Höök, Fredrik

2010-07-07

Numerous membrane-transport proteins are major drug targets, and therefore a key ingredient in pharmaceutical development is the availability of reliable, efficient tools for membrane transport characterization and inhibition. Here, we present the use of evanescent-wave sensing for screening of membrane-protein-mediated transport across lipid bilayer membranes. This method is based on a direct recording of the temporal variations in the refractive index that occur upon a transfer-dependent change in the solute concentration inside liposomes associated to a surface plasmon resonance (SPR) active sensor surface. The applicability of the method is demonstrated by a functional study of the aquaglyceroporin PfAQP from the malaria parasite Plasmodium falciparum. Assays of the temperature dependence of facilitated diffusion of sugar alcohols on a single set of PfAQP-reconstituted liposomes reveal that the activation energies for facilitated diffusion of xylitol and sorbitol are the same as that previously measured for glycerol transport in the aquaglyceroporin of Escherichia coli (5 kcal/mole). These findings indicate that the aquaglyceroporin selectivity filter does not discriminate sugar alcohols based on their length, and that the extra energy cost of dehydration of larger sugar alcohols, upon entering the pore, is compensated for by additional hydrogen-bond interactions within the aquaglyceroporin pore. Copyright 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Room temperature bonding and debonding of polyimide film and glass substrate based on surface activate bonding method

NASA Astrophysics Data System (ADS)

Takeuchi, Kai; Fujino, Masahisa; Matsumoto, Yoshiie; Suga, Tadatomo

2018-02-01

The temporary bonding of polyimide (PI) films and glass substrates is a key technology for realizing flexible devices with thin-film transistors (TFTs). In this paper, we report the surface activated bonding (SAB) method using Si intermediate layers and its bonding and debonding mechanisms after heating. The bonding interface composed of Si and Fe shows a higher bond strength than the interface of only Si, while the bond strengths of both interfaces decrease with post bonding heating. It is also clarified by composition analysis on the debonded surfaces and cross-sectional observation of the bonding interface that the bond strength depends on the toughness of the intermediated layers and PI. The SAB method using Si intermediate layers is found to be applicable to the bonding and debonding of PI and glass.

A reaction-diffusion model for market fluctuations - A relation between price change and traded volumes

NASA Astrophysics Data System (ADS)

Yuvan, Steven; Bier, Martin

2018-02-01

Two decades ago Bak et al. (1997) [3] proposed a reaction-diffusion model to describe market fluctuations. In the model buyers and sellers diffuse from opposite ends of a 1D interval that represents a price range. Trades occur when buyers and sellers meet. We show analytically and numerically that the model well reproduces the square-root relation between traded volumes and price changes that is observed in real-life markets. The result is remarkable as this relation has commonly been explained in terms of more elaborate trader strategies. We furthermore explain why the square-root relation is robust under model modifications and we show how real-life bond market data exhibit the square-root relation.

High Temperature Characteristics of Pt/TaSi2/Pt/W and Pt/Ti/W Diffusion Barrier Systems for Ohmic Contacts to 4H-SiC

NASA Technical Reports Server (NTRS)

Okojie, Robert S.; Lukco, Dorothy

2017-01-01

The degradation of ohmic contacts to 4H-SiC pressure sensors over time at high temperature is primarily due to two failure mechanisms: migrating bond pad Au and atmospheric O toward the ohmic contact SiC interface and the inter-metallic mixing between diffusion barrier systems (DBS) and the underlying ohmic contact metallization. We investigated the effectiveness of Pt/TaSi2/Pt/W (DBS-A) and Pt/Ti/W (DBS-B) in preventing Au and O diffusion through the underlying binary Ti/W or alloyed W50:Ni50 ohmic contacts to 4H-SiC and the DBS ohmic contact intermixing at temperature up to 700 C.

Preparation and Physical Properties of Segmented Thermoelectric YBa2Cu3O7-x -Ca3Co4O9 Ceramics

NASA Astrophysics Data System (ADS)

Wannasut, P.; Keawprak, N.; Jaiban, P.; Watcharapasorn, A.

2018-01-01

Segmented thermoelectric ceramics are now well known for their high conversion efficiency and are currently being investigated in both basic and applied energy researches. In this work, the successful preparation of the segmented thermoelectric YBa2Cu3O7-x -Ca3Co4O9 (YBCO-CCO) ceramic by hot pressing method and the study on its physical properties were presented. Under the optimum hot pressing condition of 800 °C temperature, 1-hour holding time and 1-ton weight, the segmented YBCO-CCO sample showed two strongly connected layers with the relative density of about 96%. The X-ray diffraction (XRD) patterns indicated that each segment showed pure phase corresponding to each respective composition. Scanning electron microscopy (SEM) results confirmed the sharp interface and good adhesion between YBCO and CCO layers. Although the chemical analysis indicated the limited inter-layer diffusion near the interface, some elemental diffusion at the boundary was expected to be the source of this strong bonding.

High-temperature morphological evolution of lithographically introduced cavities in silicon carbide

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

Narushima, Takayuki; Glaeser, Andreas M.

2000-12-01

Internal cavities of controlled geometry and crystallography were introduced in 6H silicon carbide single crystals by combining lithographic methods, ion beam etching, and solid-state diffusion bonding. The morphological evolution of these internal cavities (negative crystals) in response to anneals of up to 128 h duration at 1900 degrees C was examined using optical microscopy. Surface energy anisotropy and faceting have a strong influence on both the geometric and kinetic characteristics of evolution. Decomposition of 12{bar 1}0 cavity edges into 101{bar 0} facets was observed after 16 h anneals, indicating that 12{bar 1}0 faces are not components of the Wulff shape.more » The shape evolution kinetics of penny-shaped cavities were also investigated. Experimentally observed evolution rates decreased much more rapidly with those predicted by a model in which surface diffusion is assumed to be rate-limiting. This suggests that the development of facets, and the associated loss of ledges and terraces during the initial stages of evolution results in an evolution process limited by the nucleation rate of attachment/detachment sites (ledges) on the facets.« less

On the Role of Specific Interactions in the Diffusion of Nanoparticles in Aqueous Polymer Solutions

PubMed Central

2013-01-01

Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(N-vinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions. PMID:24354390

On the role of specific interactions in the diffusion of nanoparticles in aqueous polymer solutions.

PubMed

Mun, Ellina A; Hannell, Claire; Rogers, Sarah E; Hole, Patrick; Williams, Adrian C; Khutoryanskiy, Vitaliy V

2014-01-14

Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(N-vinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions.

Recent mass spectrometry-based techniques and considerations for disulfide bond characterization in proteins.

PubMed

Lakbub, Jude C; Shipman, Joshua T; Desaire, Heather

2018-04-01

Disulfide bonds are important structural moieties of proteins: they ensure proper folding, provide stability, and ensure proper function. With the increasing use of proteins for biotherapeutics, particularly monoclonal antibodies, which are highly disulfide bonded, it is now important to confirm the correct disulfide bond connectivity and to verify the presence, or absence, of disulfide bond variants in the protein therapeutics. These studies help to ensure safety and efficacy. Hence, disulfide bonds are among the critical quality attributes of proteins that have to be monitored closely during the development of biotherapeutics. However, disulfide bond analysis is challenging because of the complexity of the biomolecules. Mass spectrometry (MS) has been the go-to analytical tool for the characterization of such complex biomolecules, and several methods have been reported to meet the challenging task of mapping disulfide bonds in proteins. In this review, we describe the relevant, recent MS-based techniques and provide important considerations needed for efficient disulfide bond analysis in proteins. The review focuses on methods for proper sample preparation, fragmentation techniques for disulfide bond analysis, recent disulfide bond mapping methods based on the fragmentation techniques, and automated algorithms designed for rapid analysis of disulfide bonds from liquid chromatography-MS/MS data. Researchers involved in method development for protein characterization can use the information herein to facilitate development of new MS-based methods for protein disulfide bond analysis. In addition, individuals characterizing biotherapeutics, especially by disulfide bond mapping in antibodies, can use this review to choose the best strategies for disulfide bond assignment of their biologic products. Graphical Abstract This review, describing characterization methods for disulfide bonds in proteins, focuses on three critical components: sample preparation, mass spectrometry data, and software tools.

Atomistic Simulation Studies of Cholesteryl Oleates: Model for the Core of Lipoprotein Particles

PubMed Central

Heikelä, Mikko; Vattulainen, Ilpo; Hyvönen, Marja T.

2006-01-01

We have conducted molecular dynamics simulations to gain insight into the atomic-scale properties of an isotropic system of cholesteryl oleate (CO) molecules. Cholesteryl esters are major constituents of low density lipoprotein particles, the key players in the formation of atherosclerosis, as well as the storage form of cholesterol. Here the aim is to clarify structural and dynamical properties of CO molecules under conditions, which are suggestive of those in the core of low density lipoprotein particles. The simulations in the fluid phase indicate that the system of CO molecules is characterized by an absence of translational order, as expected, while the orientational order between distinct CO molecules is significant at short distances, persisting over a molecular size. As for intramolecular properties, the bonds along the oleate chain are observed to be weakly ordered with respect to the sterol structure, unlike the bonds along the short hydrocarbon chain of cholesterol where the ordering is significant. The orientational distribution of the oleate chain as a whole with respect to the sterol moiety is of broad nature, having a major amount of extended and a less considerable proportion of bended structures. Distinct transient peaks at specific angles also appear. The diffusion of CO molecules is found to be a slow process and characterized by a diffusion coefficient of the order of 2 × 10−9 cm2/s. This is considerably slower than diffusion, e.g., in ordered domains of lipid membranes rich in sphingomyelin and cholesterol. Analysis of the rotational diffusion rates and trans-to-gauche transition rates yield results consistent with experiments. PMID:16399839

SPF/DB titanium concepts for structural efficiency foi HC

NASA Technical Reports Server (NTRS)

Wilson, V. E.

1982-01-01

Illustrations for a presentation on superplastic forming/diffusion bonding titanium design concepts are presented. Sandwich skin panels with hat section, semicircular corrugation, sine wave, and truss cores are shown. The fabrication of wing panels is illustrated, and applications to the design of advanced variable sweep bombers summarized.

Challenges in molecular simulation of homogeneous ice nucleation

NASA Astrophysics Data System (ADS)

Brukhno, Andrey V.; Anwar, Jamshed; Davidchack, Ruslan; Handel, Richard

2008-12-01

We address the problem of recognition and growth of ice nuclei in simulation of supercooled bulk water. Bond orientation order parameters based on the spherical harmonics analysis are shown to be ineffective when applied to ice nucleation. Here we present an alternative method which robustly differentiates between hexagonal and cubic ice forms. The method is based on accumulation of the maximum projection of bond orientations onto a set of predetermined vectors, where different terms can contribute with opposite signs with the result that the irrelevant or incompatible molecular arrangements are damped out. We also introduce an effective cluster size by assigning a quality weight to each molecule in an ice-like cluster. We employ our cluster analysis in Monte Carlo simulation of homogeneous ice formation. Replica-exchange umbrella sampling is used for biasing the growth of the largest cluster and calculating the associated free energy barrier. Our results suggest that the ice formation can be seen as a two-stage process. Initially, short tetrahedrally arranged threads and rings are present; these become correlated and form a diffuse ice-genic network. Later, hydrogen bond arrangements within the amorphous ice-like structure gradually settle down and simultaneously 'tune-up' nearby water molecules. As a result, a well-shaped ice core emerges and spreads throughout the system. The process is very slow and diverse owing to the rough energetic landscape and sluggish molecular motion in supercooled water, while large configurational fluctuations are needed for crystallization to occur. In the small systems studied so far the highly cooperative molecular rearrangements eventually lead to a relatively fast percolation of the forming ice structure through the periodic boundaries, which inevitably affects the simulation results.

Melt extrusion vs. spray drying: The effect of processing methods on crystalline content of naproxen-povidone formulations.

PubMed

Haser, Abbe; Cao, Tu; Lubach, Joe; Listro, Tony; Acquarulo, Larry; Zhang, Feng

2017-05-01

Our hypothesis is that melt extrusion is a more suitable processing method than spray drying to prepare amorphous solid dispersions of drugs with a high crystallization tendency. Naproxen-povidone K25 was used as the model system in this study. Naproxen-povidone K25 solid dispersions at 30% and 60% drug loadings were characterized by modulated DSC, powder X-ray diffraction, FT-IR, and solid-state 13 C NMR to identify phase separation and drug recrystallization during processing and storage. At 30% drug loading, hydrogen bond (H-bond) sites of povidone K25 were not saturated and the glass transition (T g ) temperature of the formulation was higher. As a result, both melt-extruded and spray-dried materials were amorphous initially and remained so after storage at 40°C. At 60% drug loading, H-bond sites were saturated, and T g was low. We were not able to prepare amorphous materials. The initial crystallinity of the formulations was 0.4%±0.2% and 5.6%±0.6%, and increased to 2.7%±0.3% and 21.6%±1.0% for melt-extruded and spray-dried materials, respectively. Spray-dried material was more susceptible to re-crystallization during processing, due to the high diffusivity of naproxen molecules in the formulation matrix and lack of kinetic stabilization from polymer solution. A larger number of crystalline nucleation sites and high surface area made the spray-dried material more susceptible to recrystallization during storage. This study demonstrated the unique advantages of melt extrusion over spray drying for the preparation of amorphous solid dispersions of naproxen at high drug level. Copyright © 2017 Elsevier B.V. All rights reserved.

Aminosilanization nanoadhesive layer for nanoelectric circuits with porous ultralow dielectric film.

PubMed

Zhao, Zhongkai; He, Yongyong; Yang, Haifang; Qu, Xinping; Lu, Xinchun; Luo, Jianbin

2013-07-10

An ultrathin layer is investigated for its potential application of replacing conventional diffusion barriers and promoting interface adhesion for nanoelectric circuits with porous ultralow dielectrics. The porous ultralow dielectric (k ≈ 2.5) substrate is silanized by 3-aminopropyltrimethoxysilane (APTMS) to form the nanoadhesive layer by performing oxygen plasma modification and tailoring the silanization conditions appropriately. The high primary amine content is obtained in favor of strong interaction between amino groups and copper. And the results of leakage current measurements of metal-oxide-semiconductor capacitor structure demonstrate that the aminosilanization nanoadhesive layer can block copper diffusion effectively and guarantee the performance of devices. Furthermore, the results of four-point bending tests indicate that the nanoadhesive layer with monolayer structure can provide the satisfactory interface toughness up to 6.7 ± 0.5 J/m(2) for Cu/ultralow-k interface. Additionally, an annealing-enhanced interface toughness effect occurs because of the formation of Cu-N bonding and siloxane bridges below 500 °C. However, the interface is weakened on account of the oxidization of amines and copper as well as the breaking of Cu-N bonding above 500 °C. It is also found that APTMS nanoadhesive layer with multilayer structure provides relatively low interface toughness compared with monolayer structure, which is mainly correlated to the breaking of interlayer hydrogen bonding.

Stimulated Mid-Infrared Luminescence Experiment: Contribution to the Study of Pre-Earthquake Phenomena and UV Absorption by Interstellar Dust

NASA Technical Reports Server (NTRS)

Freund, Friedemann; Freund, Minoru M.; Tsay, Si-Chee; Ouzounov, Dimitar

2004-01-01

The work performed under this proposal is based on the experimentally supported observation - or inference - that a small fraction of the oxygen anions in silicate minerals in igneous and high-grade metamorphic rocks on Earth may not be in the usual 2- oxidation state, O(sup 2-), but in a higher oxidation state, as O(sup -). If this is true, the same would likely apply to the fine dust that fills the diffuse interstellar medium. An (sup -) in a matrix of O(sup 2-) represents a defect electron in the valence band, also known as positive hole or p-hole for short. When two O(sup -) combine, they undergo spin-pairing and form a positive hole pair, PHP. Chemically speaking a PHP is a peroxy bond. In an oxide matrix a peroxy bond takes the form of a peroxy anion, O2(sup 2-). In a silicate matrix it probably exists in the form of peroxy links between adjacent [SiO4] tetrahedral, O3Si00\\SiO3. From a physics perspective a PHP is an electrically inactive point defect, which contains dormant electronic charge carriers. When the peroxy bond breaks, p-hole charge carriers are released. These p-holes are diffusively mobile and spread through the O 2p-dominated valence band of the otherwise insulating mineral matrix.

Room-temperature wafer bonding of LiNbO3 and SiO2 using a modified surface activated bonding method

NASA Astrophysics Data System (ADS)

Takigawa, Ryo; Higurashi, Eiji; Asano, Tanemasa

2018-06-01

In this paper, we report room-temperature bonding of LiNbO3 (LN) and SiO2/Si for the realization of a LN on insulator (LNOI)/Si hybrid wafer. We investigate the applicability of a modified surface activated bonding (SAB) method for the direct bonding of LN and a thermally grown SiO2 layer. The modified SAB method using ion beam bombardment demonstrates the room-temperature wafer bonding of LN and SiO2. The bonded wafer was successfully cut into 0.5 × 0.5 mm2 dies without interfacial debonding owing to the applied stress during dicing. In addition, the surface energy of the bonded wafer was estimated to be approximately 1.8 J/m2 using the crack opening method. These results indicate that a strong bond strength can be achieved, which may be sufficient for device applications.

Quantum molecular dynamics simulation of structural and thermodynamic properties of NiAl

NASA Astrophysics Data System (ADS)

Karchevskaya, E. S.; Minakov, D. V.; Levashov, P. R.

2018-01-01

In this work, structural and thermodynamic properties of a solid and liquid Ni-Al compound are studied using an ab initio method of quantum molecular dynamics (QMD). Simulations were carried out in 700-3000 K temperature range at atmospheric pressure. Radial distribution functions are analyzed to determine the presence of Ni-Al chemical bonds. Diffusion coefficients for individual components are also calculated. Another goal of this work is the investigation of the reaction propagation in thermally-initiated Ni-Al foils. For this purpose, we performed QMD simulations of Ni-Al layers in the microcanonical ensemble. An exothermic reaction between the solid Ni-Al layers is observed in our simulations at temperature less than the melting temperatures of the components.

Implanted neural network potentials: Application to Li-Si alloys

NASA Astrophysics Data System (ADS)

Onat, Berk; Cubuk, Ekin D.; Malone, Brad D.; Kaxiras, Efthimios

2018-03-01

Modeling the behavior of materials composed of elements with different bonding and electronic structure character for large spatial and temporal scales and over a large compositional range is a challenging problem. Cases in point are amorphous alloys of Si, a prototypical covalent material, and Li, a prototypical metal, which are being considered as anodes for high-energy-density batteries. To address this challenge, we develop a methodology based on neural networks that extends the conventional training approach to incorporate pre-trained parts that capture the character of different components, into the overall network; we refer to this model as the "implanted neural network" method. We show that this approach works well for the Si-Li amorphous alloys for a wide range of compositions, giving good results for key quantities like the diffusion coefficients. The method is readily generalizable to more complicated situations that involve two or more different elements.

Role of hydrogen bonds in the reaction mechanism of chalcone isomerase.

PubMed

Jez, Joseph M; Bowman, Marianne E; Noel, Joseph P

2002-04-23

In flavonoid, isoflavonoid, and anthocyanin biosynthesis, chalcone isomerase (CHI) catalyzes the intramolecular cyclization of chalcones into (S)-flavanones with a second-order rate constant that approaches the diffusion-controlled limit. The three-dimensional structures of alfalfa CHI complexed with different flavanones indicate that two sets of hydrogen bonds may possess critical roles in catalysis. The first set of interactions includes two conserved amino acids (Thr48 and Tyr106) that mediate a hydrogen bond network with two active site water molecules. The second set of hydrogen bonds occurs between the flavanone 7-hydroxyl group and two active site residues (Asn113 and Thr190). Comparison of the steady-state kinetic parameters of wild-type and mutant CHIs demonstrates that efficient cyclization of various chalcones into their respective flavanones requires both sets of contacts. For example, the T48A, T48S, Y106F, N113A, and T190A mutants exhibit 1550-, 3-, 30-, 7-, and 6-fold reductions in k(cat) and 2-3-fold changes in K(m) with 4,2',4'-trihydroxychalcone as a substrate. Kinetic comparisons of the pH-dependence of the reactions catalyzed by wild-type and mutant enzymes indicate that the active site hydrogen bonds contributed by these four residues do not significantly alter the pK(a) of the intramolecular cyclization reaction. Determinations of solvent kinetic isotope and solvent viscosity effects for wild-type and mutant enzymes reveal a change from a diffusion-controlled reaction to one limited by chemistry in the T48A and Y106F mutants. The X-ray crystal structures of the T48A and Y106F mutants support the assertion that the observed kinetic effects result from the loss of key hydrogen bonds at the CHI active site. Our results are consistent with a reaction mechanism for CHI in which Thr48 polarizes the ketone of the substrate and Tyr106 stabilizes a key catalytic water molecule. Hydrogen bonds contributed by Asn113 and Thr190 provide additional stabilization in the transition state. Conservation of these residues in CHIs from other plant species implies a common reaction mechanism for enzyme-catalyzed flavanone formation in all plants.

Is Solute Rotation in an Ionic Liquid Influenced by the Addition of Glucose?

PubMed

Maurya, Rajan; Naithani, Sudhanshu; Bandyopadhyay, Dibyendu; Choudhury, Niharendu; Dutt, G B

2017-12-07

Fluorescence anisotropy measurements and molecular dynamics (MD) simulations have been performed to understand the specific interactions of two structurally similar nondipolar solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP), with neat 1-butyl-3-methylimidazolium dicyanamide ([BMIM][N(CN) 2 ]) and also in the presence of glucose. It has been observed that the measured reorientation times of DMDPP in neat [BMIM][N(CN) 2 ] follow the predictions of the Stokes-Einstein-Debye hydrodynamic theory with slip boundary condition. Addition of glucose (0.075 and 0.15 mole fraction) has no bearing on the rotational diffusion of the solute apart from the viscosity related effects. In contrast, the reorientation times of DPP in neat [BMIM][N(CN) 2 ] obey stick boundary condition as the hydrogen bond donating solute experiences specific interactions with the dicyanamide anion. No influence of the additive can be noticed on the rotational diffusion of DPP at 0.075 mole fraction of glucose. However, at 0.15 mole fraction of glucose, the reorientation times of the solute at a given viscosity and temperature decrease by 15-40% compared to those obtained in the neat ionic liquid. MD simulations indicate that each DPP molecule hydrogen bonds with two dicyanamide anions in neat ionic liquid. The simulations also reveal that, at 0.15 mole fraction of glucose, the concentration of anions hydrogen bonded to glucose increases significantly; therefore, the percentage of solute molecules that can form hydrogen bonds with two dicyanamide anions decreases to 84, which leads to faster rotation of DPP.

Accelerated Metastable Solid-liquid Interdiffusion Bonding with High Thermal Stability and Power Handling

NASA Astrophysics Data System (ADS)

Huang, Ting-Chia; Smet, Vanessa; Kawamoto, Satomi; Pulugurtha, Markondeya R.; Tummala, Rao R.

2018-01-01

Emerging high-performance systems are driving the need for advanced packaging solutions such as 3-D integrated circuits (ICs) and 2.5-D system integration with increasing performance and reliability requirements for off-chip interconnections. Solid-liquid interdiffusion (SLID) bonding resulting in all-intermetallic joints has been proposed to extend the applicability of solders, but faces fundamental and manufacturing challenges hindering its wide adoption. This paper introduces a Cu-Sn SLID interconnection technology, aiming at stabilization of the microstructure in the Cu6Sn5 metastable phase rather than the usual stable Cu3Sn phase. This enables formation of a void-free interface yielding higher mechanical strength than standard SLID bonding, as well as significantly reducing the transition time. The metastable SLID technology retains the benefits of standard SLID with superior I/O pitch scalability, thermal stability and current handling capability, while advancing assembly manufacturability. In the proposed concept, the interfacial reaction is controlled by introducing Ni(P) diffusion barrier layers, designed to effectively isolate the metastable Cu6Sn5 phase preventing any further transformation. Theoretical diffusion and kinetic models were applied to design the Ni-Cu-Sn interconnection stack to achieve the targeted joint composition. A daisy chain test vehicle was used to demonstrate this technology as a first proof of concept. Full transition to Cu6Sn5 was successfully achieved within a minute at 260°C as confirmed by scanning electron microscope (SEM) and x-ray energy dispersive spectroscopy (XEDS) analysis. The joint composition was stable through 10× reflow, with outstanding bond strength averaging 90 MPa. The metastable SLID interconnections also showed excellent electromigration performance, surviving 500 h of current stressing at 105 A/cm2 at 150°C.

[In situ diffuse reflectance FTIR spectroscopy study of CO adsorption on Ni2P/mesoporous molecule sieve catalysts].

PubMed

Liu, Qian-qian; Ji, Sheng-fu; Wu, Ping-yi; Hu, Lin-hua; Huang, Xiao-fan; Zhu, Ji-qin; Li, Cheng-yue

2009-05-01

Abstract The supported nickel phosphate precursors were prepared by incipient wetness impregnation using nickel nitrate as nickel source, diammonium hydrogen phosphate as phosphorus source, and MCM-41, MCM-48, SBA-15 and SBA-16 as supports, respectively. Then, the supported Ni2 P catalysts were prepared by temperature-programmed reduction in flowing Hz from their nickel phosphate precursors. The in situ diffuse reflectance FTIR spectroscopy (DRIFTS) analysis with the probe molecule CO was carried out to characterize the surface properties. The results indicated that there were significant differences in the spectral features of the samples. The upsilon(CO) absorbances observed for adsorbed CO on mesoporous molecule sieve was attributed to weak physical adsorption. There are four different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2 P/MCM-41 catalyst with the following assignments: (1) the formation of Ni(CO)4 at 2055 cm(-1). (2) CO terminally bonded to cus Ni(delta+) (0

Adsorption of water from aqueous acetonitrile on silica-based stationary phases in aqueous normal-phase liquid chromatography.

PubMed

Soukup, Jan; Jandera, Pavel

2014-12-29

Excess adsorption of water from aqueous acetonitrile mobile phases was investigated on 16 stationary phases using the frontal analysis method and coulometric Karl-Fischer titration. The stationary phases include silica gel and silica-bonded phases with different polarities, octadecyl and cholesterol, phenyl, nitrile, pentafluorophenylpropyl, diol and zwitterionic sulfobetaine and phosphorylcholine ligands bonded on silica, hybrid organic-silica and hydrosilated matrices. Both fully porous and core-shell column types were included. Preferential uptake of water by the columns can be described by Langmuir isotherms. Even though a diffuse rather than a compact adsorbed discrete layer of water on the adsorbent surface can be formed because of the unlimited miscibility of water with acetonitrile, for convenience, the preferentially adsorbed water was expressed in terms of a hypothetical monomolecular water layer equivalent in the inner pores. The uptake of water strongly depends on the polarity and type of the column. Less than one monomolecular water layer equivalent was adsorbed on moderate polar silica hydride-based stationary phases, Ascentis Express F5 and Ascentis Express CN column at the saturation capacity, while on more polar stationary phases, several water layer equivalents were up-taken from the mobile phase. The strongest affinity to water was observed on the ZIC cHILIC stationary phases, where more than nine water layer equivalents were adsorbed onto its surface at its saturation capacity. Columns with bonded hydroxyl and diol ligands show stronger water adsorption in comparison to bare silica. Columns based on hydrosilated silica generally show significantly decreased water uptake in comparison to stationary phases bonded on ordinary silica. Significant correlations were found between the water uptake and the separation selectivity for compounds with strong polarity differences. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation of polarization effects in the gramicidin A channel from ab initio molecular dynamics simulations.

PubMed

Timko, Jeff; Kuyucak, Serdar

2012-11-28

Polarization is an important component of molecular interactions and is expected to play a particularly significant role in inhomogeneous environments such as pores and interfaces. Here we investigate the effects of polarization in the gramicidin A ion channel by performing quantum mechanics/molecular mechanics molecular dynamics (MD) simulations and comparing the results with those obtained from classical MD simulations with non-polarizable force fields. We consider the dipole moments of backbone carbonyl groups and channel water molecules as well as a number of structural quantities of interest. The ab initio results show that the dipole moments of the carbonyl groups and water molecules are highly sensitive to the hydrogen bonds (H-bonds) they participate in. In the absence of a K(+) ion, water molecules in the channel are quite mobile, making the H-bond network highly dynamic. A central K(+) ion acts as an anchor for the channel waters, stabilizing the H-bond network and thereby increasing their average dipole moments. In contrast, the K(+) ion has little effect on the dipole moments of the neighboring carbonyl groups. The weakness of the ion-peptide interactions helps to explain the near diffusion-rate conductance of K(+) ions through the channel. We also address the sampling issue in relatively short ab initio MD simulations. Results obtained from a continuous 20 ps ab initio MD simulation are compared with those generated by sampling ten windows from a much longer classical MD simulation and running each window for 2 ps with ab initio MD. Both methods yield similar results for a number of quantities of interest, indicating that fluctuations are fast enough to justify the short ab initio MD simulations.

Transport governs flow-enhanced cell tethering through L-selectin at threshold shear.

PubMed

Yago, Tadayuki; Zarnitsyna, Veronika I; Klopocki, Arkadiusz G; McEver, Rodger P; Zhu, Cheng

2007-01-01

Flow-enhanced cell adhesion is a counterintuitive phenomenon that has been observed in several biological systems. Flow augments L-selectin-dependent adhesion by increasing the initial tethering of leukocytes to vascular surfaces and by strengthening their subsequent rolling interactions. Tethering or rolling might be influenced by physical factors that affect the formation or dissociation of selectin-ligand bonds. We recently demonstrated that flow enhanced rolling of L-selectin-bearing microspheres or neutrophils on P-selectin glycoprotein ligand-1 by force decreased bond dissociation. Here, we show that flow augmented tethering of these microspheres or cells to P-selectin glycoprotein ligand-1 by three transport mechanisms that increased bond formation: sliding of the sphere bottom on the surface, Brownian motion, and molecular diffusion. These results elucidate the mechanisms for flow-enhanced tethering through L-selectin.

Hydroxide-catalyzed bonding

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung (Inventor)

2003-01-01

A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

Grism manufacturing by low temperature mineral bonding

NASA Astrophysics Data System (ADS)

Kalkowski, G.; Grabowski, K.; Harnisch, G.; Flügel-Paul, T.; Zeitner, U.; Risse, S.

2017-09-01

By uniting a grating with a prism to a GRISM compound, the optical characteristics of diffractive and refractive elements can be favorably combined to achieve outstanding spectral resolution features. Ruling the grating structure into the prism surface is common for wavelengths around 1 μm and beyond, while adhesive bonding of two separate parts is generally used for shorter wavelengths and finer structures. We report on a manufacturing approach for joining the corresponding glass elements by the technology of hydrophilic direct bonding. This allows to manufacture the individual parts separately and subsequently combine them quasimonolithically by generating stiff and durable bonds of vanishing thickness, high strength and excellent transmission. With this approach for GRISM bonding, standard direct-write- or mask-lithography equipment may be used for the fabrication of the grating structure and the drawbacks of adhesive bonding (thermal mismatch, creep, aging) are avoided. The technology of hydrophilic bonding originates from "classical" optical contacting [1], but has been much improved and perfected during the last decades in the context of 3-dimensinal stacking Si-wafers for microelectronic applications [2]. It provides joins through covalent bonds of the Si-O-Si type at the nanometer scale, i.e. the elementary bond type in many minerals and glasses. The mineral nature of the bond is perfectly adapted to most optical materials and the extremely thin bonding layers generated with this technology are well suited for transmission optics. Creeping under mechanical load, as commonly observed with adhesive bonding, is not an issue. With respect to diffusion bonding, which operates at rather high temperatures close to the glass transition or crystal melting point, hydrophilic bonding is a low temperature process that needs only moderate heating. This facilitates provision of handling and alignment means for the individual parts during the set-up stages and greatly eases joining optical materials of different thermal expansion. The technology has been successfully used in the past for bonding various glasses as well as crystalline optical materials [3, 4]. Here we will focus on bonding prisms elements and binary gratings of fused silica with and without coatings at the bonding interface. Further, preliminary results on bonding prism-grating-prism (PGP) combinations will be presented.

Interconnect mechanisms in microelectronic packaging

NASA Astrophysics Data System (ADS)

Roma, Maria Penafrancia C.

Global economic, environmental and market developments caused major impact in the microelectronics industry. Astronomical rise of gold metal prices over the last decade shifted the use of copper and silver alloys as bonding wires. Environmental legislation on the restriction of the use of Pb launched worldwide search for lead-free solders and platings. Finally, electrical and digital uses demanded smaller, faster and cheaper devices. Ultra-fine pitch bonding, decreasing bond wire sizes and hard to bond substrates have put the once-robust stitch bond in the center of reliability issues due to stitch bond lift or open wires .Unlike the ball bond, stitch bonding does not lead to intermetallic compound formation but adhesion is dependent on mechanical deformation, interdiffusion, solid solution formation, void formation and mechanical interlocking depending on the wire material, bond configuration, substrate type , thickness and surface condition. Using Au standoff stitch bonds on NiPdAu plated substrates eliminated stitch bond lift even when the Au and Pd layers are reduced. Using the Matano-Boltzmann analysis on a STEM (Scanning Transmission Analysis) concentration profile the interdiffusion coefficient is measured to be 10-16 cm 2/s. Wire pull strength data showed that the wire pull strength is 0.062N and increases upon stress testing. Meanwhile, coating the Cu wire with Pd, not only increases oxidation resistance but also improved adhesion due to the formation of a unique interfacial adhesion layers. Adhesion strength as measured by pull showed the Cu wire bonded to Ag plated Cu substrate (0.132N) to be stronger than the Au wire bonded on the same substrate (0.124N). Ag stitch bonded to Au is predicted to be strong but surface modification made the adhesion stronger. However, on the Ag ball bonded to Al showed multiple IMC formation with unique morphology exposed by ion milling and backscattered scanning electron microscopy. Adding alloying elements in the Ag wire alloy showed differences in adhesion strength and IMC formation. Bond strength by wire pull testing showed the 95Ag alloy with higher values while shear bond testing showed the 88Ag higher bond strength. Use of Cu pillars in flip chips and eutectic bonding in wafer level chip scale packages are direct consequences of diminishing interconnect dimension as a result of the drive for miniaturization. The combination of Cu-Sn interdiffusion, Kirkendall mechanism and heterogeneous vacancy precipitation are the main causes of IMC and void formation in Cu pillar - Sn solder - Cu lead frame sandwich structure. However, adding a Ni barrier agent showed less porous IMC layer as well as void formation as a result of the modified Cu and Sn movement well as the void formation. Direct die to die bonding using Al-Ge eutectic bonds is necessary when 3D integration is needed to reduce the footprint of a package. Hermeticity and adhesion strength are a function of the Al/Ge thickness ratio, bonding pressure, temperature and time. Scanning Electron Microscope (SEM) and Focused Ion Beam (FIB) allowed imaging of interfacial microstructures, porosity, grain morphology while Scanning Transmission Electron microscope (STEM) provided diffusion profile and confirmed interdiffusion. Ion polishing technique provided information on porosity and when imaged using backscattered mode, grain structure confirmed mechanical deformation of the bonds. Measurements of the interfacial bond strength are made by wire pull tests and ball shear tests based on existing industry standard tests. However, for the Al-Ge eutectic bonds, no standard strength is available so a test is developed using the stud pull test method using the Dage 4000 Plus to yield consistent results. Adhesion strengths of 30-40 MPa are found for eutectic bonded packages however, as low as 20MPa was measured in low temperature bonded areas.

Binder-free Si nanoparticle electrode with 3D porous structure prepared by electrophoretic deposition for lithium-ion batteries.

PubMed

Yang, Yang; Chen, Dingqiong; Liu, Bo; Zhao, Jinbao

2015-04-15

A binder-free silicon (Si) based electrode for lithium-ion battery was fabricated in an organic solvent through one-step electrophoretic deposition (EPD). The nanosized Si and acetylene black (AB) particles were bonded tightly together to form a homogeneous co-deposited film with 3D porous structure through the EPD process. The 3D porous structure provides buffer spaces to alleviate the mechanical stress due to silicon volume change during the cycling and improves lithium-ion conductivity by shortening ion diffusion length and better ion conducting pathway. The electrode prepared with 5 s deposition duration shows the best cycling performance among electrodes fabricated by EPD method, and thus, it was selected to be compared with the silicon electrode prepared by the conventional method. Our results demonstrate that the Si nanoparticle electrode prepared through EPD exhibits smaller cycling capacity decay rate and better rate capability than the electrode prepared by the conventional method.

METHOD OF MAKING TUNGSTEN FILAMENTS

DOEpatents

Frazer, J.W.

1962-12-18

A method of making tungsten filaments is described in which the tungsten is completely free of isotope impurities in the range of masses 234 to 245 for use in mass spectrometers. The filament comprises a tantalum core generally less than 1 mil in diameter having a coating of potassium-free tantalum-diffused tungsten molecularly bonded thereto. In the preferred process of manufacture a short, thin tantalum filament is first mounted between terminal posts mounted in insulated relation through a backing plate. The tungsten is most conveniently vapor plated onto the tantalum by a tungsten carbonyl vapor decomposition method having a critical step because of the tendency of the tantalum to volatilize at the temperature of operntion of the filament. The preferred recipe comprises volatilizing tantalum by resistance henting until the current drops by about 40%, cutting the voltage back to build up the tungsten, and then gradually building the temperature back up to balance the rate of tungsten deposition with the rate of tantalum volatilization. (AEC)

Nonequilibrium Self-Assembly of π-Conjugated Oligopeptides in Solution.

PubMed

Li, Bo; Li, Songsong; Zhou, Yuecheng; Ardoña, Herdeline Ann M; Valverde, Lawrence R; Wilson, William L; Tovar, John D; Schroeder, Charles M

2017-02-01

Supramolecular assembly is a powerful method that can be used to generate materials with well-defined structures across multiple length scales. Supramolecular assemblies consisting of biopolymer-synthetic polymer subunits are specifically known to exhibit exceptional structural and functional diversity as well as programmable control of noncovalent interactions through hydrogen bonding in biopolymer subunits. Despite recent progress, there is a need to control and quantitatively understand assembly under nonequilibrium conditions. In this work, we study the nonequilibrium self-assembly of π-conjugated synthetic oligopeptides using a combination of experiments and analytical modeling. By isolating an aqueous peptide solution droplet within an immiscible organic layer, the rate of peptide assembly in the aqueous solution can be controlled by tuning the transport rate of acid that is used to trigger assembly. Using this approach, peptides are guided to assemble under reaction-dominated and diffusion-dominated conditions, with results showing a transition from a diffusion-limited reaction front to spatially homogeneous assembly as the transport rate of acid decreases. Interestingly, our results show that the morphology of self-assembled peptide fibers is controlled by the assembly kinetics such that increasingly homogeneous structures of self-assembled synthetic oligopeptides were generally obtained using slower rates of assembly. We further developed an analytical reaction-diffusion model to describe oligopeptide assembly, and experimental results are compared to the reaction-diffusion model across a range of parameters. Overall, this work highlights the importance of molecular self-assembly under nonequilibrium conditions, specifically showing that oligopeptide assembly is governed by a delicate balance between reaction kinetics and transport processes.

Functioning of inorganic/organic battery separators in silver-zinc cells

NASA Technical Reports Server (NTRS)

Philipp, W. H.; May, C. E.

1976-01-01

The results of three experimental studies related to the inorganic/organic battery separator operating mechanism are described: saponification of the plasticizer, resistivity of the simulated separators, and zincate diffusion through the separators. The inorganic/organic separator appears to be a particular example of a general class of ionic conducting films composed of inorganic fillers and/or substrates bonded together by an organic polymer containing an incompatible plasticizer that may be leached by the electrolyte. The I/O separator functions as a microporous film of varying tortuosity with essentially no specific chemical inhibition to zincate diffusion.

Growth of Interfacial Intermetallic Compound Layer in Diffusion-Bonded SAC-Cu Solder Joints During Different Types of Thermomechanical Excursion

NASA Astrophysics Data System (ADS)

Kanjilal, Anwesha; Kumar, Praveen

2018-01-01

The effects of mechanical strain on the growth kinetics of interfacial intermetallic compounds (IMCs) sandwiched between Cu substrate and Sn-1.0 wt.%Ag-0.5 wt.%Cu (SAC105) solder have been investigated. Isothermal aging (IA) at 70°C and 125°C, and thermal cycling (TC) as well as thermomechanical cycling (TMC) with shear strain of 12.8% per cycle between -25°C and 125°C were applied to diffusion-bonded solder joints to study the growth behavior of the interfacial IMC layer under various types of thermomechanical excursion (TME). The microstructure of the solder joint tested under each TME was observed at regular intervals. It was observed that the growth rate of the IMC layer was higher in the case of TMC compared with TC or IA. This increased growth rate of the IMC layer in the presence of mechanical strain suggests an additional driving force that enhances the growth kinetics of the IMC. Finite element analysis was performed to gain insight into the effect of TC and TMC on the stress field in the solder joint, especially near the interface between the solder and the substrate. Finally, an analytical model was developed to quantify the effect of strain on the effective diffusivity and express the growth kinetics for all three types of TME using a single expression.

Aggregation Number in Water/n-Hexanol Molecular Clusters Formed in Cyclohexane at Different Water/n-Hexanol/Cyclohexane Compositions Calculated by Titration 1H NMR.

PubMed

Flores, Mario E; Shibue, Toshimichi; Sugimura, Natsuhiko; Nishide, Hiroyuki; Moreno-Villoslada, Ignacio

2017-11-09

Upon titration of n-hexanol/cyclohexane mixtures of different molar compositions with water, water/n-hexanol clusters are formed in cyclohexane. Here, we develop a new method to estimate the water and n-hexanol aggregation numbers in the clusters that combines integration analysis in one-dimensional 1 H NMR spectra, diffusion coefficients calculated by diffusion-ordered NMR spectroscopy, and further application of the Stokes-Einstein equation to calculate the hydrodynamic volume of the clusters. Aggregation numbers of 5-15 molecules of n-hexanol per cluster in the absence of water were observed in the whole range of n-hexanol/cyclohexane molar fractions studied. After saturation with water, aggregation numbers of 6-13 n-hexanol and 0.5-5 water molecules per cluster were found. O-H and O-O atom distances related to hydrogen bonds between donor/acceptor molecules were theoretically calculated using density functional theory. The results show that at low n-hexanol molar fractions, where a robust hydrogen-bond network is held between n-hexanol molecules, addition of water makes the intermolecular O-O atom distance shorter, reinforcing molecular association in the clusters, whereas at high n-hexanol molar fractions, where dipole-dipole interactions dominate, addition of water makes the intermolecular O-O atom distance longer, weakening the cluster structure. This correlates with experimental NMR results, which show an increase in the size and aggregation number in the clusters upon addition of water at low n-hexanol molar fractions, and a decrease of these magnitudes at high n-hexanol molar fractions. In addition, water produces an increase in the proton exchange rate between donor/acceptor molecules at all n-hexanol molar fractions.

Au-free ohmic Ti/Al/TiN contacts to UID n-GaN fabricated by sputter deposition

NASA Astrophysics Data System (ADS)

Garbe, V.; Weise, J.; Motylenko, M.; Münchgesang, W.; Schmid, A.; Rafaja, D.; Abendroth, B.; Meyer, D. C.

2017-02-01

The fabrication and characterization of an Au-free Ti/Al/TiN (20/100/100 nm) contact stack to unintentionally doped n-GaN with TiN serving as the diffusion barrier is presented. Sputter deposition and lift-off in combination with post deposition annealing at 850 °C are used for contact formation. After annealing, contact shows ohmic behavior to n-GaN and a specific contact resistivity of 1.60 × 10-3 Ω cm2. To understand the contact formation on the microscopic scale, the contact was characterized by current-voltage measurements, linear transmission line method, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The results show the formation of Ti-N bonds at the GaN/Ti interface in the as-deposited stack. Annealing leads to diffusion of Ti, Al, Ga, and N, and the remaining metallic Ti is fully consumed by the formation of the intermetallic tetragonal Al3Ti phase. Native oxide from the GaN surface is trapped during annealing and accumulated in the Al interlayer. The TiN capping layer, however, was chemically stable during annealing. It prevented oxidation of the Ti/Al contact bilayer successfully and thus proved to be a well suitable diffusion barrier with ideal compatibility to the Ti/Al contact metallization.

The Influence of the Coating Deposition Process on the Interdiffusion Behavior Between Nickel-Based Superalloys and MCrAlY Bond Coats

NASA Astrophysics Data System (ADS)

Elsaß, M.; Frommherz, M.; Oechsner, M.

2018-02-01

In this work, interdiffusion between two nickel-based superalloys and two MCrAlY bond coats is investigated. The MCrAlY bond coats were applied using two different spraying processes, high velocity oxygen fuel spraying (HVOF) and low-pressure plasma spraying. Of primary interest is the evolution of Kirkendall porosity, which can form at the interface between substrate and bond coat and depends largely on the chemical compositions of the coating and substrate. Experimental evidence further suggested that the formation of Kirkendall porosity depends on the coating deposition process. Formation of porosity at the interface causes a degradation of the bonding strength between substrate and coating. After coating deposition, the samples were annealed at 1050 °C for up to 2000 h. Microstructural and compositional analyses were performed to determine and evaluate the Kirkendall porosity. The results reveal a strong influence of both the coating deposition process and the chemical compositions. The amount of Kirkendall porosity formed, as well as the location of appearance, is largely influenced by the coating deposition process. In general, samples with bond coats applied by means of HVOF show accelerated element diffusion. It is hypothesized that recrystallization of the substrate material is a main root cause for these observations.

Potential surfaces for O atom-polymer reactions

NASA Technical Reports Server (NTRS)

Laskowski, B. C.; Jaffe, R. L.

1987-01-01

Ab initio quantum chemistry methods are used to study the energetics of interactions of O atoms with organic compounds. Polyethylene (CH2)n has been chosen as the model system to study the interactions of O(3P) and O(1D) atoms with polymers. In particular, H abstraction is investigated and polyethylene is represented by a C3 (propane) oligomeric model. The gradient method, as implemented in the GRADSCF package of programs, is used to determine the geometries and energies of products and reactants. The saddle point, barrier geometry is determined by minimizing the squares of the gradients of the potential with respect to the internal coordinates. To correctly describe the change in bonding during the reaction at least a two configuration MCSCF (multiconfiguration self consistent field) or GVB (generalized valence bond) wave function has to be used. Basis sets include standard Pople and Dunning sets, however, increased with polarization functions and diffuse p functions on both the C and O atoms. The latter is important due to the O(-) character of the wave function at the saddle point and products. Normal modes and vibrational energy levels are given for the reactants, saddle points and products. Finally, quantitative energetics are obtained by implementing a small CAS (complete active space) approach followed by limited configuration interaction (CI) calculations. Comparisons are made with available experimental data.

Computer Science Techniques Applied to Parallel Atomistic Simulation

NASA Astrophysics Data System (ADS)

Nakano, Aiichiro

1998-03-01

Recent developments in parallel processing technology and multiresolution numerical algorithms have established large-scale molecular dynamics (MD) simulations as a new research mode for studying materials phenomena such as fracture. However, this requires large system sizes and long simulated times. We have developed: i) Space-time multiresolution schemes; ii) fuzzy-clustering approach to hierarchical dynamics; iii) wavelet-based adaptive curvilinear-coordinate load balancing; iv) multilevel preconditioned conjugate gradient method; and v) spacefilling-curve-based data compression for parallel I/O. Using these techniques, million-atom parallel MD simulations are performed for the oxidation dynamics of nanocrystalline Al. The simulations take into account the effect of dynamic charge transfer between Al and O using the electronegativity equalization scheme. The resulting long-range Coulomb interaction is calculated efficiently with the fast multipole method. Results for temperature and charge distributions, residual stresses, bond lengths and bond angles, and diffusivities of Al and O will be presented. The oxidation of nanocrystalline Al is elucidated through immersive visualization in virtual environments. A unique dual-degree education program at Louisiana State University will also be discussed in which students can obtain a Ph.D. in Physics & Astronomy and a M.S. from the Department of Computer Science in five years. This program fosters interdisciplinary research activities for interfacing High Performance Computing and Communications with large-scale atomistic simulations of advanced materials. This work was supported by NSF (CAREER Program), ARO, PRF, and Louisiana LEQSF.

In Situ Neutron Diffraction of Rare-Earth Phosphate Proton Conductors Sr/Ca-doped LaPO4 at Elevated Temperatures

NASA Astrophysics Data System (ADS)

Al-Wahish, Amal; Al-Binni, Usama; Bridges, C. A.; Huq, A.; Bi, Z.; Paranthaman, M. P.; Tang, S.; Kaiser, H.; Mandrus, D.

Acceptor-doped lanthanum orthophosphates are potential candidate electrolytes for proton ceramic fuel cells. We combined neutron powder diffraction (NPD) at elevated temperatures up to 800° C , X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) to investigate the crystal structure, defect structure, thermal stability and surface topography. NPD shows an average bond length distortion in the hydrated samples. We employed Quasi-Elastic Neutron Scattering (QENS) and electrochemical impedance spectroscopy (EIS) to study the proton dynamics of the rare-earth phosphate proton conductors 4.2% Sr/Ca-doped LaPO4. We determined the bulk diffusion and the self-diffusion coefficients. Our results show that QENS and EIS are probing fundamentally different proton diffusion processes. Supported by the U.S. Department of Energy.

The impact of processing parameters on the properties of Zn-bonded Nd-Fe-B magnets

NASA Astrophysics Data System (ADS)

Kelhar, Luka; Zavašnik, Janez; McGuiness, Paul; Kobe, Spomenka

2016-12-01

We report on the effect of loading factor and pressure on the density and the magnetic properties of Zn-bonded Nd-Fe-B magnets produced by pulsed-electric-current sintering (PECS). The idea behind this study is to fabricate bonded magnets with a metallic binder in order for the bonded magnet to operate at temperatures higher than 180 °C: the current upper-limit for polymer-bonded magnets. These composites are made of hard-magnetic powder in the form of melt-spun ribbons bonded with the low-melting-point metal Zn. The binder additions were varied from 10 to 30 wt%, and pressures of 50 and 500 MPa were applied. The high-pressure mode with 20 wt% Zn resulted in a 24% increase of Jr, compared to the low-pressure mode. The magnetic measurements revealed a maximum remanence of 0.64 T for 10 wt% Zn, while the coercivity is largely unaffected by the processing conditions. The density of the composites was up to 7.0 g/cm3, corresponding to 94% of the theoretical density. Compared to commercial polymer-bonded magnets, the Zn-bonded counterparts exhibit a slightly lower Jr, but the coercivity is retained. We show that there is a minor diffusion of Zn into the Nd-Fe-B, forming a 1 μm thin transition layer, but it does not harm the magnetic properties. These metal-bonded Nd-Fe-B magnets are ideal for use in high-temperature automotive applications like under-the-hood sensors and other magnet-based devices that are close to the engine.

Method and apparatus for component separation using microwave energy

DOEpatents

Morrow, Marvin S.; Schechter, Donald E.; Calhoun, Jr., Clyde L.

2001-04-03

A method for separating and recovering components includes the steps of providing at least a first component bonded to a second component by a microwave absorbent adhesive bonding material at a bonding area to form an assembly, the bonding material disposed between the components. Microwave energy is directly and selectively applied to the assembly so that substantially only the bonding material absorbs the microwave energy until the bonding material is at a debonding state. A separation force is applied while the bonding material is at the debonding state to permit disengaging and recovering the components. In addition, an apparatus for practicing the method includes holders for the components.

Modified low-temperture direct bonding method for vacuum microelectronics application

NASA Astrophysics Data System (ADS)

Ju, Byeong-Kwon; Lee, Duck-Jung; Choi, Woo-Beom; Lee, Yun-Hi; Jang, Jin; Lee, Kwang-Bae; Oh, Myung-Hwan

1997-06-01

This paper presents the process and experimental results for the improved silicon-to-glass bonding using silicon direct bonding (SDB) followed by anodic bonding. The initial bonding between glass and silicon was caused by the hydrophilic surfaces of silicon-glass ensemble using SDB method. Then the initially bonded specimen had to be strongly bonded by anodic bonding process. The effects of the bonding process parameters on the interface energy were investigated as functions of the bonding temperature and voltage. We found that the specimen which was bonded using SDB process followed by anodic bonding process had higher interface energy than one using anodic bonding process only. The main factor contributing to the higher interface energy in the glass-to-silicon assemble bonded by SDB followed by anodic bonding was investigated by secondary ion mass spectroscopy analysis.

Heat treatment of transparent Yb:YAG and YAG ceramics and its influence on laser performance

NASA Astrophysics Data System (ADS)

Fujioka, Kana; Mochida, Tetsuo; Fujimoto, Yasushi; Tokita, Shigeki; Kawanaka, Junji; Maruyama, Momoko; Sugiyama, Akira; Miyanaga, Noriaki

2018-05-01

Composite transparent ceramic materials are promising for improving the performance of high-average-power lasers. A combination of room-temperature bonding via surface treatment by a fast atom beam and diffusion bonding via heating, which effectively controls the ion diffusion distance near the interface, makes the laser materials suitable for a variety of oscillator/amplifier. During the heat treatment of yttrium aluminum garnet (YAG) ceramics, the Si ions in the solid solution of the sintering aid incorporated within the grains were seen to segregate at the grain boundary, resulting in an increase of scattering sites. The number density and size of the scattering sites strongly depended on the post-heating temperature rather than the heating time. Specifically, heating at 1300 °C did not affect the transmittance of the YAG ceramic, whereas both the size and number of scattering sites substantially increased with a heat treatment at 1400 °C. The laser oscillation experiment using cryogenically-cooled Yb:YAG ceramics exhibited heating temperature dependence of the slope efficiency owing to the increasing scattering loss.

Si-H bond dynamics in hydrogenated amorphous silicon

NASA Astrophysics Data System (ADS)

Scharff, R. Jason; McGrane, Shawn D.

2007-08-01

The ultrafast structural dynamics of the Si-H bond in the rigid solvent environment of an amorphous silicon thin film is investigated using two-dimensional infrared four-wave mixing techniques. The two-dimensional infrared (2DIR) vibrational correlation spectrum resolves the homogeneous line shapes ( <2.5cm-1 linewidth) of the 0→1 and 1→2 vibrational transitions within the extensively inhomogeneously broadened ( 78cm-1 linewidth) Si-H vibrational band. There is no spectral diffusion evident in correlation spectra obtained at 0.2, 1, and 4ps waiting times. The Si-H stretching mode anharmonic shift is determined to be 84cm-1 and decreases slightly with vibrational frequency. The 1→2 linewidth increases with vibrational frequency. Frequency dependent vibrational population times measured by transient grating spectroscopy are also reported. The narrow homogeneous line shape, large inhomogeneous broadening, and lack of spectral diffusion reported here present the ideal backdrop for using a 2DIR probe following electronic pumping to measure the transient structural dynamics implicated in the Staebler-Wronski degradation [Appl. Phys. Lett. 31, 292 (1977)] in a-Si:H based solar cells.

Density-dependent liquid nitromethane decomposition: molecular dynamics simulations based on ReaxFF.

PubMed

Rom, Naomi; Zybin, Sergey V; van Duin, Adri C T; Goddard, William A; Zeiri, Yehuda; Katz, Gil; Kosloff, Ronnie

2011-09-15

The decomposition mechanism of hot liquid nitromethane at various compressions was studied using reactive force field (ReaxFF) molecular dynamics simulations. A competition between two different initial thermal decomposition schemes is observed, depending on compression. At low densities, unimolecular C-N bond cleavage is the dominant route, producing CH(3) and NO(2) fragments. As density and pressure rise approaching the Chapman-Jouget detonation conditions (∼30% compression, >2500 K) the dominant mechanism switches to the formation of the CH(3)NO fragment via H-transfer and/or N-O bond rupture. The change in the decomposition mechanism of hot liquid NM leads to a different kinetic and energetic behavior, as well as products distribution. The calculated density dependence of the enthalpy change correlates with the change in initial decomposition reaction mechanism. It can be used as a convenient and useful global parameter for the detection of reaction dynamics. Atomic averaged local diffusion coefficients are shown to be sensitive to the reactions dynamics, and can be used to distinguish between time periods where chemical reactions occur and diffusion-dominated, nonreactive time periods. © 2011 American Chemical Society

The Relaxation of Vicinal (001) with ZigZag [110] Steps

NASA Astrophysics Data System (ADS)

Hawkins, Micah; Hamouda, Ajmi Bh; González-Cabrera, Diego Luis; Einstein, Theodore L.

2012-02-01

This talk presents a kinetic Monte Carlo study of the relaxation dynamics of [110] steps on a vicinal (001) simple cubic surface. This system is interesting because [110] steps have different elementary excitation energetics and favor step diffusion more than close-packed [100] steps. In this talk we show how this leads to relaxation dynamics showing greater fluctuations on a shorter time scale for [110] steps as well as 2-bond breaking processes being rate determining in contrast to 3-bond breaking processes for [100] steps. The existence of a steady state is shown via the convergence of terrace width distributions at times much longer than the relaxation time. In this time regime excellent fits to the modified generalized Wigner distribution (as well as to the Berry-Robnik model when steps can overlap) were obtained. Also, step-position correlation function data show diffusion-limited increase for small distances along the step as well as greater average step displacement for zigzag steps compared to straight steps for somewhat longer distances along the step. Work supported by NSF-MRSEC Grant DMR 05-20471 as well as a DOE-CMCSN Grant.

Water Dynamics in Nafion Fuel Cell Membranes: the Effects of Confinement and Structural Changes on the Hydrogen Bond Network

PubMed Central

Moilanen, David E.; Piletic, Ivan R.; Fayer, Michael D.

2008-01-01

The complex environments experienced by water molecules in the hydrophilic channels of Nafion membranes are studied by ultrafast infrared pump-probe spectroscopy. A wavelength dependent study of the vibrational lifetime of the O-D stretch of dilute HOD in H2O confined in Nafion membranes provides evidence of two distinct ensembles of water molecules. While only two ensembles are present at each level of membrane hydration studied, the characteristics of the two ensembles change as the water content of the membrane changes. Time dependent anisotropy measurements show that the orientational motions of water molecules in Nafion membranes are significantly slower than in bulk water and that lower hydration levels result in slower orientational relaxation. Initial wavelength dependent results for the anisotropy show no clear variation in the time scale for orientational motion across a broad range of frequencies. The anisotropy decay is analyzed using a model based on restricted orientational diffusion within a hydrogen bond configuration followed by total reorientation through jump diffusion. PMID:18728757

Local structure of Rb{sub 2}Li{sub 4}(SeO{sub 4}){sub 3}{center_dot}2H{sub 2}O by the modeling of X-ray diffuse scattering - from average-structure to microdomain model

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

Komornicka, Dorota; Wolcyrz, Marek, E-mail: m.wolcyrz@int.pan.wroc.pl; Pietraszko, Adam

2012-08-15

Local structure of dirubidium tetralithium tris(selenate(VI)) dihydrate - Rb{sub 2}Li{sub 4}(SeO{sub 4}){sub 3}{center_dot} 2H{sub 2}O has been determined basing on the modeling of X-ray diffuse scattering. The origin of observed structured diffuse streaks is SeO{sub 4} tetrahedra switching between two alternative positions in two quasi-planar layers existing in each unit cell and formation of domains with specific SeO{sub 4} tetrahedra configuration locally fulfilling condition for C-centering in the 2a Multiplication-Sign 2b Multiplication-Sign c superstructure cell. The local structure solution is characterized by a uniform distribution of rather large domains (ca. thousand of unit cells) in two layers, but also monodomainsmore » can be taken into account. Inside a single domain SeO{sub 4} tetrahedra are ordered along ab-diagonal forming two-string ribbons. Inside the ribbons SeO{sub 4} and LiO{sub 4} tetrahedra share the oxygen corners, whereas ribbons are bound to each other by a net of hydrogen bonds and fastened by corner sharing SeO{sub 4} tetrahedra of the neighboring layers. - Graphical abstract: Experimental sections of the reciprocal space showing diffraction effects observed for RLSO. Bragg spots are visible on sections with integer indices (1 kl section - on the left), streaks - on sections with fractional ones (1.5 kl section - on the right). At the center: resulting local structure of the A package modeled as a microdomain: two-string ribbons of ordered oxygen-corners-sharing SeO{sub 4} and LiO{sub 4} terahedra extended along ab-diagonal are seen; ribbons are bound by hydrogen bonds (shown in pink); the multiplied 2a Multiplication-Sign 2b unit cell is shown. Highlights: Black-Right-Pointing-Pointer X-ray diffuse scattering in RLSO was registered and modeled. Black-Right-Pointing-Pointer The origin of diffuse streaks is SeO{sub 4} tetrahedra switching in two structure layers. Black-Right-Pointing-Pointer The local structure is characterized by a uniform distribution of microdomains. Black-Right-Pointing-Pointer Inside a single domain SeO{sub 4} tetrahedra are ordered along ab-diagonal forming ribbons. Black-Right-Pointing-Pointer The ribbons are bound to each other by a net of hydrogen bonds.« less

Room-temperature bonding of epitaxial layer to carbon-cluster ion-implanted silicon wafers for CMOS image sensors

NASA Astrophysics Data System (ADS)

Koga, Yoshihiro; Kadono, Takeshi; Shigematsu, Satoshi; Hirose, Ryo; Onaka-Masada, Ayumi; Okuyama, Ryousuke; Okuda, Hidehiko; Kurita, Kazunari

2018-06-01

We propose a fabrication process for silicon wafers by combining carbon-cluster ion implantation and room-temperature bonding for advanced CMOS image sensors. These carbon-cluster ions are made of carbon and hydrogen, which can passivate process-induced defects. We demonstrated that this combination process can be used to form an epitaxial layer on a carbon-cluster ion-implanted Czochralski (CZ)-grown silicon substrate with a high dose of 1 × 1016 atoms/cm2. This implantation condition transforms the top-surface region of the CZ-grown silicon substrate into a thin amorphous layer. Thus, an epitaxial layer cannot be grown on this implanted CZ-grown silicon substrate. However, this combination process can be used to form an epitaxial layer on the amorphous layer of this implanted CZ-grown silicon substrate surface. This bonding wafer has strong gettering capability in both the wafer-bonding region and the carbon-cluster ion-implanted projection range. Furthermore, this wafer inhibits oxygen out-diffusion to the epitaxial layer from the CZ-grown silicon substrate after device fabrication. Therefore, we believe that this bonding wafer is effective in decreasing the dark current and white-spot defect density for advanced CMOS image sensors.

Direct evidence for dominant bond-directional interactions in a honeycomb lattice iridate Na 2IrO 3

DOE PAGES

Hwan Chun, Sae; Kim, Jong-Woo; Kim, Jungho; ...

2015-05-11

We show that heisenberg interactions are ubiquitous in magnetic materials and play a central role in modelling and designing quantum magnets. Bond-directional interactions offer a novel alternative to Heisenberg exchange and provide the building blocks of the Kitaev model, which has a quantum spin liquid as its exact ground state. Honeycomb iridates, A 2IrO 3 (A = Na, Li), offer potential realizations of the Kitaev magnetic exchange coupling, and their reported magnetic behaviour may be interpreted within the Kitaev framework. However, the extent of their relevance to the Kitaev model remains unclear, as evidence for bond-directional interactions has so farmore » been indirect. Here we present direct evidence for dominant bond-directional interactions in antiferromagnetic Na 2IrO 3 and show that they lead to strong magnetic frustration. Diffuse magnetic X-ray scattering reveals broken spin-rotational symmetry even above the Néel temperature, with the three spin components exhibiting short-range correlations along distinct crystallographic directions. Lastly, this spin- and real-space entanglement directly uncovers the bond-directional nature of these interactions, thus providing a direct connection between honeycomb iridates and Kitaev physics.« less

Time-dependent vibrational spectral analysis of first principles trajectory of methylamine with wavelet transform.

PubMed

Biswas, Sohag; Mallik, Bhabani S

2017-04-12

The fluctuation dynamics of amine stretching frequencies, hydrogen bonds, dangling N-D bonds, and the orientation profile of the amine group of methylamine (MA) were investigated under ambient conditions by means of dispersion-corrected density functional theory-based first principles molecular dynamics (FPMD) simulations. Along with the dynamical properties, various equilibrium properties such as radial distribution function, spatial distribution function, combined radial and angular distribution functions and hydrogen bonding were also calculated. The instantaneous stretching frequencies of amine groups were obtained by wavelet transform of the trajectory obtained from FPMD simulations. The frequency-structure correlation reveals that the amine stretching frequency is weakly correlated with the nearest nitrogen-deuterium distance. The frequency-frequency correlation function has a short time scale of around 110 fs and a longer time scale of about 1.15 ps. It was found that the short time scale originates from the underdamped motion of intact hydrogen bonds of MA pairs. However, the long time scale of the vibrational spectral diffusion of N-D modes is determined by the overall dynamics of hydrogen bonds as well as the dangling ND groups and the inertial rotation of the amine group of the molecule.

Mössbauer characterization of joints of steel pieces in transient liquid phase bonding experiences

NASA Astrophysics Data System (ADS)

di Luozzo, N.; Martínez Stenger, P. F.; Canal, J. P.; Fontana, M. R.; Arcondo, B.

2011-11-01

Joining of seamless, low carbon, steel tubes were performed by means of Transient Liquid Phase Bonding process employing a foil of Fe-Si-B metallic glass as filler material. The influence of the main parameters of the process was evaluated: temperature, holding time, pressure and post weld heat treatment. Powder samples were obtained from the joint of tubes and characterized employing Mössbauer Spectroscopy in transmission geometry. The sampling was performed both in tubes successfully welded and in those which show joint defects. The results obtained are correlated with the obtained microstructure and the diffusion of Si and B during the process.

Metal-atom Interactions and Clustering in Organic Semiconductor Systems

NASA Astrophysics Data System (ADS)

Tomita, Yoko; Park, Tea-uk; Nakayama, Takashi

2017-07-01

The interatomic interactions and clustering of metal atoms have been studied by first-principles calculations in graphene, pentacene, and polyacetylene as representative organic systems. It is shown that long-range repulsive Coulomb interaction appears between metal atoms with small electronegativity such as Al due to their ionization on host organic molecules, inducing their scattered distribution in organic systems. On the other hand, metal atoms with large electronegativity such as Au are weakly bonded to organic molecules, easily diffuse in molecular solids, and prefer to combine with each other owing to their short-range strong metallic-bonding interaction, promoting metal cluster generation in organic systems.

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry.

PubMed

Stinson, Craig A; Zhang, Wenpeng; Xia, Yu

2018-03-01

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS. Graphical Abstract ᅟ.

UV Lamp as a Facile Ozone Source for Structural Analysis of Unsaturated Lipids Via Electrospray Ionization-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Stinson, Craig A.; Zhang, Wenpeng; Xia, Yu

2018-03-01

Ozonolysis of alkene functional groups is a type of highly specific and effective chemical reaction, which has found increasing applications in structural analysis of unsaturated lipids via coupling with mass spectrometry (MS). In this work, we utilized a low-pressure mercury lamp (6 W) to initiate ozonolysis inside electrospray ionization (ESI) sources. By placing the lamp near a nanoESI emitter that partially transmits 185 nm ultraviolet (UV) emission from the lamp, dissolved dioxygen in the spray solution was converted into ozone, which subsequently cleaved the double bonds within fatty acyls of lipids. Solvent conditions, such as presence of water and acid solution pH, were found to be critical in optimizing ozonolysis yields. Fast (on seconds time scale) and efficient (50%-100% yield) ozonolysis was achieved for model unsaturated phospholipids and fatty acids with UV lamp-induced ozonolysis incorporated on a static and an infusion nanoESI source. The method was able to differentiate double bond location isomers and identify the geometry of the double bond based on yield. The analytical utility of UV lamp-induced ozonolysis was further demonstrated by implementation on a liquid chromatography (LC)-MS platform. Ozonolysis was effected in a flow microreactor that was made from ozone permeable tubing, so that ambient ozone produced by the lamp irradiation could diffuse into the reactor and induce online ozonolysis post-LC separation and before ESI-MS. [Figure not available: see fulltext.

Comparative spectroscopic analysis of urinary calculi inhibition by Larrea Tridentata infusion and NDGA chemical extract

NASA Astrophysics Data System (ADS)

Manciu, Felicia

2012-10-01

In the present comparative spectroscopic study we try to understand calcium oxalate kidney stone formation as well as its inhibition by using a traditional medicine approach with Larrea Tridentata (LT) herbal extracts and nordihydroguaiaretic acid (NDGA), which is a chemical extract of the LT bush. The samples were synthesized without and with LT or NDGA using a simplified single diffusion gel growth technique. While the use of infusion from LT decreases the sizes of calcium oxalate crystals and also changes their structure from monohydrate for pure crystals to dihydrate for crystals grown with different amounts of inhibitor, both Raman and infrared absorption spectroscopic techniques, which are the methods of analysis employed in this work, reveal that NDGA is not responsible for the change in the morphology of calcium oxalate crystals and does not contribute significantly to the inhibition process. The presence of NDGA slightly affects the structure of the crystals by modifying the strength of the C-C bonds as seen in the Raman data. Also, the current infrared absorption results demonstrate the presence of NDGA in the samples through a vibrational line that corresponds to the double bond between carbon atoms of the ester group of NDGA.

One-step in situ synthesis of graphene–TiO{sub 2} nanorod hybrid composites with enhanced photocatalytic activity

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

Sun, Mingxuan, E-mail: mingxuansun@sues.edu.cn; Li, Weibin; Sun, Shanfu

2015-01-15

Chemically bonded graphene/TiO{sub 2} nanorod hybrid composites with superior dispersity were synthesized by a one-step in situ hydrothermal method using graphene oxide (GO) and TiO{sub 2} (P25) as the starting materials. The as-prepared samples were characterized by XRD, XPS, TEM, FE-SEM, EDX, Raman, N{sub 2} adsorption, and UV–vis DRS techniques. Enhanced light absorption and a red shift of absorption edge were observed for the composites in the ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS). Their effective photocatalytic activity was evaluated by the photodegradation of methylene blue under visible light irradiation. An enhancement of photocatalytic performance was observed over graphene/TiO{sub 2} nanorodmore » hybrid composite photocatalysts, as 3.7 times larger than that of pristine TiO{sub 2} nanorods. This work demonstrated that the synthesis of TiO{sub 2} nanorods and simultaneous conversion of GO to graphene “without using reducing agents” had shown to be a rapid, direct and clean approach to fabricate chemically bonded graphene/TiO{sub 2} nanorod hybrid composites with enhanced photocatalytic performance.« less

Laser Indirect Shock Welding of Fine Wire to Metal Sheet.

PubMed

Wang, Xiao; Huang, Tao; Luo, Yapeng; Liu, Huixia

2017-09-12

The purpose of this paper is to present an advanced method for welding fine wire to metal sheet, namely laser indirect shock welding (LISW). This process uses silica gel as driver sheet to accelerate the metal sheet toward the wire to obtain metallurgical bonding. A series of experiments were implemented to validate the welding ability of Al sheet/Cu wire and Al sheet/Ag wire. It was found that the use of a driver sheet can maintain high surface quality of the metal sheet. With the increase of laser pulse energy, the bonding area of the sheet/wire increased and the welding interfaces were nearly flat. Energy dispersive spectroscopy (EDS) results show that the intermetallic phases were absent and a short element diffusion layer which would limit the formation of the intermetallic phases emerging at the welding interface. A tensile shear test was used to measure the mechanical strength of the welding joints. The influence of laser pulse energy on the tensile failure modes was investigated, and two failure modes, including interfacial failure and failure through the wire, were observed. The nanoindentation test results indicate that as the distance to the welding interface decreased, the microhardness increased due to the plastic deformation becoming more violent.

B2O3/SiO2 substitution effect on structure and properties of Na2O-CaO-SrO-P2O5-SiO2 bioactive glasses from molecular dynamics simulations.

PubMed

Ren, Mengguo; Lu, Xiaonan; Deng, Lu; Kuo, Po-Hsuen; Du, Jincheng

2018-05-23

The effect of B2O3/SiO2 substitution in SrO-containing 55S4.3 bioactive glasses on glass structure and properties, such as ionic diffusion and glass transition temperature, was investigated by combining experiments and molecular dynamics simulations with newly developed potentials. Both short-range (such as bond length and bond angle) and medium-range (such as polyhedral connection and ring size distribution) structures were determined as a function of glass composition. The simulation results were used to explain the experimental results for glass properties such as glass transition temperature and bioactivity. The fraction of bridging oxygen increased linearly with increasing B2O3 content, resulting in an increase in overall glass network connectivity. Ion diffusion behavior was found to be sensitive to changes in glass composition and the trend of the change with the level of substitution is also temperature dependent. The differential scanning calorimetry (DSC) results show a decrease in glass transition temperature (Tg) with increasing B2O3 content. This is explained by the increase in ion diffusion coefficient and decrease in ion diffusion energy barrier in glass melts, as suggested by high-temperature range (above Tg) ion diffusion calculations as B2O3/SiO2 substitution increases. In the low-temperature range (below Tg), the Ea for modifier ions increased with B2O3/SiO2 substitution, which can be explained by the increase in glass network connectivity. Vibrational density of states (VDOS) were calculated and show spectral feature changes as a result of the substitution. The change in bioactivity with B2O3/SiO2 substitution is discussed with the change in pH value and release of boric acid into the solution.

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

Duranty, Edward R.; Baschnagel, Jörg; Dadmun, Mark

Copolymers are commonly used as interface modifiers that allow for the compatibilization of polymer components in a blend. For copolymers to function as a compatibilizer, they must diffuse through the matrix of the blend to the interface between the two blend components. The diffusivity of a copolymer in a blend matrix therefore becomes important in determining good candidates for use as compatibilizers. In this paper, coarse-grained Monte Carlo simulations using the bond fluctuation model modified with an overlap penalty have been developed to study the diffusive behavior of PS/PMMA random copolymers in a PMMA homopolymer blend. The simulations vary themore » connectivity between different monomers, the thermodynamic interactions between the monomers which manifest within a chain, and between copolymer and homopolymer matrix and define the monomer friction coefficient of each component independently, allowing for the determination of the combined effect of these parameters on copolymer chain diffusion. Finally, the results of this work indicate that PS-r-PMMA copolymer diffusion is not linearly dependent on the copolymer composition on a logarithmic scale, but its diffusion is a balance of the kinetics governed by the dominant motion of the faster styrene monomers and thermodynamics, which are governed by the concentration of styrene monomer within a given monomer’s local volume.« less

Excess entropy scaling for the segmental and global dynamics of polyethylene melts.

PubMed

Voyiatzis, Evangelos; Müller-Plathe, Florian; Böhm, Michael C

2014-11-28

The range of validity of the Rosenfeld and Dzugutov excess entropy scaling laws is analyzed for unentangled linear polyethylene chains. We consider two segmental dynamical quantities, i.e. the bond and the torsional relaxation times, and two global ones, i.e. the chain diffusion coefficient and the viscosity. The excess entropy is approximated by either a series expansion of the entropy in terms of the pair correlation function or by an equation of state for polymers developed in the context of the self associating fluid theory. For the whole range of temperatures and chain lengths considered, the two estimates of the excess entropy are linearly correlated. The scaled bond and torsional relaxation times fall into a master curve irrespective of the chain length and the employed scaling scheme. Both quantities depend non-linearly on the excess entropy. For a fixed chain length, the reduced diffusion coefficient and viscosity scale linearly with the excess entropy. An empirical reduction to a chain length-independent master curve is accessible for both dynamic quantities. The Dzugutov scheme predicts an increased value of the scaled diffusion coefficient with increasing chain length which contrasts physical expectations. The origin of this trend can be traced back to the density dependence of the scaling factors. This finding has not been observed previously for Lennard-Jones chain systems (Macromolecules, 2013, 46, 8710-8723). Thus, it limits the applicability of the Dzugutov approach to polymers. In connection with diffusion coefficients and viscosities, the Rosenfeld scaling law appears to be of higher quality than the Dzugutov approach. An empirical excess entropy scaling is also proposed which leads to a chain length-independent correlation. It is expected to be valid for polymers in the Rouse regime.

Oxidation behavior of Al/Cr coating on Ti2AlNb alloy at 900 °C

NASA Astrophysics Data System (ADS)

Yang, Zhengang; Liang, Wenping; Miao, Qiang; Chen, Bowen; Ding, Zheng; Roy, Nipon

2018-04-01

In this paper, the Al/Cr coating was fabricated on the surface of Ti2AlNb alloy via rf magnetron sputtering and double glow treatment to enhance oxidation resistance. The protective coating with an outer layer of Al and inner layer of Cr has great bonding strength due to the in-diffusion of Cr and the inter-diffusion between Al and Cr to form Al-Cr alloyed layer which has great hardness. Acoustic emission curve which was detected via WS-2005 scratch tester indicates the bonding strength between Al/Cr coating and substrate is great. Morphology of Ti2AlNb alloy with Al/Cr coating after scratch test shows that the scratch is smooth without disbanding, and the depth and breadth of scratch are changed uniformly. The mass change was reduced after oxidation test due to the Al/Cr protective coating. Isothermal oxidation test at 900 °C was researched. Results indicate that Al/Cr coating provided oxidation resistance of Ti2AlNb alloy with prolonged air exposure at 900 °C. Al2O3 was detected by XRD patterns and SEM images, and was formed on the surface of Ti2AlNb alloy to protect substrate during oxidation test. A certain content of Cr is beneficial for the formation of Al2O3. Besides, Cr2O3 was produced under Al2O3 by outward diffusion of Cr to protect substrate sequentially, no cracks were discovered on Al/Cr protective coating. The process of Ti outward diffusion into surface was suppressive due to integration of Cr-Ti and Al-Ti intermetallics. A steady, adherent and continuous coated layer of Al/Cr on Ti2AlNb alloy increases oxidation resistance.

Bonding by Hydroxide-Catalyzed Hydration and Dehydration

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung

2008-01-01

A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.

A diffuse radar scattering model from Martian surface rocks

NASA Technical Reports Server (NTRS)

Calvin, W. M.; Jakosky, B. M.; Christensen, P. R.

1987-01-01

Remote sensing of Mars has been done with a variety of instrumentation at various wavelengths. Many of these data sets can be reconciled with a surface model of bonded fines (or duricrust) which varies widely across the surface and a surface rock distribution which varies less so. A surface rock distribution map from -60 to +60 deg latitude has been generated by Christensen. Our objective is to model the diffuse component of radar reflection based on this surface distribution of rocks. The diffuse, rather than specular, scattering is modeled because the diffuse component arises due to scattering from rocks with sizes on the order of the wavelength of the radar beam. Scattering for radio waves of 12.5 cm is then indicative of the meter scale and smaller structure of the surface. The specular term is indicative of large scale surface undulations and should not be causally related to other surface physical properties. A simplified model of diffuse scattering is described along with two rock distribution models. The results of applying the models to a planet of uniform fractional rock coverage with values ranging from 5 to 20% are discussed.

Spectrally edited 2D 13Csbnd 13C NMR spectra without diagonal ridge for characterizing 13C-enriched low-temperature carbon materials

NASA Astrophysics Data System (ADS)

Johnson, Robert L.; Anderson, Jason M.; Shanks, Brent H.; Fang, Xiaowen; Hong, Mei; Schmidt-Rohr, Klaus

2013-09-01

Two robust combinations of spectral editing techniques with 2D 13Csbnd 13C NMR have been developed for characterizing the aromatic components of 13C-enriched low-temperature carbon materials. One method (exchange with protonated and nonprotonated spectral editing, EXPANSE) selects cross peaks of protonated and nearby nonprotonated carbons, while the other technique, dipolar-dephased double-quantum/single-quantum (DQ/SQ) NMR, selects signals of bonded nonprotonated carbons. Both spectra are free of a diagonal ridge, which has many advantages: Cross peaks on the diagonal or of small intensity can be detected, and residual spinning sidebands or truncation artifacts associated with the diagonal ridge are avoided. In the DQ/SQ experiment, dipolar dephasing of the double-quantum coherence removes protonated-carbon signals; this approach also eliminates the need for high-power proton decoupling. The initial magnetization is generated with minimal fluctuation by combining direct polarization, cross polarization, and equilibration by 13C spin diffusion. The dipolar dephased DQ/SQ spectrum shows signals from all linkages between aromatic rings, including a distinctive peak from polycondensed aromatics. In EXPANSE NMR, signals of protonated carbons are selected in the first spectral dimension by short cross polarization combined with dipolar dephasing difference. This removes ambiguities of peak assignment to overlapping signals of nonprotonated and protonated aromatic carbons, e.g. near 125 ppm. Spin diffusion is enhanced by dipolar-assisted rotational resonance. Before detection, Csbnd H dipolar dephasing by gated decoupling is applied, which selects signals of nonprotonated carbons. Thus, only cross peaks due to magnetization originating from protonated C and ending on nearby nonprotonated C are retained. Combined with the chemical shifts deduced from the cross-peak position, this double spectral editing defines the bonding environment of aromatic, COO, and Cdbnd O carbons, which is particularly useful for identifying furan and arene rings. The Cdbnd O carbons, whose chemical shifts vary strongly (between 212 and 165 ppm) and systematically depend on their two bonding partners, show particularly informative cross peaks, given that one bonding partner is defined by the other frequency coordinate of the cross peak. The new techniques and the information content of the resulting spectra are validated on sulfuric-acid treated low-temperature carbon materials and on products of the Maillard reaction. The crucial need for spectral editing for correct peak assignment is demonstrated in an example.

A modified low-temperature wafer bonding method using spot pressing bonding technique and water glass adhesive layer

NASA Astrophysics Data System (ADS)

Xu, Yang; Wang, Shengkai; Wang, Yinghui; Chen, Dapeng

2018-02-01

A modified low-temperature wafer bonding method using a spot pressing bonding technique and a water glass adhesive layer is proposed. The electrical properties of the water glass layer has been studied by capacitance-voltage (C-V) and electric current-voltage (I-V) measurements. It is found that the adhesive layer can be regarded as a good insulator in terms of leakage current density. The bonding mechanism and the motion of bubbles during the thermal treatment are investigated. The dominant factor for the bubble motion in the modified bonding process is the gradient of pressure introduced by the spot pressing force. It is proved that the modified method achieves low-temperature adhesive bonding, minimizes the effect of water desorption, and provides good bonding performance.

Diffusion of copolymers composed of monomers with drastically different friction factors in copolymer/homopolymer blends

DOE PAGES

Duranty, Edward R.; Baschnagel, Jörg; Dadmun, Mark

2017-02-07

Copolymers are commonly used as interface modifiers that allow for the compatibilization of polymer components in a blend. For copolymers to function as a compatibilizer, they must diffuse through the matrix of the blend to the interface between the two blend components. The diffusivity of a copolymer in a blend matrix therefore becomes important in determining good candidates for use as compatibilizers. In this paper, coarse-grained Monte Carlo simulations using the bond fluctuation model modified with an overlap penalty have been developed to study the diffusive behavior of PS/PMMA random copolymers in a PMMA homopolymer blend. The simulations vary themore » connectivity between different monomers, the thermodynamic interactions between the monomers which manifest within a chain, and between copolymer and homopolymer matrix and define the monomer friction coefficient of each component independently, allowing for the determination of the combined effect of these parameters on copolymer chain diffusion. Finally, the results of this work indicate that PS-r-PMMA copolymer diffusion is not linearly dependent on the copolymer composition on a logarithmic scale, but its diffusion is a balance of the kinetics governed by the dominant motion of the faster styrene monomers and thermodynamics, which are governed by the concentration of styrene monomer within a given monomer’s local volume.« less

A Reference-Free and Non-Contact Method for Detecting and Imaging Damage in Adhesive-Bonded Structures Using Air-Coupled Ultrasonic Transducers.

PubMed

Yonathan Sunarsa, Timotius; Aryan, Pouria; Jeon, Ikgeun; Park, Byeongjin; Liu, Peipei; Sohn, Hoon

2017-12-08

Adhesive bonded structures have been widely used in aerospace, automobile, and marine industries. Due to the complex nature of the failure mechanisms of bonded structures, cost-effective and reliable damage detection is crucial for these industries. Most of the common damage detection methods are not adequately sensitive to the presence of weakened bonding. This paper presents an experimental and analytical method for the in-situ detection of damage in adhesive-bonded structures. The method is fully non-contact, using air-coupled ultrasonic transducers (ACT) for ultrasonic wave generation and sensing. The uniqueness of the proposed method relies on accurate detection and localization of weakened bonding in complex adhesive bonded structures. The specimens tested in this study are parts of real-world structures with critical and complex damage types, provided by Hyundai Heavy Industries ® and IKTS Fraunhofer ® . Various transmitter and receiver configurations, including through transmission, pitch-catch scanning, and probe holder angles, were attempted, and the obtained results were analyzed. The method examines the time-of-flight of the ultrasonic waves over a target inspection area, and the spatial variation of the time-of-flight information was examined to visualize and locate damage. The proposed method works without relying on reference data obtained from the pristine condition of the target specimen. Aluminum bonded plates and triplex adhesive layers with debonding and weakened bonding were used to examine the effectiveness of the method.

A Reference-Free and Non-Contact Method for Detecting and Imaging Damage in Adhesive-Bonded Structures Using Air-Coupled Ultrasonic Transducers

PubMed Central

Yonathan Sunarsa, Timotius; Aryan, Pouria; Jeon, Ikgeun; Park, Byeongjin; Liu, Peipei

2017-01-01

Adhesive bonded structures have been widely used in aerospace, automobile, and marine industries. Due to the complex nature of the failure mechanisms of bonded structures, cost-effective and reliable damage detection is crucial for these industries. Most of the common damage detection methods are not adequately sensitive to the presence of weakened bonding. This paper presents an experimental and analytical method for the in-situ detection of damage in adhesive-bonded structures. The method is fully non-contact, using air-coupled ultrasonic transducers (ACT) for ultrasonic wave generation and sensing. The uniqueness of the proposed method relies on accurate detection and localization of weakened bonding in complex adhesive bonded structures. The specimens tested in this study are parts of real-world structures with critical and complex damage types, provided by Hyundai Heavy Industries® and IKTS Fraunhofer®. Various transmitter and receiver configurations, including through transmission, pitch-catch scanning, and probe holder angles, were attempted, and the obtained results were analyzed. The method examines the time-of-flight of the ultrasonic waves over a target inspection area, and the spatial variation of the time-of-flight information was examined to visualize and locate damage. The proposed method works without relying on reference data obtained from the pristine condition of the target specimen. Aluminum bonded plates and triplex adhesive layers with debonding and weakened bonding were used to examine the effectiveness of the method. PMID:29292752

Ultra precision and reliable bonding method

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung (Inventor)

2001-01-01

The bonding of two materials through hydroxide-catalyzed hydration/dehydration is achieved at room temperature by applying hydroxide ions to at least one of the two bonding surfaces and by placing the surfaces sufficiently close to each other to form a chemical bond between them. The surfaces may be placed sufficiently close to each other by simply placing one surface on top of the other. A silicate material may also be used as a filling material to help fill gaps between the surfaces caused by surface figure mismatches. A powder of a silica-based or silica-containing material may also be used as an additional filling material. The hydroxide-catalyzed bonding method forms bonds which are not only as precise and transparent as optical contact bonds, but also as strong and reliable as high-temperature frit bonds. The hydroxide-catalyzed bonding method is also simple and inexpensive.

Wafer-level Cu-Sn micro-joints with high mechanical strength and low Sn overflow

NASA Astrophysics Data System (ADS)

Duan, Ani; Luu, Thi-Thuy; Wang, Kaiying; Aasmundtveit, Knut; Hoivik, Nils

2015-09-01

In this paper, we report wafer-level bonding using solid-liquid inter-diffusion (SLID) processes for fabricating micro-joints Cu-Sn at low temperature (270 °C). The evolution of multilayer Cu/Sn to micro-joint alloys has been characterized by optical microscopy and mechanical die-shear testing. The Cu-Sn joints with line width from 80 to 200 μm prove to be reliable packaging materials for bonding vacuum micro-cavities with controllable Sn overflow, as well as high mechanical strength (>70 MPa). A thermodynamic model has been performed to further understand the formation of Cu-Sn intermetallic alloys. There are two important findings for this work: 1) Using a two-step temperature profile may significantly reduce the amount of Sn overflow; 2) for packaging, a bond frame width greater than 80 μm will result in high yield.

Theoretical and computational studies of renewable energy materials: Room temperature ionic liquids and proton exchange membranes

NASA Astrophysics Data System (ADS)

Feng, Shulu

2011-12-01

Two kinds of renewable energy materials, room temperature ionic liquids (RTILs) and proton exchange membranes (PEMs), especially Nafion, are studied by computational and theoretical approaches. The ultimate purpose of the present research is to design novel materials to meet the future energy demands. To elucidate the effect of alkyl side chain length and anion on the structure and dynamics of the mixtures, molecular dynamics (MD) simulations of three RTILs/water mixtures at various water mole fractions: 1-butyl-3-methylimidazolium (BMIM+)/BF4-, 1-octyl-3-methylimidazolium (OMIM+)/BF4-, and OMIM +/Cl- are performed. Replacing the BMIM + cation with OMIM+ results in stronger aggregation of the cations as well as a slower diffusion of the anions, and replacing the BF4- anion with Cl- alters the water distribution at low water mole fractions and slows diffusion of the mixtures. Potential experimental manifestations of these behaviors in both cases are provided. Proton solvation properties and transport mechanisms are studied in hydrated Nafion, by using the self-consistent multistate empirical valence bond (SCI-MS-EVB) method. It is found that by stabilizing a more Zundel-like (H5O 2+) structure in the first solvation shells, the solvation of excess protons, as well as the proton hydration structure are both influenced by the sulfonate groups. Hydrate proton-related hydrogen bond networks are observed to be more stable than those with water alone. In order to characterize the nature of the proton transport (PT), diffusive motion, Arrhenius activation energies, and transport pathways are calculated and analyzed. Analysis of diffusive motion suggests that (1) a proton-hopping mechanism dominates the proton transport for the studied water loading levels and (2) there is an obvious degree of anti-correlation between the proton hopping and the vehicular transport. The activation energy drops rapidly with an increasing water content when the water loading level is smaller than ˜ 10 H2O/SO 3-, which is consistent with experimental observations. The sulfonate groups are also found to have influence on the proton hopping directions. The temperature and water content effects on the PT pathways are also investigated. The morphological effects on proton solvation and transport in hydrated Nafion are investigated, by using the SCI-MS-EVB method. Two of the most significant morphological models of Nafion, the lamellar model and the cylinder model, are selected. The two models exhibit distinct PT patterns, which result in different proton diffusion rates. In both models, the interaction between protons and the sulfonate groups are proven to be the key to determining PT behavior. The proton solvation structure change as a function of the distance between protons and sulfonate groups has been analyzed. It is found that the increase of water cylinder radius or water layer height leads to the presence of more protons around the sulfonate groups. Furthermore, at a lower hydration level, the increased amount of protons around the sulfonate groups consists of more Zundel-like structures, which is influenced by the distinct morphological structures of Nafion.

Distribution of Gd(III) ions at the graphene oxide/water interface.

PubMed

Amirov, Rustem R; Shayimova, Julia; Dimiev, Ayrat M

2018-10-01

Graphene oxide (GO) have emerged recently as a novel material for sorbing metal cations from aqueous media. However, the literature data on sorption capacity differ by more than one order in magnitude, and the nature of the chemical bonding between GO and metal cations remains unclear. In this work we show that Gd 3+ ions are bound to GO by both coordinate-covalent bonding and electrostatic attraction with prevailing the former. We provide the complete account for the GO sorption toward Gd 3+ as the function of the Gd 3+ /GO ratio and pH of solution. The upper limits of the strong bonding are determined as 0.70 and 0.16 mmol(Gd 3+ )/g(GO) in the neutral and in the intrinsically acidic solutions, respectively. At large excess of Gd 3+ in the neutral solutions, the sorption capacity reaches 1.45 mmol(Gd 3+ )/g(GO). The effectiveness of water, hydrochloric acid and EDTA as desorbing eluents is compared. We experimentally demonstrate the existence of the Gd 3+ concentration gradient within the diffuse layer at the GO/water interface, and its exponential character on the distance from the GO surface. The thickness of the diffuse layer and the position of the slipping plane are estimated. Such characteristics, typical for colloid systems, show that in solutions, GO flakes form distinct phase, even though they are just one atom thick. Copyright © 2018 Elsevier Inc. All rights reserved.

Interfacial layers evolution during annealing in Ti-Al multi-laminated composite processed using hot press and roll bonding

NASA Astrophysics Data System (ADS)

Assari, A. H.; Eghbali, B.

2016-09-01

Ti-Al multi-laminated composites have great potential in high strength and low weight structures. In the present study, tri-layer Ti-Al composite was synthesized by hot press bonding under 40 MPa at 570 °C for 1 h and subsequent hot roll bonding at about 450 °C. This process was conducted in two accumulative passes to 30% and to 67% thickness reduction in initial and final passes, respectively. Then, the final annealing treatments were done at 550, 600, 650, 700 and 750 °C for 2, 4 and 6 h. Investigations on microstructural evolution and thickening of interfacial layers were performed by scanning electron microscopes, energy dispersive spectrometer, X-ray diffraction and micro-hardness tests. The results showed that the thickening of diffusion layers corresponds to amount of deformation. In addition to thickening of the diffusion layers, the thickness of aluminum layers decreased and after annealing treatment at 750 °C for 6 h the aluminum layers were consumed entirely, which occurred because of the enhanced interdiffusion of Ti and Al elements. Scanning electron microscope equipped with energy dispersive spectrometer showed that the sequence of interfacial layers as Ti3Al-TiAl-TiAl2-TiAl3 which are believed to be the result of thermodynamic and kinetic of phase formation. Micro-hardness results presented the variation profile in accordance with the sequence of intermetallic phases and their different structures.

Comparison of Experimental Methods for Estimating Matrix Diffusion Coefficients for Contaminant Transport Modeling

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

Telfeyan, Katherine Christina; Ware, Stuart Douglas; Reimus, Paul William

Diffusion cell and diffusion wafer experiments were conducted to compare methods for estimating matrix diffusion coefficients in rock core samples from Pahute Mesa at the Nevada Nuclear Security Site (NNSS). A diffusion wafer method, in which a solute diffuses out of a rock matrix that is pre-saturated with water containing the solute, is presented as a simpler alternative to the traditional through-diffusion (diffusion cell) method. Both methods yielded estimates of matrix diffusion coefficients that were within the range of values previously reported for NNSS volcanic rocks. The difference between the estimates of the two methods ranged from 14 to 30%,more » and there was no systematic high or low bias of one method relative to the other. From a transport modeling perspective, these differences are relatively minor when one considers that other variables (e.g., fracture apertures, fracture spacings) influence matrix diffusion to a greater degree and tend to have greater uncertainty than diffusion coefficients. For the same relative random errors in concentration measurements, the diffusion cell method yields diffusion coefficient estimates that have less uncertainty than the wafer method. However, the wafer method is easier and less costly to implement and yields estimates more quickly, thus allowing a greater number of samples to be analyzed for the same cost and time. Given the relatively good agreement between the methods, and the lack of any apparent bias between the methods, the diffusion wafer method appears to offer advantages over the diffusion cell method if better statistical representation of a given set of rock samples is desired.« less

Comparison of experimental methods for estimating matrix diffusion coefficients for contaminant transport modeling

NASA Astrophysics Data System (ADS)

Telfeyan, Katherine; Ware, S. Doug; Reimus, Paul W.; Birdsell, Kay H.

2018-02-01

Diffusion cell and diffusion wafer experiments were conducted to compare methods for estimating effective matrix diffusion coefficients in rock core samples from Pahute Mesa at the Nevada Nuclear Security Site (NNSS). A diffusion wafer method, in which a solute diffuses out of a rock matrix that is pre-saturated with water containing the solute, is presented as a simpler alternative to the traditional through-diffusion (diffusion cell) method. Both methods yielded estimates of effective matrix diffusion coefficients that were within the range of values previously reported for NNSS volcanic rocks. The difference between the estimates of the two methods ranged from 14 to 30%, and there was no systematic high or low bias of one method relative to the other. From a transport modeling perspective, these differences are relatively minor when one considers that other variables (e.g., fracture apertures, fracture spacings) influence matrix diffusion to a greater degree and tend to have greater uncertainty than effective matrix diffusion coefficients. For the same relative random errors in concentration measurements, the diffusion cell method yields effective matrix diffusion coefficient estimates that have less uncertainty than the wafer method. However, the wafer method is easier and less costly to implement and yields estimates more quickly, thus allowing a greater number of samples to be analyzed for the same cost and time. Given the relatively good agreement between the methods, and the lack of any apparent bias between the methods, the diffusion wafer method appears to offer advantages over the diffusion cell method if better statistical representation of a given set of rock samples is desired.

Mechanism of bonding and debonding using surface activated bonding method with Si intermediate layer

NASA Astrophysics Data System (ADS)

Takeuchi, Kai; Fujino, Masahisa; Matsumoto, Yoshiie; Suga, Tadatomo

2018-04-01

Techniques of handling thin and fragile substrates in a high-temperature process are highly required for the fabrication of semiconductor devices including thin film transistors (TFTs). In our previous study, we proposed applying the surface activated bonding (SAB) method using Si intermediate layers to the bonding and debonding of glass substrates. The SAB method has successfully bonded glass substrates at room temperature, and the substrates have been debonded after heating at 450 °C, in which TFTs are fabricated on thin glass substrates for LC display devices. In this study, we conducted the bonding and debonding of Si and glass in order to understand the mechanism in the proposed process. Si substrates are also successfully bonded to glass substrates at room temperature and debonded after heating at 450 °C using the proposed bonding process. By the composition analysis of bonding interfaces, it is clarified that the absorbed water on the glass forms interfacial voids and cause the decrease in bond strength.

Dynamics and diffusion mechanism of low-density liquid silicon

DOE PAGES

Shen, B.; Wang, Z. Y.; Dong, F.; ...

2015-11-05

A first-order phase transition from a high-density liquid to a low-density liquid has been proposed to explain the various thermodynamic anomies of water. It also has been proposed that such liquid–liquid phase transition would exist in supercooled silicon. Computer simulation studies show that, across the transition, the diffusivity drops roughly 2 orders of magnitude, and the structures exhibit considerable tetrahedral ordering. The resulting phase is a highly viscous, low-density liquid silicon. Investigations on the atomic diffusion of such a novel form of liquid silicon are of high interest. Here we report such diffusion results from molecular dynamics simulations using themore » classical Stillinger–Weber (SW) potential of silicon. We show that the atomic diffusion of the low-density liquid is highly correlated with local tetrahedral geometries. We also show that atoms diffuse through hopping processes within short ranges, which gradually accumulate to an overall random motion for long ranges as in normal liquids. There is a close relationship between dynamical heterogeneity and hopping process. We point out that the above diffusion mechanism is closely related to the strong directional bonding nature of the distorted tetrahedral network. Here, our work offers new insights into the complex behavior of the highly viscous low density liquid silicon, suggesting similar diffusion behaviors in other tetrahedral coordinated liquids that exhibit liquid–liquid phase transition such as carbon and germanium.« less