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Sample records for dynamic diffusion bonding

  1. Dynamics and mechanism of structural diffusion in linear hydrogen bond.

    PubMed

    Chaiwongwattana, Sermsiri; Phonyiem, Mayuree; Vchirawongkwin, Viwat; Prueksaaroon, Supakit; Sagarik, Kritsana

    2012-01-15

    Dynamics and mechanism of proton transfer in a protonated hydrogen bond (H-bond) chain were studied, using the CH(3)OH(2)(+)(CH(3)OH)(n) complexes, n = 1-4, as model systems. The present investigations used B3LYP/TZVP calculations and Born-Oppenheimer MD (BOMD) simulations at 350 K to obtain characteristic H-bond structures, energetic and IR spectra of the transferring protons in the gas phase and continuum liquid. The static and dynamic results were compared with the H(3)O(+)(H(2)O)(n) and CH(3)OH(2)(+)(H(2)O)(n) complexes, n = 1-4. It was found that the H-bond chains with n = 1 and 3 represent the most active intermediate states and the CH(3)OH(2)(+)(CH(3)OH)(n) complexes possess the lowest threshold frequency of proton transfer. The IR spectra obtained from BOMD simulations revealed that the thermal energy fluctuation and dynamics help promote proton transfer in the shared-proton structure with n = 3 by lowering the vibrational energy for the interconversion between the oscillatory shuttling and structural diffusion motions, leading to a higher population of the structural diffusion motion than in the shared-proton structure with n = 1. Additional explanation on the previously proposed mechanisms was introduced, with the emphases on the energetic of the transferring proton, the fluctuation of the number of the CH(3)OH molecules in the H-bond chain, and the quasi-dynamic equilibriums between the shared-proton structure (n = 3) and the close-contact structures (n ≥ 4). The latter prohibits proton transfer reaction in the H-bond chain from being concerted, since the rate of the structural diffusion depends upon the lifetime of the shared-proton intermediate state. Copyright © 2011 Wiley Periodicals, Inc.

  2. 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.

  3. Vibrational spectral diffusion and hydrogen bond dynamics in heavy water from first principles.

    PubMed

    Mallik, Bhabani S; Semparithi, A; Chandra, Amalendu

    2008-06-12

    We present a first-principles theoretical study of vibrational spectral diffusion and hydrogen bond dynamics in heavy water without using any empirical model potentials. The calculations are based on ab initio molecular dynamics simulations for trajectory generation and a time series analysis using the wavelet method for frequency calculations. It is found that, in deuterated water, although a one-to-one relation does not exist between the instantaneous frequency of an OD bond and the distance of its associated hydrogen bond, such a relation does hold on average. The dynamics of spectral diffusion is investigated by means of frequency-time correlation and spectral hole dynamics calculations. Both of these functions are found to have a short-time decay with a time scale of approximately 100 fs corresponding to dynamics of intact hydrogen bonds and a slower long-time decay with a time constant of approximately 2 ps corresponding to lifetimes of hydrogen bonds. The connection of the slower time scale to the dynamics of local structural relaxation is also discussed. The dynamics of hydrogen bond making is shown to have a rather fast time scale of approximately 100 fs; hence, it can also contribute to the short-time dynamics of spectral diffusion. A damped oscillation is also found at around 150-200 fs, which is shown to have come from underdamped intermolecular vibrations of a hydrogen-bonded water pair. Such assignments are confirmed by independent calculations of power spectra of intermolecular motion and hydrogen bond kinetics using the population correlation function formalism. The details of the time constants of frequency correlations and spectral shifts are found to depend on the frequencies of chosen OD bonds and are analyzed in terms of the dynamics of hydrogen bonds of varying strengths and also of free non-hydrogen-bonded OD groups.

  4. Effect of Dynamic Recrystallization on Diffusion Bonding of Ni3Al Intermetallic Compound

    NASA Astrophysics Data System (ADS)

    Koizumi, Yuichiro; Minamino, Yoritoshi; Inui, Yasuhiro

    Diffusion bonding of B-doped Ni3Al polycrystals with various grain sizes was performed under various conditions with bonding pressures of 29-147MPa, bonding temperatures of 1173-1323K and bonding times of 0.12-3.6ks. The influences of the bonding conditions on the bond strength and the configurations of the fracture surfaces were investigated focusing on the microstructure near the bonding interface. The bond strength increased with increasing bonding pressure and increasing bonding temperature. On the other hand, the bond strength was almost independent of the bonding time. Moreover, the bond strength was higher as the grain size was smaller. The fracture surfaces of the specimen broken at the bonding interface were composed of two kinds of areas with different configurations. One had rugged configuration with a height of tens micrometers, and another had flat and smooth configuration. The area fraction of the rugged area tended to be larger in the fracture surfaces of the specimens exhibiting higher bond strength. The formation of the rugged fracture surface was attributed to the migration of the bonding interface accompanying the dynamic recrystallization in the bonding process and the fracture along the migrated interface by the observation of microstructure near the interface. The relationship between the bond strength and the distribution of the rugged fracture surface indicated that the increase in the bond strength was mainly due to the relief of the stress concentration at the triple junctions on the bonding interface by the change in the configuration of bonding interface.

  5. Diffusion bonding aeroengine components

    NASA Astrophysics Data System (ADS)

    Fitzpatrick, G. A.; Broughton, T.

    1988-10-01

    The use of diffusion bonding processes at Rolls-Royce for the manufacture of titanium-alloy aircraft engine components and structures is described. A liquid-phase diffusion bonding process called activated diffusion bonding has been developed for the manufacture of the hollow titanium wide chord fan blade. In addition, solid-state diffusion bonding is being used in the manufacture of hollow vane/blade airfoil constructions mainly in conjunction with superplastic forming and hot forming techniques.

  6. Structural dynamics of hydrogen bonded methanol oligomers: Vibrational transient hole burning studies of spectral diffusion

    NASA Astrophysics Data System (ADS)

    Piletic, I. R.; Gaffney, K. J.; Fayer, M. D.

    2003-07-01

    Frequency resolved pump-probe experiments have been conducted on the deuterated hydroxyl stretch of methanol-d in a solution containing 0.8% methanol-d/23% methanol-h in carbon tetrachloride. Methanol-d molecules that both donate and receive hydrogen bonds have an inhomogeneously broadened hydroxyl stretch absorption line centered at 2487 cm-1. With a laser tuned to 2513 cm-1, the high-frequency side of the absorption spectrum is excited. The equilibration of the excited state peak and the ground-state hole results in the time-dependent shift in the frequency of the signal, which is used to monitor the dynamics of spectral diffusion. Model calculations were conducted to address the influence of spectral diffusion in the ground and excited states on the experimental observables when the vibrational lifetime is comparable to the spectral diffusion time. The model calculations illustrate the influence on the signal of absorbers in the ground state that have relaxed from the excited state. This aspect of the problem has not been addressed in previous descriptions of frequency resolved pump-probe spectroscopy. The calculations were used to fit the time-dependent peak maximum, resulting in a bi-exponential frequency-frequency correlation function, with a fast time constant of roughly 0.1 ps and a slower time constant of 1.6±0.3 ps. The observed dynamics have been compared with the predictions of dielectric continuum theory. The inability of a simple dielectric continuum theory to predict the observed spectral diffusion dynamics suggests that these dynamics do not result from the long-wavelength, collective orientational relaxation of the solvent. Instead the dynamics are attributed to fluctuations in the local hydrogen bond network, which is consistent with recent molecular-dynamics simulations of vibrational transient hole burning in water.

  7. Molecular Dynamics Study of the Disruption of H-BONDS by Water Molecules and its Diffusion Behavior in Amorphous Cellulose

    NASA Astrophysics Data System (ADS)

    Liao, Ruijin; Zhu, Mengzhao; Zhou, Xin; Zhang, Fuzhou; Yan, Jiaming; Zhu, Wenbin; Gu, Chao

    2012-06-01

    Hydrolysis is an important component of the aging of cellulose, and it severely affects the insulating performance of cellulosic materials. The diffusion behavior of water molecules in amorphous cellulose and their destructive effect on the hydrogen bonding structure of cellulose were investigated by molecular dynamics. The change in the hydrogen bonding structure indicates that water molecules have a considerable effect on the hydrogen bonding structure within cellulose: both intermolecular and intramolecular hydrogen bonds decreased with an increase in ingressive water molecules. Moreover, the stabilities of the cellulose molecules were disrupted when the number of intermolecular hydrogen bonds declined to a certain degree. Both the free volumes of amorphous cells and water molecule-cellulose interaction affect the diffusion of water molecules. The latter, especially the hydrogen bonding interaction between water molecules and cellulose, plays a predominant role in the diffusion behavior of water molecules in the models of which the free volume rarely varies. The diffusion coefficient of water molecules has an excellent correlation with water molecule-cellulose interaction and the average hydrogen bonds between each water molecule and cellulose; however, this relationship was not apparent between the diffusion coefficient and free volume.

  8. Dynamics of supercritical methanol of varying density from first principles simulations: hydrogen bond fluctuations, vibrational spectral diffusion, and orientational relaxation.

    PubMed

    Yadav, Vivek Kumar; Chandra, Amalendu

    2013-06-14

    A first principles study of the dynamics of supercritical methanol is carried out by means of ab initio molecular dynamics simulations. In particular, the fluctuation dynamics of hydroxyl stretch frequencies, hydrogen bonds, dangling hydroxyl groups, and orientation of methanol molecules are investigated for three different densities at 523 K. Apart from the dynamical properties, various equilibrium properties of supercritical methanol such as the local density distributions and structural correlations, hydrogen bonding aspects, frequency-structure correlations, and dipole distributions of methanol molecules are also investigated. In addition to the density dependence of various equilibrium and dynamical properties, their dependencies on dispersion interactions are also studied by carrying out additional simulations using a dispersion corrected density functional for all the systems. It is found that the hydrogen bonding between methanol molecules decreases significantly as we move to the supercritical state from the ambient one. The inclusion of dispersion interactions is found to increase the number of hydrogen bonds to some extent. Calculations of the frequency-structure correlation coefficient reveal that a statistical correlation between the hydroxyl stretch frequency and the nearest hydrogen-oxygen distance continues to exist even at supercritical states of methanol, although it is weakened with increase of temperature and decrease of density. In the supercritical state, the frequency time correlation function is found to decay with two time scales: One around or less than 100 fs and the other in the region of 250-700 fs. It is found that, for supercritical methanol, the times scales of vibrational spectral diffusion are determined by an interplay between the dynamics of hydrogen bonds, dangling OD groups, and inertial rotation of methanol molecules and the roles of these various components are found to vary with density of the supercritical solvent. Effects

  9. Nonideality in diffusion of ionic and neutral solutes and hydrogen bond dynamics in dimethyl sulfoxide-chloroform mixtures of varying composition.

    PubMed

    Gupta, Rini; Chandra, Amalendu

    2011-09-01

    Molecular dynamics simulations of charged and neutral solutes in dimethyl sulfoxide (DMSO)-chloroform mixtures reveal pronounced nonideality in the solute diffusion with changes of composition of the mixtures. The diffusion coefficient of the anionic solute first decreases, passes through a minimum at DMSO mole fraction of about 0.50, and then increases to reach its value for pure DMSO. The diffusion coefficients of the cationic and neutral solutes are found to decrease with increase in DMSO content of the solvent mixture. The extent of nonideality in the diffusion and orientational relaxation of solvent molecules is found to be somewhat stronger than that in diffusion of the anionic solute in these mixtures. We have also calculated the relaxation of hydrogen bonds formed between DMSO and chloroform molecules. The lifetimes of DMSO-chloroform hydrogen bonds are found to increase monotonically with increase in DMSO concentration. The average number of hydrogen bonds and their average energies are also computed. It is found that an increase in DMSO concentration causes a decrease in the number of DMSO-chloroform hydrogen bonds per DMSO or chloroform molecules but increases the strength of these hydrogen bonds. Copyright © 2011 Wiley Periodicals, Inc.

  10. Water in Hydration Shell of an Iodide Ion: Structure and Dynamics of Solute-Water Hydrogen Bonds and Vibrational Spectral Diffusion from First-Principles Simulations.

    PubMed

    Karmakar, Anwesa; Chandra, Amalendu

    2015-07-09

    The dynamics of hydrogen bonds and vibrational spectral diffusion of water in the hydration shell of an iodide ion and in bulk have been investigated for aqueous iodide solutions of two different concentrations by using ab initio molecular dynamics simulations. The effects of dispersion interactions on the dynamics have also been investigated by using a dispersion corrected density functional. For the dilute solution containing a single iodide ion, three time scales are found for the spectral diffusion of solvation shell water: A short time scale of ∼150 fs, a slower time scale of ∼2-3 ps and a yet longer time scale of ∼14-16 ps. The long time scale of ∼14-16 ps is not noticed when calculations are done for all OD modes for both the dilute and concentrated solutions. It is found that a clear separation between the solvation shell and bulk water does not exist in terms of OD stretching frequencies for the concentrated solution. The dynamics of vibrational spectral diffusion is explained in terms of hydrogen bond dynamics, other dynamical modes such as orientational relaxation and molecular diffusion, and also structural aspects of water molecules in the solvation shells. The current results are compared with those of available experimental and other theoretical studies.

  11. Diffusion bonding of mismatch dental alloys.

    PubMed

    Liu, Honghua; Ni, Jiahua; Wu, Luhai; He, Guo

    2010-04-01

    The diffusion bonding of Ti-6Al-4V and Co-Cr-Mo dental alloys has been investigated in terms of the atoms diffusion, the microstructure evolution, and the bonding strength. The bonding performance reveals asymmetry diffusion profiles for both the Co and Cr in Ti-6Al-4V and the Ti in Co-Cr-Mo alloy. Their diffusion coefficients (Arrhenius relations) have been established based on the experiments. Co and Cr diffusion into Ti-6Al-4V leads to alpha --> beta transformation and the intermetallics-formation. Maximum bonding strength occurs at about 840 degrees C. The bonding joint fails under the shear stress in the Ti-6Al-4V side near the bonding interface in brittle manner. The intermetallics in the diffusion layer together with the unbonded areas and other flaws in the bonding interface are responsible for the shear brittle fracture, which also weaken the bonding strength.

  12. Diffusion bonding of Stratapax for drill bits

    SciTech Connect

    Middleton, J.N.; Finger, J.T.

    1983-01-01

    A process has been developed for the diffusion bonding of General Electric's Stratapax drill blanks to support studs for cutter assemblies in drill bits. The diffusion bonding process is described and bond strength test data are provided for a variety of materials. The extensive process details, provided in the Appendices, should be sufficient to enable others to successfully build diffusion-bonded drill bit cutter assemblies.

  13. Diffusion bonding of copper to niobium

    NASA Astrophysics Data System (ADS)

    Wagner, Adrian R.

    Processes used to join metal to ceramic at low temperatures have proven to be inefficient because multiple brazing cycles with different brazing temperatures and braze filler metals are required. Even though this is reproducible and robust, it is not ideal due to the manufacturing time and cost associated with multiple brazing cycles. A more efficient and cost effective process is to utilize the diffusion bonding technique to join different metallic layers prior to joining the entire ceramic assembly in one brazing cycle. In this study, the diffusion bonding of copper to niobium was examined. To the author's knowledge, the diffusion bonding of Cu to Nb has not been researched, and the diffusion of Cu into Nb or Nb into Cu has not been observed. A series of diffusion bonding experiments were conducted to determine the optimal bonding time, temperature, and pressure for the Cu-Nb system. The diffusion bonded samples were evaluated using mechanical testing and microscopy. Results from characterization indicate that diffusion of Nb into Cu occurs, and a robust bond with no interfacial voids is formed using different combinations of bonding parameters. The diffusion of Nb into Cu and with failure occurring outside the diffusion bonded region during all mechanical testing indicate that Cu can be bonded to Nb via the diffusion bonding technique.

  14. Diffusion bonding of superplastic aluminum alloys

    SciTech Connect

    Sunwoo, A.J.

    1993-12-01

    Ability to diffusion bond aluminum alloys, in particular superplastic aluminum alloys, will complete the technology-base that is strongly needed to enhance the use of superplastic forming (SPF) technology. Concurrent diffusion bonding (DB)-SPF is considered to be an energy-saving manufacturing process since it simplifies the production of complex components. Moreover, because of increased design flexibility, overall manufacturing cost and component weight are significantly reduced. Diffusion bonding is an attractive manufacturing option for applications where the preservation of the base metal microstructure and, in turn, mechanical properties is imperative in the bond area. The process utilizes either the solid state or transient liquid phase (TLP) bonding to produce a bond with microstructure continuity in the joint. In addition, there is no localized thermal gradient present to induce distortion or to create residual stresses in the component, thereby increasing structural integrity.

  15. 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

    2017-08-07

    The loading-dependent diffusion behavior of CH4, CO2, SO2, 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 Di of CH4 molecules decreases sharply and monotonically with the loading while those of both CO2 and SO2 molecules initially display a slight increase at low uptakes and follow a slow decrease at high uptakes. Accordingly, the interaction energies between CH4 molecules and ZIF-10 remain nearly constant regardless of the loading due to the absence of hydrogen bonds (HBs), while the interaction energies between CO2 (or SO2) 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 CO2 (or SO2) 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 CH4, CO2, and SO2 binary mixtures in ZIF-10, only associated with some HB competition between CO2 and SO2 molecules in the case of the CO2/SO2 mixture.

  16. 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.

  17. Hydrogen bond dynamics in bulk alcohols

    NASA Astrophysics Data System (ADS)

    Shinokita, Keisuke; Cunha, Ana V.; Jansen, Thomas L. C.; Pshenichnikov, Maxim S.

    2015-06-01

    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.

  18. 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.

  19. Hydrogen bond dynamics in bulk alcohols

    SciTech Connect

    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.

  20. Diffusion bonding of aluminium alloy, 8090

    SciTech Connect

    Sunwoo, A. )

    1994-08-15

    Ability to diffusion bond aluminum (Al) alloys, in particular superplastic aluminum alloys, will complete the technology-base that is strongly needed to enhance the use of superplastic forming (SPF) technology. Diffusion bonding (DB) is an attractive manufacturing option for applications where the preservation of the base metal microstructure and, in turn, mechanical properties is important in the bond area. As the technology moves from the laboratory to production, the DB process has to be production-feasible and cost-effective. At the Lawrence Livermore National Laboratory, the DB study of SPF Al alloys has been initiated. This paper describes the effect of surface chemistry on the DB properties of the Al alloy, 8090 (2.4Li-1.18Cu-0.57Mg-0.14Zr-Al). The integrity of the diffusion bonds was evaluated for both interlayered and bare surfaces. Two interlayer elements, copper (Cu) and zinc (Zn), were compared. Although the eutectic temperature of Al-Cu is 548 C, a thin Cu layer in contact with 8090 has been shown to lower its eutectic temperature to [approximately]521 C. In 8090, Cu is one of the primary alloying elements but has a limited solubility in Al at the bonding temperature. Zinc, on the other hand, forms a considerably lower eutectic (380 C) with Al and is highly soluble in Al. The diffusivity of Zn in Al is much faster than that of Cu, but Zn forms a more thermodynamically stable oxide. These subtle metallurgical differences will affect the transient liquid phase (TLP) formation at the interface, which will subsequently influence the bond quality.

  1. Hydrogen Bonding Slows Down Surface Diffusion of Molecular Glasses.

    PubMed

    Chen, Yinshan; Zhang, Wei; Yu, Lian

    2016-08-18

    Surface-grating decay has been measured for three organic glasses with extensive hydrogen bonding: sorbitol, maltitol, and maltose. For 1000 nm wavelength gratings, the decay occurs by viscous flow in the entire range of temperature studied, covering the viscosity range 10(5)-10(11) Pa s, whereas under the same conditions, the decay mechanism transitions from viscous flow to surface diffusion for organic glasses of similar molecular sizes but with no or limited hydrogen bonding. These results indicate that extensive hydrogen bonding slows down surface diffusion in organic glasses. This effect arises because molecules can preserve hydrogen bonding even near the surface so that the loss of nearest neighbors does not translate into a proportional decrease of the kinetic barrier for diffusion. This explanation is consistent with a strong correlation between liquid fragility and the surface enhancement of diffusion, both reporting resistance of a liquid to dynamic excitation. Slow surface diffusion is expected to hinder any processes that rely on surface transport, for example, surface crystal growth and formation of stable glasses by vapor deposition.

  2. Strength, ultrasonic and metallurgical evaluation of diffusion bonds

    SciTech Connect

    Ojard, G.C.; Buck, O.; Rehbein, D.K.

    1993-10-01

    Diffusion bonding allows similar and dissimilar materials to be bonded together in near net shape. However, differentiation of almost perfect diffusion bonds, with little variation in their acoustic response, is of critical importance since relatively significant changes in bond strength may be a consequence. Challenge is to find ultrasonic techniques sensitive enough to detect small imperfections at interface. Diffusion bonds have been produced that show only a slight variation in a single frequency reflection measurement. The total energy, reflected from bond line, can differentiate these diffusion bonds. This evaluation is based on Parseval`s theorem which states that energy in time domain is proportional to energy in the frequency domain. This measurement takes advantage of presence of voids in the diffusion bonds as well as of the interdiffusion zone. Cu and Ni were chosen as the materials to be bonded due to the case of microstructural control. Diffusion bonds fabricated of Ti-6Al-4V are also discussed.

  3. HIP diffusion bonding for gear materials

    SciTech Connect

    Ashworth, M.A.; Jacobs, M.H.; Armstrong, G.R.; Freeman, R.; Rickinson, B.A.; King, S.

    1996-12-31

    Mechanical actuators used on aircraft flight control systems contain highly stressed gears which are made from low alloy steels; either through or surface hardened. Corrosion protection has traditionally been provided by cadmium plating. Conventional stainless steels, even when given surface treatments do not provide the necessary strength, wear and corrosion properties for such gears. HIP processing has been used on cobalt based alloy powders as a new approach to produce gears for mechanical and corrosion testing. The technology has been used both to consolidate the powder and HIP diffusion bond the alloy to conventional stainless steels. The microstructure and properties of the consolidated alloy are presented together with preliminary results from component testing. The diffusion bonding route has produced gears which have much better wear and corrosion resistance than conventional steel gears whilst retaining equivalent fatigue properties. The economics of the process are discussed together with the concept of using the HIP process to shape as well as consolidate the material.

  4. 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

  5. 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.

  6. Diffusion bonding of silicon nitride to titanium

    NASA Astrophysics Data System (ADS)

    Lemus-Ruiz, Jose

    2001-07-01

    The use of ceramic has gradually increased over the past few years. Si3N4 is one of the most important ceramics used as structural material for high temperature applications. The practical use of advanced ceramics depends on the reliability of ceramic/metal joining techniques and the properties of the resulting interfaces. This work focuses on various aspects of diffusion bonding of Si3N4 to Ti as well as on the use of Ti-foil interlayer during the self-joining of Si3N4. Si3N4/Ti and Si3N 4/Ti-foil/Si3N4 combinations were diffusion joined by hot-uniaxial pressing and the microstructural characterization of the resulting interfaces was carried out by SEM, EPMA, and X-ray diffraction. Diffusion bonding was carried out at temperatures ranging from 1200 to 1500°C using different holding times, pressures, and surface roughness of the joining materials. The results showed that Si3N4 could not be bonded to Ti at temperatures lower than 1400°C, however successful joining at higher temperatures. Joining occurred by the formation of a reactive interface on the Ti side of the joint. At temperatures greater than 1330°C, liquid formation occurred by the interaction of Ti with Si promoting bonding, as well as the high affinity of Ti for Si resulted in rapid interface formation of silicides, initially Ti5Si3. EPMA and X-ray diffraction confirmed the presence of Ti5Si3, TiSi, and TiN at the interface. The surface roughness of the joining materials plays an important role since thicker interfaces were obtained for polished samples compared to as-ground samples. The interfaces grew in a parabolic fashion with the formation of various Ti-silicides (Ti5Si3 and TiSi) as well as Ti-nitride (TiN) at the interface. Evaluation of joint strengths as a function of the experimental parameters such as, joining temperature and time was obtained by four-point bending test performed on Si3N4/Ti/Si3N4 joints. Strong joints were produced at joining temperatures greater than 1450°C with average

  7. Signal analysis approach to ultrasonic evaluation of diffusion bond quality

    SciTech Connect

    Chinn, D; Thomas, G

    1999-06-08

    Solid state bonds like the diffusion bond are attractive techniques for joining dissimilar materials since they are not prone to the defects that occur with fusion welding. Ultrasonic methods can detect the presence of totally unbonded regions but have difficulty sensing poor bonded areas where the substrates are in intimate contact. Standard ultrasonic imaging is based on amplitude changes in the signal reflected from the bond interface. Unfortunately amplitude alone is not sensitive to bond quality. We demonstrated that there is additional information in the ultrasonic signal that correlates with bond quality. In our approach we interrogated a set of dissimilar diffusion bonded samples with broad band ultrasonic signals. The signals were digitally processed and the characteristics of the signals that corresponded to bond quality were determined. These characteristics or features were processed with pattern recognition algorithms to produce predictions of bond quality. The predicted bond quality was then compared with the destructive measurement to assess the classification capability of the ultrasonic technique

  8. Ultrasonic NDT of titanium diffusion bonding with guided waves

    SciTech Connect

    Rose, J.L.; Zhu, W.; Zaidi, M.

    1998-04-01

    An ultrasonic guided wave technique is developed for the NDT of diffusion bonded titanium-to-titanium structures. A three-layer model based on the normal beam experimental results has been proposed. Dispersion curves and wave structure are analyzed to direct the experimental study. Two features related to Lamb waves propagating in diffusion bonded titanium plates, the spectral peak to peak ratios and the wave mode frequency shift, are extracted from the guided wave experimental results for both 2 mm (0.08 in.) and 4 mm (0.16 in.) diffusion bond panels. It is found for some specific modes and frequencies that these two features are sensitive to the diffusion bonding states and, therefore, could be used to distinguish good bond panels from poor bond ones.

  9. 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.

  10. 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.

  11. Application of diffusion bonding to electronic interconnection of flatpack leads

    NASA Technical Reports Server (NTRS)

    Korb, R. W.; Lardenoit, V. F.

    1973-01-01

    Diffusion-bonded joints between gold-plated Kovar leads and indium-plated copper circuit pads offer some advantages for electronic circuit packaging. Test results show that consistent high strength bonds stronger than the copper circuit foil are achieved by parallel-gap bonding at relatively low power settings. The bonds are basically formed by the alloying of the gold, indium and copper at the bond interface. Other low melting metals such as tin can also be used; however, tin does not offer the ease of bonding that results in consistent separation of the copper foil during pull testing. The investigation was conducted in three parts consisting of: (1) an evaluation of the physical strength of resulting bonds at ambient and elevated temperature, (2) a metallurgical analysis of bonds using scanning electron microscopy and nondispersive X-ray analysis, and (3) evaluation and development of various schemes for multiple lead flatpack bonding.

  12. Joining of Silicon Carbide: Diffusion Bond Optimization and Characterization

    NASA Technical Reports Server (NTRS)

    Halbig, Michael C.; Singh, Mrityunjay

    2008-01-01

    Joining and integration methods are critically needed as enabling technologies for the full utilization of advanced ceramic components in aerospace and aeronautics applications. One such application is a lean direct injector for a turbine engine to achieve low NOx emissions. In the application, several SiC substrates with different hole patterns to form fuel and combustion air channels are bonded to form the injector. Diffusion bonding is a joining approach that offers uniform bonds with high temperature capability, chemical stability, and high strength. Diffusion bonding was investigated with the aid of titanium foils and coatings as the interlayer between SiC substrates to aid bonding. The influence of such variables as interlayer type, interlayer thickness, substrate finish, and processing time were investigated. Optical microscopy, scanning electron microscopy, and electron microprobe analysis were used to characterize the bonds and to identify the reaction formed phases.

  13. Metal honeycomb to porous wireform substrate diffusion bond evaluation

    NASA Technical Reports Server (NTRS)

    Vary, A.; Moorhead, P. E.; Hull, D. R.

    1982-01-01

    Two nondestructive techniques were used to evaluate diffusion bond quality between a metal foil honeycomb and porous wireform substrate. The two techniques, cryographics and acousto-ultrasonics, are complementary in revealing variations of bond integrity and quality in shroud segments from an experimental aircraft turbine engine.

  14. Fabrication and Characterization of Diffusion Bonds for Silicon Carbide

    NASA Technical Reports Server (NTRS)

    Halbig, Michael; Singh, Mrityunjay; Martin, Richard E.; Cosgriff, Laura M.

    2007-01-01

    Diffusion bonds of silicon carbide (SiC) were fabricated using several different types of titanium (Ti) based interlayers between the SiC substrates. The interlayers were an alloyed Ti foil, a pure Ti foil, and a physically vapor deposited (PVD) Ti coating. Microscopy was conducted to evaluate the cross-sections of the resulting bonds. Microprobe analysis identified reaction formed phases in the diffusion bonded region. Uniform and well adhered bonds were formed between the SiC substrates. In the case where the alloyed Ti foil or a thick Ti coating (i.e. 20 micron) was used as the interlayer, microcracks and several phases were present in the diffusion bonds. When a thinner interlayer was used (i.e. 10 micron PVD Ti), no microcracks were observed and only two reaction formed phases were present. The two phases were preferred and fully reacted phases that did not introduce thermal stresses or microcracks during the cool-down stage after processing. Diffusion bonded samples were evaluated with the non-destructive evaluation (NDE) methods of pulsed thermography and immersion ultrasonic testing. Joined SiC substrates that were fully bonded and that had simulated bond flaws in the interlayer were also evaluated using immersion ultrasound. Pull testing was conducted on the bonds to determine the tensile strength. To demonstrate the joining approach for a complex multilayered component for a low NOx injector application, the diffusion bonding approach was used to join three 4" diameter SiC discs that contained complex fuel and air flow channels.

  15. Diffusion bonding of titanium-titanium aluminide-alumina sandwich

    SciTech Connect

    Wickman, H.A.; Chin, E.S.C.; Biederman, R.R.

    1995-12-31

    Diffusion bonding of a metallic-intermetallic-ceramic sandwich is of interest for potential armor applications. Low cost titanium, titanium diboride reinforced titanium aluminide (Ti-48at.%Al), and aluminum oxide are diffusion bonded in a vacuum furnace between 1,000 C and 1,400 C. Metallographic examination of the prior bonding interface showed excellent metallurgical coupling between the Ti-48at.%Al composite and the low cost Ti. A series of microstructures representative of phases consistent with a hypothetical Ti-Al-B phase diagram is visible. The alumina-Ti-48at.%Al interfacial bond is achieved through penetration of titanium-aluminum phases into the existing alumina porosity. A detailed microstructural analysis identifying mechanisms of interfacial bonding will be presented for each interfacial zone.

  16. Torsion Testing of Diffusion Bonded LIGA Formed Nickel

    SciTech Connect

    Buchheit, T.E.; Christenson, T.R.; Schmale, D.T.

    1999-01-27

    A test technique has been devised which is suitable for the testing of the bond strength of batch diffusion bonded LIGA or DXRL defined structures. The method uses a torsion tester constructed with the aid of LIGA fabrication and distributed torsion specimens which also make use of the high aspect ratio nature of DXRL based processing. Measurements reveal achieved bond strengths of 130MPa between electroplated nickel with a bond temperature of 450 C at 7 ksi pressure which is a sufficiently low temperature to avoid mechanical strength degradation.

  17. Interface nanochemistry effects on stainless steel diffusion bonding

    NASA Astrophysics Data System (ADS)

    Cox, M. J.; Carpenter, R. W.; Kim, M. J.

    2002-02-01

    The diffusion-bonding behavior of single-phase austenitic stainless steel depends strongly on the chemistry of the surfaces to be bounded. We found that very smooth (0.5 nm root-mean-square (RMS) roughness), mechanically polished and lapped substrates would bond completely in ultrahigh vacuum (UHV) in 1 hour at 1000 °C under 3.5 MPa uniaxial pressure, if the native oxide on the substrates was removed by ion-beam cleaning, as shown by in-situ Auger analysis. No voids were observed in these bonded interfaces by transmission electron microscopy (TEM), and the strength was equal to that of the unbounded bare material. No bond formed between the substrates if in-situ ion cleaning was not used. The rougher cleaned substrates partially bonded, indicating that roughness, as well as native oxides, reduced the bonding kinetics.

  18. Diffusion bonding a creep-resistant Fe-ODS alloy

    NASA Astrophysics Data System (ADS)

    Bucklow, I. A.

    A method is described for diffusion bonding iron-based alloys in which the grain structure is continuous along the interface. The method is based on oxide-dispersion-strengthened (ODS) alloying for producing fine-grained materials with highly directional strain. Samples of the Fe-based MA956 alloy are rapidly diffusion bonded at about 1200 C and 200-300 MPa with either one or two induction heat treatments, and secondary recrystallization is seeded epitaxially. Sections are etched in glyceregia and studied by means of micrographs, and the diffusion rates of the ferritic alloys are found to be high enough to allow bonding at temperatures below the recrystallization level. Some mechanical damage to the specimens is noted that can lead to suboptimal grain directionality. The present results are of interest to the development of Fe-ODS alloys for turbine applications and for use in sulfurous atmospheres.

  19. Superplastically formed diffusion bonded metallic structure

    NASA Technical Reports Server (NTRS)

    Ko, W. L. (Inventor)

    1981-01-01

    A metallic sandwich structure particularly suited for use in aerospace industries comprising a base plate, a cover plate, and an orthogonally corrugated core is described. A pair of core plates formed of a superplastic alloy are interposed between the base plate and the cover plate and bonded. Each of the core plates is characterized by a plurality of protrusions comprising square-based, truncated pyramids uniformly aligned along orthogonally related axes perpendicularly bisecting the legs of the bases of the pyramids and alternately inverted along orthogonally related planes diagonally bisecting the pyramids, whereby an orthogonally corrugated core is provided.

  20. Evaluation of ultrasonic signals from diffusion and eutectic bond interfaces

    SciTech Connect

    Brown, C. M.

    1980-12-10

    A research program is in progress at Rocky Flats to determine correlations between ultrasonic signal content and diffusion or eutectic bond joint condition, and to develop a computer-controlled scanning, data acquisition and analysis system which utilizes these correlations and waveform analysis techniques. The initial efforts to determine effective ultrasonic waveform parameters to characterize the strength of bond interfaces is complete. A development version of a computer-controlled, automated scanning and data acquisition system is in operation.

  1. Nuclear fission with diffusive dynamics

    NASA Astrophysics Data System (ADS)

    Cha, D.; Bertsch, G. F.

    1992-07-01

    We investigate the dynamics of nuclear fission, assuming purely diffusive motion up to the saddle point. The resulting Smoluchowski equation is solved for conditions appropriate to the 16O+142Nd-->158Er reaction at 207 MeV. The solution is characterized by an equilibration time τ0 for the system to reach steady state, and the fission decay rate in steady state, Λ. We find that the equilibration time τ0 plays a very small role in determining the number of prescission neutrons. The diffusion coefficient extracted from the experimental data is larger than the theoretical in the work of Bush, Bertsch, and Brown by a factor of 5-11.

  2. Forge-Diffusion Bond Titanium Rotor Hub Evaluation.

    DTIC Science & Technology

    1975-07-01

    beta temperature • of 1750°F, diffusion treated at 1900°F, water —quenched, and then overaged at 1300°F for two hours. Separately forged upper and... FRACTU RE SURFACE , TRIAL PANCAKE ASSEMBLIES. . . . . . . . . . . . . . . . . . . 37 x - .— ~~- - -• FIGU RE PAGE 33. MEAN S/N CURVE FOR VARIOUS...optimum process to be an alpha—beta forging, forge—diffusion bonded at 1750°F , diffusion treated at 1900°F, water -quenched, and then overaged at

  3. A local view of bonding and diffusion at metal surfaces

    SciTech Connect

    Feibelman, P.J.

    1996-09-01

    First-principles density functional calculations and corresponding experimental results underline the importance of basic chemical concepts, such as coordination, valence saturation and promotion-hybridization energetics, in understanding bonding and diffusion of atoms at and on metal surfaces. Several examples are reviewed, including outer-layer relaxations of clean hcp(0001) surfaces, liquid-metal-embrittlement energetics, separation energies of metal-adatom dimers, concerted substitutional self-diffusion on fcc(001) surfaces, and adsorption and diffusion barrier sites for adatoms near steps.

  4. Partial transient liquid phase diffusion bonding of Zircaloy-4 to stabilized austenitic stainless steel 321

    SciTech Connect

    Atabaki, M. Mazar; Hanzaei, A. Talebi

    2010-10-15

    An innovative method was applied for bonding Zircaloy-4 to stabilized austenitic stainless steel 321 using an active titanium interlayer. Specimens were joined by a partial transient liquid phase diffusion bonding method in a vacuum furnace at different temperatures under 1 MPa dynamic pressure of contact. The influence of different bonding temperatures on the microstructure, microindentation hardness, joint strength and interlayer thickness has been studied. The diffusion of Fe, Cr, Ni and Zr has been investigated by scanning electron microscopy and energy dispersive spectroscopy elemental analyses. Results showed that control of the heating and cooling rate and 20 min soaking at 1223 K produces a perfect joint. However, solid-state diffusion of the melting point depressant elements into the joint metal causes the solid/liquid interface to advance until the joint is solidified. The tensile strength of all the bonded specimens was found around 480-670 MPa. Energy dispersive spectroscopy studies indicated that the melting occurred along the interface of the bonded specimens as a result of the transfer of atoms between the interlayer and the matrix during bonding. This technique provides a reliable method of bonding zirconium alloy to stainless steel.

  5. 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.

  6. Diffusive dynamics on paper matrix

    NASA Astrophysics Data System (ADS)

    Chaudhury, Kaustav; Kar, Shantimoy; Chakraborty, Suman

    2016-11-01

    Writing with ink on a paper and the rapid diagnostics of diseases using paper cartridge, despite their remarkable diversities from application perspective, both involve the motion of a liquid from a source on a porous hydrophilic substrate. Here we bring out a generalization in the pertinent dynamics by appealing to the concerned ensemble-averaged transport with reference to the underlying molecular picture. Our results reveal that notwithstanding the associated complexities and diversities, the resultant liquid transport characteristics on a paper matrix, in a wide variety of applications, resemble universal diffusive dynamics. Agreement with experimental results from diversified applications is generic and validates our unified theory.

  7. Air-coupled ultrasonic testing of diffusion bonds.

    PubMed

    Windels, Filip; Leroy, O

    2002-05-01

    The diffusion bond between two steel plates can be ultrasonically evaluated, at normal incidence in an immersion experiment, by analyzing the frequency dependence of the echo reflected from the imperfect bond. The interfacial stiffness, derived from the echo amplitude, correlates well with the bond-strength. However, a non-contact method is desirable for applications where immersion or contact is not wanted or even dangerous for damaging the material. This above mentioned bond-echo technique would not work in the situation of air-coupling as the reflected echo becomes then too weak due to the high impedance mismatch at the air-solid interface. Therefore we propose a theoretical method based on the study of two neighbouring resonance frequencies of the diffusion bonded plate-plate structure. In this way the physical signal sensitive to the adhesion status is not the (too weak) echo reflected from the bond, but the resonance frequency of the whole plate-plate system, and this frequency is detectable as working at resonance ensures high enough signal levels. It was shown that the odd resonance is as well sensitive to the plate thickness as to the interfacial bond parameter, whereas the even resonance feels only the plate thickness. On the basis of a theoretical formula, it is possible to extract, from a single point measurement, out of these two resonance frequencies both the plate thickness and the interfacial stiffness. In this way bond information is separated from geometrical information. Finally it is shown that thickness differences between the plates did not affect the reliability of the bonding-strength predictions.

  8. 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.

  9. Tunable infrared generation with diffusion-bonded-stacked gallium arsenide

    NASA Astrophysics Data System (ADS)

    Zheng, Dong

    Mid-infrared (MIR) radiation finds increasing applications in remote sensing, spectroscopy and military counter-measures. Nonlinear optical interactions provide one approach to tunable MIR sources generation. The development of MIR nonlinear optical crystals with excellent performance at a reasonable cost is essential for applications. Diffusion-bonded-stacked (DBS) GaAs periodic structures are a new family of quasi-phasematched (QPM) nonlinear optical crystals. The bonding process preserves the optical and mechanical properties of the bulk material, while the periodic modulation of the nonlinear coefficient permits QPM interactions. DBS GaAs bonding requirements, such as number of bonded layers and tolerable optical loss, are discussed. Nonlinear optical properties like mixing gain, wavelength, temperature and angular acceptance of the bonded structure, are predicted. DBS GaAs devices with up to 50 layers were bonded and characterized. Optical loss from interfacial voids and gaps at shorter wavelengths, from processing induced p- type free carrier absorption at longer wavelengths was characterized. 'Lithographic dicing' was invented and demonstrated as a replacement for mechanical dicing, resulting in the capability to handle thin wafers and cleaner interfaces for better bonding. Absorption due to semi-insulating-to-p-type conversion, a bulk crystal loss mechanism, was found to be induced by high bonding temperatures, and dependent on wafer sources and materials in contact with the stack. Optimized bonding parameters reduced the optical loss of 36-layer DBS GaAs to less than 0.2 cm-1 at long wavelengths. Tunable 15.6 to 17.6 μm coherent radiation at 90-ps pulse width was generated by difference frequency mixing in a 24-layer DBS GaAs device. The wavelength tuning curve agreed with theoretical predictions demonstrating that the bonding process maintained nonlinear optical phasematching over the 6 mm interaction length. Maximum mixing gain of 0.7%, or 5% internal

  10. 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.

  11. Dynamic strength of molecular adhesion bonds.

    PubMed

    Evans, E; Ritchie, K

    1997-04-01

    In biology, molecular linkages at, within, and beneath cell interfaces arise mainly from weak noncovalent interactions. These bonds will fail under any level of pulling force if held for sufficient time. Thus, when tested with ultrasensitive force probes, we expect cohesive material strength and strength of adhesion at interfaces to be time- and loading rate-dependent properties. To examine what can be learned from measurements of bond strength, we have extended Kramers' theory for reaction kinetics in liquids to bond dissociation under force and tested the predictions by smart Monte Carlo (Brownian dynamics) simulations of bond rupture. By definition, bond strength is the force that produces the most frequent failure in repeated tests of breakage, i.e., the peak in the distribution of rupture forces. As verified by the simulations, theory shows that bond strength progresses through three dynamic regimes of loading rate. First, bond strength emerges at a critical rate of loading (> or = 0) at which spontaneous dissociation is just frequent enough to keep the distribution peak at zero force. In the slow-loading regime immediately above the critical rate, strength grows as a weak power of loading rate and reflects initial coupling of force to the bonding potential. At higher rates, there is crossover to a fast regime in which strength continues to increase as the logarithm of the loading rate over many decades independent of the type of attraction. Finally, at ultrafast loading rates approaching the domain of molecular dynamics simulations, the bonding potential is quickly overwhelmed by the rapidly increasing force, so that only naked frictional drag on the structure remains to retard separation. Hence, to expose the energy landscape that governs bond strength, molecular adhesion forces must be examined over an enormous span of time scales. However, a significant gap exists between the time domain of force measurements in the laboratory and the extremely fast scale

  12. Thermographic Inspection Of Superplastically Formed Diffusion Bonded Titanium Panels

    NASA Astrophysics Data System (ADS)

    Haavig, David L.; King, Daniel C.

    1988-01-01

    Infrared thermographic nondestructive inspection of superplastically formed diffusion bonded (SPF/DB) titanium structures is discussed. Nondestructive testing (NDT) of the structures produced by this recently developed method is vital for construction of modern fighter aircraft. Forming and bonding parameters can be optimized by proper interpretation of NDT results. Currently, ultrasonic inspection is used for NDT on these parts. In an effort to reduce cost and inspection time required by ultrasonic testing, a thermographic investigation of panel response to rapid heating was undertaken. Panels were uniformly illuminated for a duration of up to four seconds by high intensity lamps. Infrared images of temperature variation due to panel thickness were observed. Correlation of thermograms with ultrasonic and destructive investigations indicate that lack of bonding and panel formations can easily be observed. We have demonstrated that thermographic inspection provides an equally sensitive and lower cost alternative to ultrasonic inspection. Finally, thermographic inspection facilities for large scale inspection are suggested.

  13. 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.

  14. Dynamic properties of hydrogen-bonded networks in supercritical water

    PubMed

    Marti

    2000-01-01

    Dynamic properties of supercritical water at temperatures between 573 and 773 K and densities between 0.49 and 0.83 g/cm(3) have been investigated by molecular dynamics simulation and compared to states located on the vapor-liquid coexistence curve. A flexible simple point charge potential has been assumed for interactions in the subcritical states, whereas a reparameterization of that model has been performed to model the supercritical states. The hydrogen bonding structure and the diffusion coefficients in an ensemble of simulated states were previously analyzed and a good agreement with available experimental data was found. Dynamic properties of hydrogen bonding like the bond lifetimes and the influence of hydrogen bonds in the vibrational spectra are discussed along a range of simulation conditions. A nonlinear behavior of the hydrogen-bond lifetime as a function of temperature is observed in subcritical water whereas a linear dependence is found in supercritical water. Special attention is paid to the intermolecular vibrational spectrum (10-400 cm(-1)). It has been observed that the mode centered at 200 cm(-1), attributed to the intermolecular O-O stretching vibration in the ambient state remains active in the supercritical states.

  15. 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

  16. Delayed mechanical failure of silver-interlayer diffusion bonds

    SciTech Connect

    Kassner, M.E. ); Rosen, R.S.; Henshall, G.A. . Physical Metallurgy and Joining Section)

    1990-12-01

    Silver-interlayer diffusion bonds were fabricated using planar-magnetron sputtering (PMS). The bonds exhibit very high tensile strengths, despite the soft interlayer, because of the constraint by the base metal. However, these joints undergo delayed failure at relatively low tensile stresses at ambient temperatures, apparently by a ductile microvoid coalescence mechanism at the bond interfaces. Two classes of delayed tensile failure were investigated. In the first case, the applied stress does not produced any plastic deformation in the base metal, and failure appears to be controlled by time-dependent plasticity within the silver interlayer as a result of the effective stress in the interlayer. The plasticity causes cavity nucleation and, eventually, interlinkage and failure. In the second case, time-dependent plasticity is observed in base metals, and concomitant shear occurs within the softer silver under a high triaxial stress state. Here, the time-dependent plasticity of the base metal accelerates plasticity and failure in the interlayer. These models were substantiated by careful analysis of the stress and temperature dependence of the rupture times, finite element analysis of the stress state within the interlayer, and microscopy of the fracture surfaces and interfaces loaded to various fractions of the expected rupture times. These findings are applicable to bonds in which the interlayers are prepared by processes other than physical vapor deposition.

  17. Modeling the Hydrogen Bond within Molecular Dynamics

    ERIC Educational Resources Information Center

    Lykos, Peter

    2004-01-01

    The structure of a hydrogen bond is elucidated within the framework of molecular dynamics based on the model of Rahman and Stillinger (R-S) liquid water treatment. Thus, undergraduates are exposed to the powerful but simple use of classical mechanics to solid objects from a molecular viewpoint.

  18. Modeling the Hydrogen Bond within Molecular Dynamics

    ERIC Educational Resources Information Center

    Lykos, Peter

    2004-01-01

    The structure of a hydrogen bond is elucidated within the framework of molecular dynamics based on the model of Rahman and Stillinger (R-S) liquid water treatment. Thus, undergraduates are exposed to the powerful but simple use of classical mechanics to solid objects from a molecular viewpoint.

  19. Elastic constants for superplastically formed/diffusion-bonded sandwich structures

    NASA Technical Reports Server (NTRS)

    Ko, W. L.

    1979-01-01

    Formulae and the associated graphs are presented for contrasting the effective elastic constants for a superplastically formed/diffusion-bonded (SPF/DB) corrugated sandwich core and a honeycomb sandwich core. The results used in the comparison of the structural properties of the two types of sandwich cores are under conditions of equal sandwich density. It was found that the stiffness in the thickness direction of the optimum SPF/DB corrugated core (i.e., triangular truss core) was lower than that of the honeycomb core, and that the former had higher transverse shear stiffness than the latter.

  20. Diffusion Bonding and Characterization of a Dispersion Strengthened Aluminum Alloy

    NASA Astrophysics Data System (ADS)

    Cooke, Kavian Omar

    Aluminum metal matrix composites (Al-MMC's) containing silicon carbide or alumina particle reinforcements are used extensively in automotive and aircraft industries. The addition of a reinforcing phase has led to significant improvements in the mechanical properties of these alloys. However, despite substantial improvements in the properties, the lack of a reliable joining method has restricted their full potential. The differences in physical and metallurgical properties between the ceramic phase and the Al-MMC, prevents the successful application of the fusion welding processes, conventionally used for joining monolithic aluminum alloys. Therefore, alternative techniques that prevent microstructural changes in the base metal need to be developed. In this study, the transient liquid phase diffusion bonding and eutectic bonding of a particle reinforced Al 6061-MMC was investigated to identify a method that could control particle segregation within the joint and increase the final joint strength. The results showed that TLP bonding using Ni-foil was possible at 600°C for 10 minutes using a pressure of 0.01 MPa. However, characterization of the bond interface showed a wide particle segregated zone due to the "pushing effect" of the solid/liquid interface during isothermal solidification stage of bonding. The presence of this particle segregated zone was shown to cause low joint strengths. In order to overcome these problems, TLP bonding was performed using electrodeposited coatings of Ni and Ni-Al 2O3 as a way of controlling the volume of eutectic liquid formed at the joint. Theoretical and experimental work showed that the use of thin coatings was successful in reducing the width of the segregated zone formed at the joint and this had the effect of increasing joint shear strength values. Furthermore, lower bonding temperature could also be used as a method of reducing particle segregation and therefore, a Cu-Sn interlayer was used to form a eutectic bond. The

  1. Diffusion of co-sputtered metals as bonding materials for 3D interconnects during thermal treatments.

    PubMed

    Hsu, S Y; Chen, H Y; Chen, K N

    2012-03-01

    Diffusion behaviors of co-sputtered metals during thermal treatments were investigated, where these co-sputtered metals can be used as bonding materials for 3D Interconnects. In this paper, we report the diffusion behaviors and discuss the diffusion mechanisms of co-sputtered metals before and after annealing. Atom and vacancy volume, vacancy formation energy, and activation energy are proposed to explain the diffusion direction and diffusion rate among different co-sputtered metals. Based on the excellent bonding performance of this method, Cu/metal co-sputtering bonding is considered as a potential candidate for advanced bonding technology.

  2. Molecular dynamics simulations of substitutional diffusion

    DOE PAGES

    Zhou, Xiaowang; Jones, Reese E.; Gruber, Jacob

    2016-12-18

    In atomistic simulations, diffusion energy barriers are usually calculated for each atomic jump path using a nudged elastic band method. Practical materials often involve thousands of distinct atomic jump paths that are not known a priori. Hence, it is often preferred to determine an overall diffusion energy barrier and an overall pre-exponential factor from the Arrhenius equation constructed through molecular dynamics simulations of mean square displacement of the diffusion species at different temperatures. This approach has been well established for interstitial diffusion, but not for substitutional diffusion at the same confidence. Using In 0.1 Ga 0.9 N as an example,more » we have identified conditions where molecular dynamics simulations can be used to calculate highly converged Arrhenius plots for substitutional alloys. As a result, this may enable many complex diffusion problems to be easily and reliably studied in the future using molecular dynamics, provided that moderate computing resources are available.« less

  3. Molecular dynamics simulations of substitutional diffusion

    SciTech Connect

    Zhou, Xiaowang; Jones, Reese E.; Gruber, Jacob

    2016-12-18

    In atomistic simulations, diffusion energy barriers are usually calculated for each atomic jump path using a nudged elastic band method. Practical materials often involve thousands of distinct atomic jump paths that are not known a priori. Hence, it is often preferred to determine an overall diffusion energy barrier and an overall pre-exponential factor from the Arrhenius equation constructed through molecular dynamics simulations of mean square displacement of the diffusion species at different temperatures. This approach has been well established for interstitial diffusion, but not for substitutional diffusion at the same confidence. Using In 0.1 Ga 0.9 N as an example, we have identified conditions where molecular dynamics simulations can be used to calculate highly converged Arrhenius plots for substitutional alloys. As a result, this may enable many complex diffusion problems to be easily and reliably studied in the future using molecular dynamics, provided that moderate computing resources are available.

  4. The diffusion bonding of silicon carbide and boron carbide using refractory metals

    SciTech Connect

    Cockeram, B.V.

    1999-10-01

    Joining is an enabling technology for the application of structural ceramics at high temperatures. Metal foil diffusion bonding is a simple process for joining silicon carbide or boron carbide by solid-state, diffusive conversion of the metal foil into carbide and silicide compounds that produce bonding. Metal diffusion bonding trials were performed using thin foils (5 {micro}m to 100 {micro}m) of refractory metals (niobium, titanium, tungsten, and molybdenum) with plates of silicon carbide (both {alpha}-SiC and {beta}-SiC) or boron carbide that were lapped flat prior to bonding. The influence of bonding temperature, bonding pressure, and foil thickness on bond quality was determined from metallographic inspection of the bonds. The microstructure and phases in the joint region of the diffusion bonds were evaluated using SEM, microprobe, and AES analysis. The use of molybdenum foil appeared to result in the highest quality bond of the metal foils evaluated for the diffusion bonding of silicon carbide and boron carbide. Bonding pressure appeared to have little influence on bond quality. The use of a thinner metal foil improved the bond quality. The microstructure of the bond region produced with either the {alpha}-SiC and {beta}-SiC polytypes were similar.

  5. First-Principles Simulation Study of Vibrational Spectral Diffusion and Hydrogen Bond Fluctuations in Aqueous Solution of N-Methylacetamide.

    PubMed

    Yadav, Vivek Kumar; Chandra, Amalendu

    2015-07-30

    We have presented a first-principles simulation study of the vibrational spectral diffusion and hydrogen bond dynamics in an aqueous solution of N-methylacetamide (NMA). We have studied the spectral diffusion of local OD stretch modes of deuterated water in the first hydration shells of the carbonyl (CO) and deuterated amide (ND) modes and their relations to the dynamics of hydrogen bonds formed by water with these groups. The frequency fluctuations of the amide I and amide A modes of the solute are also investigated. It is found that the vibrational spectral diffusion of water molecules in the first hydration shell of the carbonyl oxygen of NMA proceeds with three time scales: A short-time relaxation (∼100 fs) originating from the dynamics of NMA-water hydrogen bonds without breaking, a slower relaxation (∼3.3 ps) arising from the breaking dynamics of NMA(CO)-water hydrogen bonds, and another longer time constant (∼14 ps) coming from the escape dynamics of water from the first hydration shell of carbonyl oxygen. The current results show that the NMA(CO)-water hydrogen bonds have a longer lifetime than those between water molecules, although frequency calculations reveal a slightly higher stretch frequency of the water molecules in the first hydration shell of the carbonyl oxygen of NMA. An analysis of the vibrational spectral diffusion of solute modes is also presented in terms of the dynamics of solute-water hydrogen bonds. Effects of dispersion interactions on various calculated properties of the NMA-water system are also investigated in the present work.

  6. 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

  7. Dynamics and diffusion mechanism of low-density liquid silicon

    SciTech Connect

    Shen, B.; Wang, Z. Y.; Dong, F.; Guo, Y. R.; Zhang, R. J.; Zheng, Y. X.; Wang, S. Y.; Wang, C. Z.; Ho, K. M.; Chen, L. Y.

    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 the 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.

  8. The metallurgical integrity of the frit vent assembly diffusion bond

    SciTech Connect

    Ulrich, G.B.

    1994-06-01

    Iridium alloy clad vent sets (CVSs) are now being made by Energy Systems at the Oak Ridge Y-12 Plant. These CVSs are being made for the US Department of Energy`s (NE-53) General Purpose Heat Source- Radioisotope Thermoelectric Generator (GPHS-RTG) program, which is to supply electrical power for the National Aeronautics and Space Administration`s Cassini mission to Saturn. A GPHS-RTG has 72 CVSs. Each CVS encapsulates one {sup 238}PuO{sub 2} fuel pellet. The helium gas produced from the alpha decay of the {sup 238}Pu is vented through a nominal 0.45-mm-diam hole in the vent cup of each CVS. A frit vent assembly that is electron beam welded over the vent hole allows helium gas to escape but prevents plutonia fines from exiting. The metallurgical integrity of frit vent assemblies produced by Martin Marietta Energy Systems, Inc. (Energy Systems) were compared with those produced earlier by EG&G-Mound Applied Technology, Inc. (EG&G-MAT). Scanning electron microscope (SEM) photographs were taken (at magnifications of from 126X to 1,000X) of the starting frit vent powder and the diffusion-bonded powder in finished frit vent assemblies produced by Energy Systems and EG&G-MAT. Frit vent assemblies also were metallographically prepared and visually examined/photographed at magnifications of from 50X to 1,000X. The SEM and metallographic examinations of the particle-to-particle and particle-to-foil component diffusion bonds indicated that the Energy Systems-produced and EG&G-MAT-produced frit vent assemblies have comparable metallurgical integrity. Statistical analysis of the Energy Systems production data shows that the frit vent manufacturing yield is 91%.

  9. The metallurgical integrity of the frit vent assembly diffusion bond

    NASA Astrophysics Data System (ADS)

    Ulrich, G. B.

    1994-06-01

    Iridium alloy clad vent sets (CVS's) are now being made by Energy Systems at the Oak Ridge Y-12 Plant. These CVS's are being made for the US Department of Energy's (NE-53) General Purpose Heat Source- Radioisotope Thermoelectric Generator (GPHS-RTG) program, which is to supply electrical power for the National Aeronautics and Space Administration's Cassini mission to Saturn. A GPHS-RTG has 72 CVS'. Each CVS encapsulates one (238)PuO2 fuel pellet. The helium gas produced from the alpha decay of the (238)Pu is vented through a nominal 0.45-mm-diam hole in the vent cup of each CVS. A frit vent assembly that is electron beam welded over the vent hole allows helium gas to escape but prevents plutonia fines from exiting. The metallurgical integrity of frit vent assemblies produced by Martin Marietta Energy Systems, Inc. (Energy Systems) were compared with those produced earlier by EG&G-Mound Applied Technology, Inc. (EG&G-MAT). Scanning electron microscope (SEM) photographs were taken (at magnifications of from 126x to 1,000x) of the starting frit vent powder and the diffusion-bonded powder in finished frit vent assemblies produced by Energy Systems and EG&G-MAT. Frit vent assemblies also were metallographically prepared and visually examined/photographed at magnifications of from 50x to 1,000x. The SEM and metallographic examinations of the particle-to-particle and particle-to-foil component diffusion bonds indicated that the Energy Systems-produced and EG&G-MAT-produced frit vent assemblies have comparable metallurgical integrity. Statistical analysis of the Energy Systems production data shows that the frit vent manufacturing yield is 91%.

  10. Dripping dynamics at high Bond numbers

    NASA Astrophysics Data System (ADS)

    Rubio-Rubio, Mariano; Taconet, Paloma; Sevilla, Alejandro

    2014-11-01

    When dispensing liquid from a vertically oriented injector under gravity, drops grow at the outlet until the surface tension forces can no longer balance their weight, and the pinch-off occurs. This dripping regime no longer exists above a critical flow rate, at which an abrupt transition to jetting takes place. These phenomena are governed by the liquid properties, the injector size and the injection flow rate, or non-dimensionally, by the Bond, Bo , Weber, We , and Kapitza, Γ, numbers. Detailed accounts of the rich dynamics of the dripping regime and the transition leading to jetting can be found in the literature (e.g. Phys. Rev. Lett. vol. 93, 2004, and Phys. Fluids vol. 18, 2006), but only for two different values of Bo . Therefore, we present new experiments on the dripping dynamics and jetting transition for a wide range of both the liquid viscosity and the size of the injector, reaching values of Bo up to one order-of-magnitude larger than those present in the literature. Our results reveal the existence of new dynamics in the dripping regime not observed at small Bond numbers. In addition, we quantify the hysteresis present in the dripping-jetting transition, previously measured only for the inviscid case. Supported by Spanish MINECO under Project DPI 2011-28356-C03-02.

  11. Liquid phase diffusion bonding of A1070 by using metal formate coated Zn sheet

    NASA Astrophysics Data System (ADS)

    Ozawa, K.; Koyama, S.; shohji, I.

    2017-05-01

    Aluminium alloy have high strength and easily recycle due to its low melting point. Therefore, aluminium is widely used in the manufacturing of cars and electronic devices. In recent years, the most common way for bonding aluminium alloy is brazing and friction stir welding. However, brazing requires positional accuracy and results in the formation of voids by the flax residue. Moreover, aluminium is an excellent heat radiating and electricity conducting material; therefore, it is difficult to bond together using other bonding methods. Because of these limitations, liquid phase diffusion bonding is considered to the suitable method for bonding aluminium at low temperature and low bonding pressure. In this study, the effect of metal formate coating processing of zinc surface on the bond strength of the liquid phase diffusion bonded interface of A1070 has been investigated by SEM observation of the interfacial microstructures and fractured surfaces after tensile test. Liquid phase diffusion bonding was carried out under a nitrogen gas atmosphere at a bonding temperature of 673 K and 713 K and a bonding load of 6 MPa (bonding time: 15 min). As a result of the metal formate coating processing, a joint having the ultimate tensile strength of the base aluminium was provided. It is hypothesized that this is because metallic zinc is generated as a result of thermal decomposition of formate in the bonded interface at lower bonding temperatures.

  12. Leakage rates and thermal requirements for the diffusion bonding of microchannel arrays via internal convective heating

    SciTech Connect

    Bose, Sumantra; Palo, Daniel R.; Paul, Brian

    2007-07-24

    Diffusion bonding cycle times can be a large cost factor in the production of metal microchannel devices. The challenge is to significantly minimize this cost by reducing the bonding cycle time through rapid and uniform heating and cooling within the bonding process. Heating rates in diffusion bonding processes are typically limited by the need to minimize thermal gradients during bonding. A novel method is described which takes advantage of the internal flow passages within microchannel devices for convective heat transfer during the bonding process. The internal convective heating (ICH) technique makes use of heated inert gas to provide the microchannel assembly with rapid and uniform heat input. This paper will demonstrate the ability to effectively diffusion bond microchannel laminae using the ICH method by investigating the leakage rates.

  13. Effect of Sn Alloying on the Diffusion Bonding Behavior of Al-Mg-Si Alloys

    NASA Astrophysics Data System (ADS)

    Atabay, Sıla Ece; Esen, Ziya; Dericioglu, Arcan F.

    2017-07-01

    Effect of Sn as an alloying element on the diffusion-bonding behavior of Al-Mg-Si alloy has been studied by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and mechanical testing of the diffusion-bonded joint. XRD results revealed the formation of Mg2Sn and (Sn) phases during solidification following induction casting. DSC results showed local liquid (Sn) formation during the bonding process for Sn-containing alloys, where its amount was found to be increasing with the increasing Sn content. Results revealed that Sn addition leads to an increase in the bond shear strength of the diffusion-bonded joints and elimination of the irregularities formed on the bonded interface. Fractured surfaces showed that formation of (Sn) layer at the bonded interface causes the fracture to transform from the ductile to the mixed fracture mode.

  14. The dynamics of unsteady detonation with diffusion

    SciTech Connect

    Aslam, Tariq Dennis; Romick, Christopher; Powers, Joseph

    2010-01-01

    Here we consider an unsteady detonation with diffusion included. This introduces an interaction between the reaction length scales and diffusion length scales. Detailed kinetics introduce multiple length scales as shown though the spatial eigenvalue analysis of hydrogen-oxygen system; the smallest length scale is {approx} 10{sup 7} m and the largest {approx} 10{sup -2} m; away from equilibrium, the breadth can be larger. In this paper, we consider a simpler set of model equations, similar to the inviscid reactive compressible fluid equations, but include diffusion (in the form of thermal/energy, momentum, and mass diffusion). We will seek to reveal how the complex dynamics already discovered in one-step systems in the inviscid limit changes with the addition of diffusion.

  15. Ultrasonically Activated Diffusion Bonding for Fluidic Control Assembly

    DTIC Science & Technology

    1979-02-01

    costs can be exceptionally low due to brief bonding time, low energy consumption, and freedom from special atmospheres or temperatures during bonding...bond energy 9 2. Ultrasonic bond energy density for aluminum foil 2.1 3. Load and reverse power ratios versus load impedance 15 4...ultrasonic energy input .... 46 11. Array of 5-mil etched laminates as assembled for active element tests 53 12. Top and bottom views of

  16. Diffuse charge dynamics in ionic thermoelectrochemical systems

    NASA Astrophysics Data System (ADS)

    Stout, Robert F.; Khair, Aditya S.

    2017-08-01

    Thermoelectrics are increasingly being studied as promising electrical generators in the ongoing search for alternative energy sources. In particular, recent experimental work has examined thermoelectric materials containing ionic charge carriers; however, the majority of mathematical modeling has been focused on their steady-state behavior. Here, we determine the time scales over which the diffuse charge dynamics in ionic thermoelectrochemical systems occur by analyzing the simplest model thermoelectric cell: a binary electrolyte between two parallel, blocking electrodes. We consider the application of a temperature gradient across the device while the electrodes remain electrically isolated from each other. This results in a net voltage, called the thermovoltage, via the Seebeck effect. At the same time, the Soret effect results in migration of the ions toward the cold electrode. The charge dynamics are described mathematically by the Poisson-Nernst-Planck equations for dilute solutions, in which the ion flux is driven by electromigration, Brownian diffusion, and thermal diffusion under a temperature gradient. The temperature evolves according to the heat equation. This nonlinear set of equations is linearized in the (experimentally relevant) limit of a "weak" temperature gradient. From this, we show that the time scale on which the thermovoltage develops is the Debye time, 1 /D κ2 , where D is the Brownian diffusion coefficient of both ion species, and κ-1 is the Debye length. However, the concentration gradient due to the Soret effect develops on the bulk diffusion time, L2/D , where L is the distance between the electrodes. For thin diffuse layers, which is the condition under which most real devices operate, the Debye time is orders of magnitude less than the diffusion time. Therefore, rather surprisingly, the majority of ion motion occurs after the steady thermovoltage has developed. Moreover, the dynamics are independent of the thermal diffusion

  17. Statics and dynamics of magnetocapillary bonds

    NASA Astrophysics Data System (ADS)

    Lagubeau, Guillaume; Grosjean, Galien; Darras, Alexis; Lumay, Geoffroy; Hubert, Maxime; Vandewalle, Nicolas

    2016-05-01

    When ferromagnetic particles are suspended at an interface under magnetic fields, dipole-dipole interactions compete with capillary attraction. This combination of forces has recently given promising results towards controllable self-assemblies as well as low-Reynolds-number swimming systems. The elementary unit of these assemblies is a pair of particles. Although equilibrium properties of this interaction are well described, the dynamics remain unclear. In this paper, the properties of magnetocapillary bonds are determined by probing them with magnetic perturbations. Two deformation modes are evidenced and discussed. These modes exhibit resonances whose frequencies can be detuned to generate nonreciprocal motion. A model is proposed that can become the basis for elaborate collective behaviors.

  18. The application of diffusion bonding in the manufacture of aeroengine components

    NASA Astrophysics Data System (ADS)

    Fitzpatrick, J. A.

    Rolls-Royce has developed and optimized diffusion bonding processes for the manufacture of advanced titanium alloy aeroengine structures and components. Both categories of the joining technique - 'liquid-phase' and 'solid-state' - are being applied in the production of both static fabrications and complex rotating parts. In order to utilize diffusion bonding processes in a production environment, the process parameters which contribute to consistent formation of joints of the required strength have been critically examined. Process variables include temperature, pressure, time, surface roughness and, in the case of liquid-phase diffusion bonding, interlayer composition, density and thickness. Mechanical testing (tensile, impact and fatigue) complemented by metallography has predominantly been used to identify the permitted variations in the processes for the realistic and economical production manufacture of high quality lightweight aeroengine fabrications. The development of a high integrity bond via optimized diffusion bonding processes has been fundamental to the development of Rolls-Royce's unique wide chord fan design concept.

  19. Pressure Dependence of Hydrogen-Bond Dynamics in Liquid Water Probed by Ultrafast Infrared Spectroscopy.

    PubMed

    Lapini, Andrea; Pagliai, Marco; Fanetti, Samuele; Citroni, Margherita; Scandolo, Sandro; Bini, Roberto; Righini, Roberto

    2016-09-15

    Clarifying the structure/dynamics relation of water hydrogen-bond network has been the aim of extensive research over many decades. By joining anvil cell high-pressure technology, femtosecond 2D infrared spectroscopy, and molecular dynamics simulations, we studied, for the first time, the spectral diffusion of the stretching frequency of an HOD impurity in liquid water as a function of pressure. Our experimental and simulation results concordantly demonstrate that the rate of spectral diffusion is almost insensitive to the applied pressure. This behavior is in contrast with the previously reported pressure-induced speed up of the orientational dynamics, which can be rationalized in terms of large angular jumps involving sudden switching between two hydrogen-bonded configurations. The different trend of the spectral diffusion can be, instead, inferred considering that the first solvation shell preserves the tetrahedral structure with pressure and the OD stretching frequency is only slight perturbed.

  20. Developing A Laser Shockwave Model For Characterizing Diffusion Bonded Interfaces

    SciTech Connect

    James A. Smith; Jeffrey M. Lacy; Barry H. Rabin

    2014-07-01

    12. Other advances in QNDE and related topics: Preferred Session Laser-ultrasonics Developing A Laser Shockwave Model For Characterizing Diffusion Bonded Interfaces 41st Annual Review of Progress in Quantitative Nondestructive Evaluation Conference QNDE Conference July 20-25, 2014 Boise Centre 850 West Front Street Boise, Idaho 83702 James A. Smith, Jeffrey M. Lacy, Barry H. Rabin, Idaho National Laboratory, Idaho Falls, ID ABSTRACT: The US National Nuclear Security Agency has a Global Threat Reduction Initiative (GTRI) which is assigned with reducing the worldwide use of high-enriched uranium (HEU). A salient component of that initiative is the conversion of research reactors from HEU to low enriched uranium (LEU) fuels. An innovative fuel is being developed to replace HEU. The new LEU fuel is based on a monolithic fuel made from a U-Mo alloy foil encapsulated in Al-6061 cladding. In order to complete the fuel qualification process, the laser shock technique is being developed to characterize the clad-clad and fuel-clad interface strengths in fresh and irradiated fuel plates. The Laser Shockwave Technique (LST) is being investigated to characterize interface strength in fuel plates. LST is a non-contact method that uses lasers for the generation and detection of large amplitude acoustic waves to characterize interfaces in nuclear fuel plates. However the deposition of laser energy into the containment layer on specimen’s surface is intractably complex. The shock wave energy is inferred from the velocity on the backside and the depth of the impression left on the surface from the high pressure plasma pulse created by the shock laser. To help quantify the stresses and strengths at the interface, a finite element model is being developed and validated by comparing numerical and experimental results for back face velocities and front face depressions with experimental results. This paper will report on initial efforts to develop a finite element model for laser

  1. Levitation effect: role of symmetry and dependence of diffusivity on the bond length of homonuclear and heteronuclear diatomic species.

    PubMed

    Sharma, Manju; Yashonath, S

    2011-04-07

    Molecular dynamics investigation of model diatomic species confined to the α-cages of zeolite NaY is reported. The dependence of self-diffusivity on the bond length of the diatomic species has been investigated. Three different sets of runs have been carried out. In the first set, the two atoms of the diatomic molecule interact with the zeolite atoms with equal strength (example, O(2), the symmetric case). In the second and third sets which correspond to asymmetric cases, the two atoms of the diatomic molecule interact with unequal strengths (example, CO). The result for the symmetric case exhibits a well-defined maximum in self-diffusivity for an intermediate bond length. In contrast to this, the intermediate asymmetry leads to a less pronounced maximum. For the large asymmetric case, the maximum is completely absent. These findings are analyzed by computing a number of related properties. These results provide a direct confirmation at the microscopic level of the suggestion by Derouane that the supermobility observed experimentally by Kemball has its origin in the mutual cancellation of forces. The maximum in diffusivity from molecular dynamics is seen at the value predicted by the levitation effect. Further, these findings suggest a role for symmetry in the existence of a diffusivity maximum as a function of diameter of the diffusant often referred to as the levitation effect. The nature of the required symmetry for the existence of anomalous diffusivity is interaction symmetry which is different from that normally encountered in crystallography.

  2. General theory of heat diffusion dynamics

    NASA Astrophysics Data System (ADS)

    Tröster, A.; Schranz, W.

    2002-11-01

    A detailed theoretical investigation of the influence of heat diffusion processes on the low-frequency dispersion in macroscopic elastic susceptibilities is presented. In particular, a general solution of the heat diffusion equation is derived for arbitrary boundary conditions and externally imposed periodic and spatially inhomogeneous stress. In contrast to other calculations found in the literature, our results indicate that in elastic experiments on monodomain samples of macroscopic dimensions the isothermal-adiabatic crossover function necessarily reduces to a Debye-like dispersion. Experimentally, this is illustated by measurements of the complex dynamic elastic susceptibilities of KSCN and KMnF3. Our approach also allows to discuss heat diffusion in polydomain crystals and heterogeneous systems, for which one obtains dispersions of a non-Debye type. While explicitly derived in an elastic context, the present theory also applies to heat diffusion in dielectric materials.

  3. A Batch Wafer Scale LIGA Assembly and Packaging Technique vai Diffusion Bonding

    SciTech Connect

    Christenson, T.R.; Schmale, D.T.

    1999-01-27

    A technique using diffusion bonding (or solid-state welding) has been used to achieve batch fabrication of two- level nickel LIGA structures. Interlayer alignment accuracy of less than 1 micron is achieved using press-fit gauge pins. A mini-scale torsion tester was built to measure the diffusion bond strength of LIGA formed specimens that has shown successful bonding at temperatures of 450"C at 7 ksi pressure with bond strength greater than 100 Mpa. Extensions to this basic process to allow for additional layers and thereby more complex assemblies as well as commensurate packaging are discussed.

  4. 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.

  5. Diffusion bonding between ODS ferritic steel and F82H steel for fusion applications

    NASA Astrophysics Data System (ADS)

    Noh, Sanghoon; Kim, Byungjun; Kasada, Ryuta; Kimura, Akihiko

    2012-07-01

    Diffusion bonding techniques were employed to join high Cr oxide dispersion strengthened (ODS) ferritic steel (Fe-15Cr-2W-0.2Ti-0.35Y2O3) and F82H steel under uni-axial hydrostatic pressure using a high vacuum hot press, and the microstructure and mechanical properties of the joints were investigated. The dissimilar joints were bonded by solid-state diffusion bonding (SSDB) and liquid phase diffusion bonding (LPDB). After bonding process, heat treatments were conducted to utilize the phase transformation of F82H steel for recovering the martensitic structure. Tensile tests with miniaturized specimens were carried out to investigate and compare the bonding strengths of each joint. Microstructure was observed for the bonding interface, and fracture mode was investigated after the tensile tests. LPDB joint of interfacial F82H steel fully recovered to martensite phase by post-joining heat treatments, while SSDB joint had ferrite phases at the interface even after heat treatment, which is considered to be due to decarburization of F82H steel during the bonding process. Therefore it is considered that the insert material plays a role as diffusion barrier of carbon during LPDB process. Microstructure observations and tensile tests of the joints revealed that the LPDB joints possess suitable tensile properties which are comparable to that of F82H steel. This indicates that LPDB is more promising method to bond ODS-FS and F82H steel than SSDB.

  6. Diffusion bonding and brazing of high purity copper for linear collider accelerator structures

    NASA Astrophysics Data System (ADS)

    Elmer, J. W.; Klingmann, J.; van Bibber, K.

    2001-05-01

    Diffusion bonding and brazing of high purity copper were investigated to develop procedures for joining precision machined copper components for the Next Linear Collider (NLC). Diffusion bonds were made over a range of temperatures from 400 °C to 1000 °C, under two different loading conditions [3.45 kPa (0.5 psi) and 3.45 MPa (500 psi)], and on two different diamond machined surface finishes. Brazes were made using pure silver, pure gold, and gold-nickel alloys, and different heating rates produced by both radiation and induction heating. Braze materials were applied by both physical vapor deposition (PVD) and conventional braze alloy shims. Results of the diffusion bonding experiments showed that bond strengths very near that of the copper base metal could be made at bonding temperatures of 700 °C or higher at 3.45 MPa bonding pressure. At lower temperatures, only partial strength diffusion bonds could be made. At low bonding pressures (3.45 kPa), full strength bonds were made at temperatures of 800 °C and higher, while no bonding (zero strength) was observed at temperatures of 700 °C and lower. Observations of the fracture surfaces of the diffusion bonded samples showed the effects of surface finish on the bonding mechanism. These observations clearly indicate that bonding began by point asperity contact, and flatter surfaces resulted in a higher percentage of bonded area under similar bonding conditions. Results of the brazing experiments indicated that pure silver worked very well for brazing under both conventional and high heating rate scenarios. Similarly, pure silver brazed well for both the PVD layers and the braze alloy shims. The gold and gold-containing brazes had problems, mainly due to the high diffusivity of gold in copper. These problems led to the necessity of overdriving the temperature to ensure melting, the presence of porosity in the joint, and very wide braze joints. Based on the overall findings of this study, a two-step joining method

  7. In-process oxidation protection in fluxless brazing or diffusion bonding of aluminum alloys

    NASA Technical Reports Server (NTRS)

    Okelly, K. P.; Featherston, A. B.

    1974-01-01

    Aluminum is cleaned of its oxide coating and is sealed immediately with polymeric material which makes it suitable for fluxless brazing or diffusion bonding. Time involved between cleaning and brazing is no longer critical factor.

  8. Diffusion bonding and its application to manufacturing. [for joining of metal parts

    NASA Technical Reports Server (NTRS)

    Spurgeon, W. M.

    1972-01-01

    In its simplest form diffusion bonding is accomplished by placing clean metal surfaces together under a sufficient load and heating. The natural interatomic attractive force between atoms transforms the interface into a natural grain boundary. Therefore, in principle, the properties of the bond area are identical to those of the parent metal. Other advantages of diffusion bonding over conventional methods of bonding include freedom from residual stresses, excessive deformation, foreign metals, or changed crystal structures. Stainless steels, nickel-base superalloys, and aluminum alloys have all been successfully joined. Complex hardware, including integrated flueric devices, jet engine servovalves, and porous woven structures have been fabricated. The processing involved is discussed, along with such theoretical considerations as the role of metal surfaces, the formation of metal contact junctions, and the mechanisms of material transport in diffusion bonding.

  9. Method of fluxless brazing and diffusion bonding of aluminum containing components

    NASA Technical Reports Server (NTRS)

    Featherston, A. B.; Okelly, K. P. (Inventor)

    1976-01-01

    A method of diffusion bonding and fluxless brazing of aluminum containing components is reported. The aluminum surfaces are freed of any aluminum oxide coating and are coated with a polymeric sealer which can be thermally removed leaving essentially no residue. The polymeric sealer is being removed in a substantially oxygen free environment, and the aluminum components are then being brazed or diffusion bonded without the use of a flux to remove oxide coating.

  10. 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.

  11. Polaronic quantum diffusion in dynamic localization regime

    NASA Astrophysics Data System (ADS)

    Yao, Yao

    2017-04-01

    We investigate the quantum dynamics in a disordered electronic lattice by the time-dependent density matrix renormalization group algorithm. The on-site energy in the lattice follows the Fibonacci sequence and the electron off-diagonally couples to a sub-Ohmic phonon bath. It is found that the slope of the inverse participation ratio versus the coupling strength undergoes a sudden change that indicates a transition from static to dynamic localization, and that the generated polarons coherently diffuse via hopping-like processes, evidenced by the saturated entanglement entropy, providing a novel scenario for a transportation mechanism in strongly disordered systems. Moreover, the mean-square displacement is revealed to be insensitive to the coupling strength, implying the quantum diffusion behavior survives the energy disorder that prevails in real organic materials.

  12. Molecular dynamics simulation of fractal aggregate diffusion

    NASA Astrophysics Data System (ADS)

    Pranami, Gaurav; Lamm, Monica H.; Vigil, R. Dennis

    2010-11-01

    The diffusion of fractal aggregates constructed with the method by Thouy and Jullien [J. Phys. A 27, 2953 (1994)10.1088/0305-4470/27/9/012] comprised of Np spherical primary particles was studied as a function of the aggregate mass and fractal dimension using molecular dynamics simulations. It is shown that finite-size effects have a strong impact on the apparent value of the diffusion coefficient (D) , but these can be corrected by carrying out simulations using different simulation box sizes. Specifically, the diffusion coefficient is inversely proportional to the length of a cubic simulation box, and the constant of proportionality appears to be independent of the aggregate mass and fractal dimension. Using this result, it is possible to compute infinite dilution diffusion coefficients (Do) for aggregates of arbitrary size and fractal dimension, and it was found that Do∝Np-1/df , as is often assumed by investigators simulating Brownian aggregation of fractal aggregates. The ratio of hydrodynamic radius to radius of gyration is computed and shown to be independent of mass for aggregates of fixed fractal dimension, thus enabling an estimate of the diffusion coefficient for a fractal aggregate based on its radius of gyration.

  13. The fabrication of all-silicon micro gas chromatography columns using gold diffusion eutectic bonding

    NASA Astrophysics Data System (ADS)

    Radadia, A. D.; Salehi-Khojin, A.; Masel, R. I.; Shannon, M. A.

    2010-01-01

    Temperature programming of gas chromatography (GC) separation columns accelerates the elution rate of chemical species through the column, increasing the speed of analysis, and hence making it a favorable technique to speedup separations in microfabricated GCs (micro-GC). Temperature-programmed separations would be preferred in an all-silicon micro-column compared to a silicon-Pyrex® micro-column given that the thermal conductivity and diffusivity of silicon is 2 orders of magnitude higher than Pyrex®. This paper demonstrates how to fabricate all-silicon micro-columns that can withstand the temperature cycling required for temperature-programmed separations. The columns were sealed using a novel bonding process where they were first bonded using a gold eutectic bond, then annealed at 1100 °C to allow gold diffusion into silicon and form what we call a gold diffusion eutectic bond. The gold diffusion eutectic-bonded micro-columns when examined using scanning electron microscopy (SEM), scanning acoustic microscopy (SAM) and blade insertion techniques showed bonding strength comparable to the previously reported anodic-bonded columns. Gas chromatography-based methane injections were also used as a novel way to investigate proper sealing between channels. A unique methane elution peak at various carrier gas inlet pressures demonstrated the suitability of gold diffusion eutectic-bonded channels as micro-GC columns. The application of gold diffusion eutectic-bonded all-silicon micro-columns to temperature-programmed separations (120 °C min-1) was demonstrated with the near-baseline separation of n-C6 to n-C12 alkanes in 35 s.

  14. Diffusion bonding of beryllium to CuCrZr for ITER applications.

    SciTech Connect

    Cadden, Charles H.; Puskar, Joseph David; Goods, Steven Howard

    2008-08-01

    Low temperature diffusion bonding of beryllium to CuCrZr was investigated for fusion reactor applications. Hot isostatic pressing was accomplished using various metallic interlayers. Diffusion profiles suggest that titanium is effective at preventing Be-Cu intermetallics. Shear strength measurements suggest that acceptable results were obtained at temperatures as low as 540C.

  15. Dynamics of Kinks: Nucleation, Diffusion, and Annihilation

    SciTech Connect

    Habib, Salman; Lythe, Grant

    2000-02-07

    We investigate the nucleation, annihilation, and dynamics of kinks in a classical (1+1)-dimensional {phi}{sup 4} field theory at finite temperature. From large scale Langevin simulations, we establish that the nucleation rate is proportional to the square of the equilibrium density of kinks. We identify two annihilation time scales: one due to kink-antikink pair recombination after nucleation, the other from nonrecombinant annihilation. We introduce a mesoscopic model of diffusing kinks based on ''paired'' and ''survivor'' kinks and antikinks. Analytical predictions for the dynamical time scales, as well as the corresponding length scales, are in good agreement with the simulations. (c) 2000 The American Physical Society.

  16. Hydrogen peroxide diffusion dynamics in dental tissues.

    PubMed

    Ubaldini, A L M; Baesso, M L; Medina Neto, A; Sato, F; Bento, A C; Pascotto, R C

    2013-07-01

    The aim of this study was to investigate the diffusion dynamics of 25% hydrogen peroxide (H2O2) through enamel-dentin layers and to correlate it with dentin's structural alterations. Micro-Raman Spectroscopy (MRS) and Fourier Transform Infrared Photoacoustic Spectroscopy (FTIR-PAS) were used to measure the spectra of specimens before and during the bleaching procedure. H2O2 was applied to the outer surface of human enamel specimens for 60 minutes. MRS measurements were performed on the inner surface of enamel or on the subsurface dentin. In addition, H2O2 diffusion dynamics from outer enamel to dentin, passing through the dentin-enamel junction (DEJ) was obtained with Raman transverse scans. FTIR-PAS spectra were collected on the outer dentin. MRS findings revealed that H2O2 (O-O stretching µ-Raman band) crossed enamel, had a more marked concentration at DEJ, and accumulated in dentin. FTIR-PAS analysis showed that H2O2 modified dentin's organic compounds, observed by the decrease in amides I, II, and III absorption band intensities. In conclusion, H2O2 penetration was demonstrated to be not merely a physical passage through enamel interprismatic spaces into the dentinal tubules. H2O2 diffusion dynamics presented a concentration gradient determined by the chemical affinity of the H2O2 with each specific dental tissue.

  17. Dynamic breaking of a single gold bond

    NASA Astrophysics Data System (ADS)

    Pobelov, Ilya V.; Lauritzen, Kasper Primdal; Yoshida, Koji; Jensen, Anders; Mészáros, Gábor; Jacobsen, Karsten W.; Strange, Mikkel; Wandlowski, Thomas; Solomon, Gemma C.

    2017-07-01

    While one might assume that the force to break a chemical bond gives a measure of the bond strength, this intuition is misleading. If the force is loaded slowly, thermal fluctuations may break the bond before it is maximally stretched, and the breaking force will be less than the bond can sustain. Conversely, if the force is loaded rapidly it is more likely that the maximum breaking force is measured. Paradoxically, no clear differences in breaking force were observed in experiments on gold nanowires, despite being conducted under very different conditions. Here we explore the breaking behaviour of a single Au-Au bond and show that the breaking force is dependent on the loading rate. We probe the temperature and structural dependencies of breaking and suggest that the paradox can be explained by fast breaking of atomic wires and slow breaking of point contacts giving very similar breaking forces.

  18. 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.

  19. Minimal model for dynamic bonding in colloidal transient networks

    NASA Astrophysics Data System (ADS)

    Krinninger, Philip; Fortini, Andrea; Schmidt, Matthias

    2016-04-01

    We investigate a model for colloidal network formation using Brownian dynamics computer simulations. Hysteretic springs establish transient bonds between particles with repulsive cores. If a bonded pair of particles is separated by a cutoff distance, the spring vanishes and reappears only if the two particles contact each other. We present results for the bond lifetime distribution and investigate the properties of the van Hove dynamical two-body correlation function. The model displays crossover from fluidlike dynamics, via transient network formation, to arrested quasistatic network behavior.

  20. Dynamic fracture toughnesses of reaction-bonded silicon nitride

    NASA Technical Reports Server (NTRS)

    Kobayashi, A. S.; Emery, A. F.; Liaw, B. M.

    1983-01-01

    The room-temperature dynamic fracture response of reaction-bonded silicon nitride is investigated using a hybrid experimental-numerical procedure. In this procedure, experimentally determined crack velocities are utilized to drive a dynamic finite-element code or dynamic finite-difference code in its generation mode in order to extract numerically the dynamic stress intensity factor of the fracturing specimen. Results show that the dynamic fracture toughness vs crack velocity relations of the two reaction-bonded silicon nitrides do not follow the general trend in those relations of brittle polymers and steel. A definite slow crack velocity during the initial phase of dynamic crack propagation is observed in reaction-bonded silicon nitride, which results in a nonunique dynamic fracture toughness vs crack velocity relation. In addition, it is found that a propagating crack will continue to propagate under a static stress intensity factor substantially lower than K(IC).

  1. Diffusion bonding of a superplastic Inconel 718SPF superalloy by electroless nickel plating

    SciTech Connect

    Yeh, M.S.; Chang, C.B.; Chuang, T.H.

    2000-02-01

    Although intimate contact can be obtained for diffusion bonding of a superplastic Inconel 718SPF superalloy under a low pressure of 7 MPa, the precipitates formed at the interface retarded achievement of a sound joint. The shear strength was only 41.5 MPa for an overlap length of 12 T (T = 1.3 mm, sheet thickness). The diffusion bondability of t his Inconel 718SPF superalloy was enhanced by electroless nickel plating. In this situation, the bonding shear strength increased to 70.4 MPa for the same overlap length of 12 T under the same bonding condition, regardless of the roughness of the surface to be bonded. Upon decreasing the overlap length from 12 to 6T, the bonding strength remained constant.

  2. Dynamics analysis on adhesive bonds of tilt mirror

    NASA Astrophysics Data System (ADS)

    Cao, Shang; Ruan, Ping; Wang, Chao; Xu, Guangzhou

    2014-09-01

    Adhesive bonding technology has been widely applied in the field of space remote sensing. In order to make the adhesive bonds connecting the mirror and the fixed structures in a satellite launch or operation of dynamic environment without damage, the finite element model of the tilt mirror is essential to be established for dynamic analysis, as well as the experimental verification . There are detailed model and the equivalent stiffness model on the adhesive bonds. The modal, frequency response - random vibration and shock response are analyzed through the detailed model of the bonds. The stress of the three point mirror bonds is compared with the six point support mirror. The mechanics experiment is carried out based on the dynamics analysis. The results of calculation demonstrates that the impact of frequency response and random vibration on adhesive bonds is relatively little, while the impact of the shock response is large. The experimental verification shows that the stress of bonds with three points support mirror under shock response exceeds the shear strength, which leads to the separation of the mirror and the fixed structure and the improved six point support mirror is satisfied to the requirements. The dynamics analysis on adhesive bonds of tilt mirror makes sense for designing, assembling and mechanics experiment.

  3. Enhanced nonlinear inspection of diffusion bonded interfaces using reflected non-collinear ultrasonic wave mixing

    NASA Astrophysics Data System (ADS)

    Zhang, Ziyin; Nagy, Peter B.; Hassan, Waled

    2016-02-01

    Ultrasonic wave mixing has shown promising potential for assessing otherwise hidden subtle imperfections in imperfect diffusion bonds between Ti-6Al-4V components. When interrogating a diffusion bonded specimen using non-collinear shear wave mixing, both bulk and interface nonlinearity will contribute to the transmitted nonlinear signal. Although a recent study has shown that changing the transducer alignment can suppress the intrinsic nonlinearity of the surrounding material to some extent so that the interface nonlinearity could be detected more selectively, it is still difficult to distinguish different levels of bond quality based on the detected transmitted signal only. Analytical and numerical studies showed that an imperfect interface generates the same amount of nonlinear displacement in the reflected and transmitted fields. In this study, we used the reflected nonlinear interface signature to characterize diffusion bonded interfaces. Our results indicate that it is better to use the reflected nonlinear interface signature to assess the bond quality, which is in agreement with our previous analytical and numerical predictions. However, the observed random phase of the reflected signature indicates that existing nonlinear interface models are insufficient for accurately describing the nonlinear interaction of shear incident waves with high-quality diffusion bonded interfaces.

  4. The effect of hydrogen bonds on diffusion mechanism of water inside single-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Chen, Qu; Wang, Qi; Liu, Ying-Chun; Wu, Tao

    2014-06-01

    Nanopores can serve as a molecule channel for transport of fluid, where water diffusion differs remarkably from that of simple particles. Hydrogen bonds play an essential role in the diffusion anomaly. Detailed investigations are carried out on the systems of rigid (6, 6), (7, 7), (8, 8), (9, 9), and (10, 10) armchair carbon nanotubes, solvated with Lennard-Jones water fluids. The role of hydrogen bonds is examined by diffusivity statistics and animation snapshots. It is found that in small (6,6) CNT, hydrogen bonds tend to aggregate water into a wire and lead to rapid collective drift. Confinement can stabilize the hydrogen bond of water molecules and enhance its lifetime. In relatively smaller CNTs, the diffusion mechanism could be altered by the temperature. Moreover, in larger nanotubes hydrogen bonding network allows the water to form regional concentrated clusters. This allows water fluid in extremely low density exhibit rather slow self-diffusion motion. This fundamental study attempts to provide insights in understanding nanoscale delivery system in aqueous solution.

  5. The effect of hydrogen bonds on diffusion mechanism of water inside single-walled carbon nanotubes.

    PubMed

    Chen, Qu; Wang, Qi; Liu, Ying-Chun; Wu, Tao

    2014-06-07

    Nanopores can serve as a molecule channel for transport of fluid, where water diffusion differs remarkably from that of simple particles. Hydrogen bonds play an essential role in the diffusion anomaly. Detailed investigations are carried out on the systems of rigid (6, 6), (7, 7), (8, 8), (9, 9), and (10, 10) armchair carbon nanotubes, solvated with Lennard-Jones water fluids. The role of hydrogen bonds is examined by diffusivity statistics and animation snapshots. It is found that in small (6,6) CNT, hydrogen bonds tend to aggregate water into a wire and lead to rapid collective drift. Confinement can stabilize the hydrogen bond of water molecules and enhance its lifetime. In relatively smaller CNTs, the diffusion mechanism could be altered by the temperature. Moreover, in larger nanotubes hydrogen bonding network allows the water to form regional concentrated clusters. This allows water fluid in extremely low density exhibit rather slow self-diffusion motion. This fundamental study attempts to provide insights in understanding nanoscale delivery system in aqueous solution.

  6. Fatigue and Impact Strength of Diffusion Bonded Titanium Alloy Joints

    DTIC Science & Technology

    1989-02-01

    specimen was machined to give either a Rolls-Royce rotating bend fatigue test piece or a Hounsfield impact test piece with the bond- line at the middle...specimens were machined to give Hounsfield impact test pieces. One of the metallographic specimens was also used for microhardness and electron probe...8217high’ void level condition was 3..:i lower than that of the controls. The Hounsfield impact values obtained for the 12.7 mm dia specimens (Fig 4

  7. LAMMPS framework for dynamic bonding and an application modeling DNA

    NASA Astrophysics Data System (ADS)

    Svaneborg, Carsten

    2012-08-01

    We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework. Catalogue identifier: AEME_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEME_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public Licence No. of lines in distributed program, including test data, etc.: 2 243 491 No. of bytes in distributed program, including test data, etc.: 771 Distribution format: tar.gz Programming language: C++ Computer: Single and multiple core servers Operating system: Linux/Unix/Windows Has the code been vectorized or parallelized?: Yes. The code has been parallelized by the use of MPI directives. RAM: 1 Gb Classification: 16.11, 16.12 Nature of problem: Simulating coarse-grain models capable of chemistry e.g. DNA hybridization dynamics. Solution method: Extending LAMMPS to handle dynamic bonding and directional bonds. Unusual features: Allows bonds to be created and broken while angular and dihedral interactions are kept consistent. Additional comments: The distribution file for this program is approximately 36 Mbytes and therefore is not delivered directly

  8. AN INTERNAL CONVECTIVE HEATING TECHNIQUE FOR DIFFUSION BONDING ARRAYED MICROCHANNEL ARCHITECTURES

    SciTech Connect

    Paul, Brian; Bose, Sumantra; Palo, Daniel R.

    2010-01-08

    Diffusion bonding cycle times can be a large factor in the production cost of metal microchannel devices. The challenge is to significantly minimize bonding cycle times through rapid heating and cooling within the bonding process. A novel method is described which takes advantage of the internal flow passages within microchannel devices for convective heat transfer during the bonding process. The internal convective heating (ICH) technique makes use of heated inert gas to provide the microchannel assembly with rapid and uniform heat input. Results demonstrate that the ICH technique is feasible, capable of producing microchannels with higher dimensional integrity and shorter bonding cycle times than traditional vacuum hot press methods. Results suggest that this may be due to smaller thermal gradients within microchannel devices during the ICH bonding cycle.

  9. Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations.

    PubMed

    Yamada, Steven A; Thompson, Ward H; Fayer, Michael D

    2017-06-21

    Many of water's remarkable properties arise from its tendency to form an intricate and robust hydrogen bond network. Understanding the dynamics that govern this network is fundamental to elucidating the behavior of pure water and water in biological and physical systems. In ultrafast nonlinear infrared experiments, the accessible time scales are limited by water's rapid vibrational relaxation (1.8 ps for dilute HOD in H2O), precluding interrogation of slow hydrogen bond evolution in non-bulk systems. Here, hydrogen bonding dynamics in bulk D2O were studied from the perspective of the much longer lived (36.2 ps) CN stretch mode of selenocyanate (SeCN(-)) using polarization selective pump-probe (PSPP) experiments, two-dimensional infrared (2D IR) vibrational echo spectroscopy, and molecular dynamics simulations. The simulations make use of the empirical frequency mapping approach, applied to SeCN(-) for the first time. The PSPP experiments and simulations show that the orientational correlation function decays via fast (2.0 ps) restricted angular diffusion (wobbling-in-a-cone) and complete orientational diffusive randomization (4.5 ps). Spectral diffusion, quantified in terms of the frequency-frequency correlation function, occurs on two time scales. The initial 0.6 ps time scale is attributed to small length and angle fluctuations of the hydrogen bonds between water and SeCN(-). The second 1.4 ps measured time scale, identical to that for HOD in bulk D2O, reports on the collective reorganization of the water hydrogen bond network around the anion. The experiments and simulations provide details of the anion-water hydrogen bonding and demonstrate that SeCN(-) is a reliable vibrational probe of the ultrafast spectroscopy of water.

  10. Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations

    NASA Astrophysics Data System (ADS)

    Yamada, Steven A.; Thompson, Ward H.; Fayer, Michael D.

    2017-06-01

    Many of water's remarkable properties arise from its tendency to form an intricate and robust hydrogen bond network. Understanding the dynamics that govern this network is fundamental to elucidating the behavior of pure water and water in biological and physical systems. In ultrafast nonlinear infrared experiments, the accessible time scales are limited by water's rapid vibrational relaxation (1.8 ps for dilute HOD in H2O), precluding interrogation of slow hydrogen bond evolution in non-bulk systems. Here, hydrogen bonding dynamics in bulk D2O were studied from the perspective of the much longer lived (36.2 ps) CN stretch mode of selenocyanate (SeCN-) using polarization selective pump-probe (PSPP) experiments, two-dimensional infrared (2D IR) vibrational echo spectroscopy, and molecular dynamics simulations. The simulations make use of the empirical frequency mapping approach, applied to SeCN- for the first time. The PSPP experiments and simulations show that the orientational correlation function decays via fast (2.0 ps) restricted angular diffusion (wobbling-in-a-cone) and complete orientational diffusive randomization (4.5 ps). Spectral diffusion, quantified in terms of the frequency-frequency correlation function, occurs on two time scales. The initial 0.6 ps time scale is attributed to small length and angle fluctuations of the hydrogen bonds between water and SeCN-. The second 1.4 ps measured time scale, identical to that for HOD in bulk D2O, reports on the collective reorganization of the water hydrogen bond network around the anion. The experiments and simulations provide details of the anion-water hydrogen bonding and demonstrate that SeCN- is a reliable vibrational probe of the ultrafast spectroscopy of water.

  11. Diffusive thermal dynamics for the Ising ferromagnet.

    PubMed

    Buonsante, P; Burioni, R; Cassi, D; Vezzani, A

    2002-09-01

    We introduce a thermal dynamics for the Ising ferromagnet where the energy variations occurring within the system exhibit a diffusive character typical of thermalizing agents such as, e.g., localized excitations. Time evolution is provided by a walker hopping across the sites of the underlying lattice according to local probabilities depending on the usual Boltzmann weight at a given temperature. Despite the canonical hopping probabilities the walker drives the system to a stationary state which is not reducible to the canonical equilibrium state in a trivial way. The system still exhibits a magnetic phase transition occurring at a finite value of the temperature larger than the canonical one. The dependence of the model on the density of walkers realizing the dynamics is also discussed. Interestingly the differences between the stationary state and the Boltzmann equilibrium state decrease with increasing number of walkers.

  12. Galactic civilizations - Population dynamics and interstellar diffusion

    NASA Technical Reports Server (NTRS)

    Newman, W. I.; Sagan, C.

    1981-01-01

    A model is developed of the interstellar diffusion of galactic civilizations which takes into account the population dynamics of such civilizations. The problem is formulated in terms of potential theory, with a family of nonlinear partial differential and difference equations specifying population growth and diffusion for an organism with advantageous genes that undergoes random dispersal while increasing in population locally, and a population at zero population growth. In the case of nonlinear diffusion with growth and saturation, it is found that the colonization wavefront from the nearest independently arisen galactic civilization can have reached the earth only if its lifetime exceeds 2.6 million years, or 20 million years if discretization can be neglected. For zero population growth, the corresponding lifetime is 13 billion years. It is concluded that the earth is uncolonized not because interstellar spacefaring civilizations are rare, but because there are too many worlds to be colonized in the plausible colonization lifetime of nearby civilizations, and that there exist no very old galactic civilizations with a consistent policy of the conquest of inhabited worlds.

  13. Galactic civilizations - Population dynamics and interstellar diffusion

    NASA Technical Reports Server (NTRS)

    Newman, W. I.; Sagan, C.

    1981-01-01

    A model is developed of the interstellar diffusion of galactic civilizations which takes into account the population dynamics of such civilizations. The problem is formulated in terms of potential theory, with a family of nonlinear partial differential and difference equations specifying population growth and diffusion for an organism with advantageous genes that undergoes random dispersal while increasing in population locally, and a population at zero population growth. In the case of nonlinear diffusion with growth and saturation, it is found that the colonization wavefront from the nearest independently arisen galactic civilization can have reached the earth only if its lifetime exceeds 2.6 million years, or 20 million years if discretization can be neglected. For zero population growth, the corresponding lifetime is 13 billion years. It is concluded that the earth is uncolonized not because interstellar spacefaring civilizations are rare, but because there are too many worlds to be colonized in the plausible colonization lifetime of nearby civilizations, and that there exist no very old galactic civilizations with a consistent policy of the conquest of inhabited worlds.

  14. Diffusion bonding titanium to stainless steel using Nb/Cu/Ni multi-interlayer

    SciTech Connect

    Li Peng; Li Jinglong; Xiong Jiangtao; Zhang Fusheng; Raza, Syed Hamid

    2012-06-15

    By using Nb/Cu/Ni structure as multi-interlayer, diffusion bonding titanium to austenitic stainless steel has been conducted. The effects of bonding temperature and bonding time on the interfacial microstructure were analyzed by scanning electron microscope equipped with energy dispersive spectroscope, and the joint strength was evaluated by tensile test. The results showed that Ni atoms aggregated at the Cu-Nb interface, which promoted Cu solution in Nb. This phenomenon forms a Cu-Nb solution strengthening effect. However, such effect would decay by using long bonding time that dilutes Ni atom aggregation, or be suppressed by using high bonding temperature that embrittles the Cu-Nb interface due to the formation of large grown intermetallic compounds. The sound joint was obtained by promoted parameters as 850 Degree-Sign C for 30-45 min, under which a bonding strength around 300 MPa could be obtained. - Highlights: Black-Right-Pointing-Pointer Titanium was diffusion bonded to stainless steel using Nb/Cu/Ni multi-interlayer. Black-Right-Pointing-Pointer The effects of bonding parameters on microstructure and joint strength were studied. Black-Right-Pointing-Pointer Nickel aggregation promotes Cu solution in Nb which can strengthen the joint. Black-Right-Pointing-Pointer The sound joint with strength of around 300 MPa was obtained by promoted parameters.

  15. Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

    SciTech Connect

    Greathouse, Jeffery A.; Cygan, Randall T.; Fredrich, Joanne T.; Jerauld, Gary R.

    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 the 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.

  16. 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

  17. 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.

  18. Joint design for improved fatigue life of diffusion-bonded box-stiffened panels

    NASA Technical Reports Server (NTRS)

    Davis, R. C.; Moses, P. L.; Kanenko, R. S.

    1985-01-01

    Simple photoelastic models were used to identify a cross-section geometry that would eliminate the severe stress concentrations at the bond line between box stiffeners diffusion bonded to a panel skin. Experimental fatigue-test data from titanium test specimens quantified the allowable stress in terms of cycle life for various joint geometries. It is shown that the effect of stress concentration is reduced and an acceptable fatigue life is achieved.

  19. A link between structure, diffusion and rotations of hydrogen bonding tracers in ionic liquids.

    PubMed

    Araque, Juan C; Daly, Ryan P; Margulis, Claudio J

    2016-05-28

    When solutes are small compared to the size of the ions in an ionic liquid, energetic heterogeneities associated with charge enhanced (stiff) and charge depleted (soft) nanoenvironments are sampled. In a recent article [J. C. Araque et al., J. Phys. Chem. B 119(23), 7015-7029 (2015)], we explored large deviations from Stokes-Einstein translational diffusion caused by such a heterogeneity. The current article is set to explore the effect of soft and stiff solvent environments (i.e., structure) on OH-bond rotations in the case of water and small alcohols in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Im1,2 (+)NTf2 (-)). Is solute rotational dynamics heterogeneous? If so, are solute rotations and translations coupled in the sense that stiff and soft solvent environments hinder or speed up both types of dynamics? For the systems studied here, there appears to be a clear connection between translations, rotations, and stiff/soft solvent environments. We also discuss interesting asymmetries of the correlation between solutes with anions and cations.

  20. A link between structure, diffusion and rotations of hydrogen bonding tracers in ionic liquids

    NASA Astrophysics Data System (ADS)

    Araque, Juan C.; Daly, Ryan P.; Margulis, Claudio J.

    2016-05-01

    When solutes are small compared to the size of the ions in an ionic liquid, energetic heterogeneities associated with charge enhanced (stiff) and charge depleted (soft) nanoenvironments are sampled. In a recent article [J. C. Araque et al., J. Phys. Chem. B 119(23), 7015-7029 (2015)], we explored large deviations from Stokes-Einstein translational diffusion caused by such a heterogeneity. The current article is set to explore the effect of soft and stiff solvent environments (i.e., structure) on OH-bond rotations in the case of water and small alcohols in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([" separators="Im1,2 + ][" separators="NTf2- ]). Is solute rotational dynamics heterogeneous? If so, are solute rotations and translations coupled in the sense that stiff and soft solvent environments hinder or speed up both types of dynamics? For the systems studied here, there appears to be a clear connection between translations, rotations, and stiff/soft solvent environments. We also discuss interesting asymmetries of the correlation between solutes with anions and cations.

  1. Reaction-diffusion analysis for one-step plasma etching and bonding of microfluidic devices

    SciTech Connect

    Rosso, Michel; Steijn, Volkert van; Smet, Louis C. P. M. de; Sudhoelter, Ernst J. R.; Kreutzer, Michiel T.; Kleijn, Chris R.

    2011-04-25

    A self-similar reaction front develops in reactive ion etching when the ions penetrate channels of shallow height h. This relates to the patterning of microchannels using a single-step etching and bonding, as described by Rhee et al. [Lab Chip 5, 102 (2005)]. Experimentally, we report that the front location scales as x{sub f{approx}}ht{sup 1/2} and the width is time-invariant and scales as {delta}{approx}h. Mean-field reaction-diffusion theory and Knudsen diffusion give a semiquantitative understanding of these observations and allow optimization of etching times in relation to bonding requirements.

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

    PubMed

    Chen, Yinshan; Zhu, Men; Laventure, Audrey; Lebel, Olivier; Ediger, M D; Yu, Lian

    2017-07-27

    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 C2H5, OCH3, and NHCH3, 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 as 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. 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.

  3. 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.

  4. 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.

  5. Transient liquid phase diffusion bonding of Udimet 720 for Stirling power converter applications

    NASA Technical Reports Server (NTRS)

    Mittendorf, Donald L.; Baggenstoss, William G.

    1992-01-01

    Udimet 720 has been selected for use on Stirling power converters for space applications. Because Udimet 720 is generally considered susceptible to strain age cracking if traditional fusion welding is used, other joining methods are being considered. A process for transient liquid phase diffusion bonding of Udimet 720 has been theoretically developed in an effort to eliminate the strain age crack concern. This development has taken into account such variables as final grain size, joint homogenization, joint efficiency related to bonding aid material, bonding aid material application method, and thermal cycle.

  6. Dynamical Crossover in Hot Dense Water: The Hydrogen Bond Role.

    PubMed

    Ranieri, Umbertoluca; Giura, Paola; Gorelli, Federico A; Santoro, Mario; Klotz, Stefan; Gillet, Philippe; Paolasini, Luigi; Koza, Michael Marek; Bove, Livia E

    2016-09-01

    We investigate the terahertz dynamics of liquid H2O as a function of pressure along the 450 K isotherm, by coupled quasielastic neutron scattering and inelastic X-ray scattering experiments. The pressure dependence of the single-molecule dynamics is anomalous in terms of both microscopic translation and rotation. In particular, the Stokes-Einstein-Debye equations are shown to be violated in hot water compressed to the GPa regime. The dynamics of the hydrogen bond network is only weakly affected by the pressure variation. The time scale of the structural relaxation driving the collective dynamics increases by a mere factor of 2 along the investigated isotherm, and the structural relaxation strength turns out to be almost pressure independent. Our results point at the persistence of the hydrogen bond network in hot dense water up to ice VII crystallization, thus questioning the long-standing perception that hydrogen bonds are broken in liquid water under the effect of compression.

  7. Directional diffusion and void formation at a Si (001) bonded wafer interface

    NASA Astrophysics Data System (ADS)

    Esser, R. H.; Hobart, K. D.; Kub, F. J.

    2002-08-01

    Low-temperature hydrophobic bonding is an enabling technology allowing the fabrication of device structures. Current research into improvement of hydrophobic bonding has focused on the elimination of thermally generated voids. It has been observed that a regular grid etched into the bonding interface can eliminate the thermally generated voids. By manipulation of patterns etched into the bond interface, it was possible to ascertain that the diffusion of interfacial gasses that form the thermally generated voids is enhanced along the <110> directions. This is shown by an analysis of the void density at various locations in relation to the etched trenches at the bonded interface. Void density between trenches is shown to be 12% of the void density near trenches but nto along a <110> direction.

  8. Diffusion bonding of boron nitride on metal substrates by plasma activated sintering (PAS) process

    SciTech Connect

    Yoo, S.; Groza, J.R.; Yamazaki, K.; Sudarshan, T.S.

    1996-05-01

    Ceramic coatings have a considerable potential to be used as thermal barriers and improve corrosion and wear resistance of metallic materials at high temperatures. In particular, BN ceramics are excellent candidates for thermal barrier materials because they have superior corrosion and abrasion resistance, low thermal conductivity and high temperature stability. In general, above 1,273 K ceramics have better strength, creep oxidation resistance than metals or superalloys. It is well known that ceramic coatings are difficult to apply on metal substrates due to the different atomic bonding between ceramic and metals. To provide the expected protection, ceramic coating of metals must provide good interfacial bonding, suitable adherence and interface stability. These may be achieved by different processing approaches such as: diffusion bonding under pressure application, thermal spray or mechanical bonding. An alternative method may be sinter-bonding using P/M techniques such as hot isostatic pressing (HIP) when simultaneous sintering of ceramic powders and bonding onto the metal substrate can take place. The purpose of this present work is to verify the potential of the plasma assisted sintering (PAS) process to develop a good diffusion bonding between a BN ceramic layer and the metal substrate while sintering the ceramic layer. In contrast to HIP techniques, sintering and coating in PAS can be completed in a very short time (minutes as compared to hours) concurrent with an observed (not yet demonstrated) capability of particle surface cleaning by removing surface oxides or trapped gases.

  9. Ion diffusion at the bonding interface of undoped YAG/Yb:YAG composite ceramics

    NASA Astrophysics Data System (ADS)

    Fujioka, Kana; Sugiyama, Akira; Fujimoto, Yasushi; Kawanaka, Junji; Miyanaga, Noriaki

    2015-08-01

    Cation diffusion across a boundary between ytterbium (Yb)-doped and undoped yttrium aluminum garnet (YAG) ceramics was examined by electron microprobe analysis (EPMA). Polished Yb:YAG and undoped YAG ceramics were bonded by surface treatment with argon fast atom beam, and then heat-treated at 1400 or 1600 °C for 50 h or at 1400 °C for 10 h under vacuum. We obtained EPMA mapping images of the bonded samples that clearly showed the bulk and grain-boundary diffusion of Y and Yb ions. The number density profiles showed that the total diffusion distances of Yb and Y ions were almost equal and approximately 2 and 15 μm at 1400 and 1600 °C, respectively, and the dependence of diffusion distance on heating time was weak. The diffusion curves were well modeled by Harrison type B kinetics including bulk and grain-boundary diffusion. In addition, it was found that Si ions added to the samples as a sintering aid might be segregated at the grain boundary by heat treatment, and diffused only along grain boundaries.

  10. The Breathing Orbital Valence Bond Method in Diffusion Monte Carlo: C-H Bond Dissociation ofAcetylene

    SciTech Connect

    Domin, D.; Braida, Benoit; Lester Jr., William A.

    2008-05-30

    This study explores the use of breathing orbital valence bond (BOVB) trial wave functions for diffusion Monte Carlo (DMC). The approach is applied to the computation of the carbon-hydrogen (C-H) bond dissociation energy (BDE) of acetylene. DMC with BOVB trial wave functions yields a C-H BDE of 132.4 {+-} 0.9 kcal/mol, which is in excellent accord with the recommended experimental value of 132.8 {+-} 0.7 kcal/mol. These values are to be compared with DMC results obtained with single determinant trial wave functions, using Hartree-Fock orbitals (137.5 {+-} 0.5 kcal/mol) and local spin density (LDA) Kohn-Sham orbitals (135.6 {+-} 0.5 kcal/mol).

  11. Role of Hydrogen-Bonding in Nonelectrolyte Diffusion through Dense Artificial Membranes

    PubMed Central

    Gary-Bobo, C. M.; DiPolo, R.; Solomon, A. K.

    1969-01-01

    The diffusion of two series of alcohols and amides through complex cellulose acetate membranes was studied. The thin dense part of these membranes behaves as a nonporous layer of low water content. In this layer, called the skin, the solute diffusion coefficients, ω, depend upon size, steric configuration, and the partition coefficient, K8, between membrane and bathing solution. From the experimental values of ω and K8, the over-all friction, f, experienced by the solutes in the membrane was computed. It was found that f depends upon the chemical nature of the solute and is related to hydrogen-bonding ability. In the coarse, porous layer of the cellulose acetate membrane, diffusion occurs mainly through aqueous channels. In this instance also the hydrogen-bonding ability of the solute seems to exercise a smaller but significant influence. PMID:5806595

  12. Reactive force field simulation of proton diffusion in BaZrO3 using an empirical valence bond approach.

    PubMed

    Raiteri, Paolo; Gale, Julian D; Bussi, Giovanni

    2011-08-24

    A new reactive force field to describe proton diffusion within the solid oxide fuel cell material BaZrO(3) has been derived. Using a quantum mechanical potential energy surface, the parameters of an interatomic potential model to describe hydroxyl groups within both pure and yttrium-doped BaZrO(3) have been determined. Reactivity is then incorporated through the use of the empirical valence bond model. Molecular dynamics simulations (EVB-MD) have been performed to explore the diffusion of hydrogen using a stochastic thermostat and barostat whose equations are extended to the isostress-isothermal ensemble. In the low concentration limit, the presence of yttrium is found not to significantly influence the diffusivity of hydrogen, despite the proton having a longer residence time at oxygen adjacent to the dopant. This lack of influence is due to the fact that trapping occurs infrequently, even when the proton diffuses through octahedra adjacent to the dopant. The activation energy for diffusion is found to be 0.42 eV, in good agreement with experimental values, though the prefactor is slightly underestimated.

  13. 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...

  14. Brownian dynamics simulation of restricted rotational diffusion.

    PubMed Central

    Martínez, M C; García de la Torre, J

    1987-01-01

    The restricted rotational diffusion of an axially symmetric particle is simulated by the Brownian dynamics technique. In addition to the wobbling-in-a-cone model, several continuous potentials are considered. The particle studied is particularly simple: a sphere anchored to a point fixed in space. However, presenting the results in a convenient, reduced form, they are valid for any axially symmetric particle. From simulated rotational trajectories, we calculate (P2(cos alpha] as a function of t, where alpha is the angle between two orientations separated by time t and P2 is the second Legendre polynomial. This correlation function is closely related to time-resolved electro-optic and spectroscopic properties. Simulated results for the cone model are in excellent agreement with the quasiexact results of Lipari and Szabo (1981, J. Chem. Phys., 75:2971-2976). Thus we confirm the good performance of the simulation technique and the validity of our working conditions. Novel results are presented for continuous restricting potentials, V(theta). The (P2) results for V = 1/2K theta 2 and V = Q(1 - cos theta) are practically the same if K and Q are chosen so tht the long-time (P2) values coincide. Thus, the quadratic potential seems to be a good representation of any monotonically increasing potential. However, for an uniaxial potential such as V = Csin2 theta, the decay is appreciably faster. The (P2) decays simulated for the continuous potentials are analyzed by the monoexponential version of the cone model. We found that such an analysis produces an overestimation of the true rotational diffusion coefficient of approximately 15% only, although for uniaxial potentials the error may be larger. PMID:3663834

  15. Ambient-temperature creep failure of silver-aided diffusion bonds between steel

    SciTech Connect

    Henshall, G.A.; Kassner, M.E.; Rosen, R.S.

    1990-01-15

    It has long been known that thin (e.g., 1 {mu}m {minus} 1 mm) interlayer bonds between higher strength base materials may have high ultimate tensile or rupture strengths despite the relatively low strength of the filler metal. The high strength of the joint is due to the mechanical constraint provided by the stronger base metals which restricts transverse contraction of the interlayer. The constraint produces a triaxial state or stress and reduces the effective stress, thus reducing the tendency for the interlayer to plastically deform. Plasticity of the base metal reduces the constraint and decreases the strength of the bond. The purpose of this work was twofold. First, the validity of the base-metal- accelerated'' delayed-failure theory for bonds utilizing plastic base metals was checked. Creep-rupture tests were performed on diffusion-bonded specimens using silver interlayers deposited by planar-magnetron sputtering (PMS), a physical vapor-deposition process. The PMS process was preferred because of the superior quality and strength of the bond and because this modern low-temperature joining process is increasingly utilized for joining ceramic and composite materials. The role of plastic base metals in the fracture process was further investigated by conducting tensile-rupture tests of diffusion bonds made with stainless steel base metals of different yield strengths, and therefore different creep rates. The second purpose was to determine whether delayed failure occurs in interlayer bonds between elastic base metals, which do not creep over the range of applied stresses. This question is particularly relevant since many alloys, ceramics and composites fall within this category. Again, ambient and near-ambient temperature creep-rupture tests were performed at a variety of stresses below the UTS of the bond. 25 refs., 7 figs.

  16. The hydrogen-bond collective dynamics in liquid methanol

    NASA Astrophysics Data System (ADS)

    Bellissima, Stefano; de Panfilis, Simone; Bafile, Ubaldo; Cunsolo, Alessandro; González, Miguel Angel; Guarini, Eleonora; Formisano, Ferdinando

    2016-12-01

    The relatively simple molecular structure of hydrogen-bonded (HB) systems is often belied by their exceptionally complex thermodynamic and microscopic behaviour. For this reason, after a thorough experimental, computational and theoretical scrutiny, the dynamics of molecules in HB systems still eludes a comprehensive understanding. Aiming at shedding some insight into this topic, we jointly used neutron Brillouin scattering and molecular dynamics simulations to probe the dynamics of a prototypical hydrogen-bonded alcohol, liquid methanol. The comparison with the most thoroughly investigated HB system, liquid water, pinpoints common behaviours of their THz microscopic dynamics, thereby providing additional information on the role of HB dynamics in these two systems. This study demonstrates that the dynamic behaviour of methanol is much richer than what so far known, and prompts us to establish striking analogies with the features of liquid and supercooled water. In particular, based on the strong differences between the structural properties of the two systems, our results suggest that the assignment of some dynamical properties to the tetrahedral character of water structure should be questioned. We finally highlight the similarities between the characteristic decay times of the time correlation function, as obtained from our data and the mean lifetime of hydrogen bond known in literature.

  17. The hydrogen-bond collective dynamics in liquid methanol

    DOE PAGES

    Bellissima, Stefano; Cunsolo, Alessandro; DePanfilis, Simone; ...

    2016-12-20

    The relatively simple molecular structure of hydrogen-bonded (HB) systems is often belied by their exceptionally complex thermodynamic and microscopic behaviour. For this reason, after a thorough experimental, computational and theoretical scrutiny, the dynamics of molecules in HB systems still eludes a comprehensive understanding. Aiming at shedding some insight into this topic, we jointly used neutron Brillouin scattering and molecular dynamics simulations to probe the dynamics of a prototypical hydrogen-bonded alcohol, liquid methanol. The comparison with the most thoroughly investigated HB system, liquid water, pinpoints common behaviours of their THz microscopic dynamics, thereby providing additional information on the role of HBmore » dynamics in these two systems. This study demonstrates that the dynamic behaviour of methanol is much richer than what so far known, and prompts us to establish striking analogies with the features of liquid and supercooled water. In particular, based on the strong differences between the structural properties of the two systems, our results suggest that the assignment of some dynamical properties to the tetrahedral character of water structure should be questioned. We finally highlight the similarities between the characteristic decay times of the time correlation function, as obtained from our data and the mean lifetime of hydrogen bond known in literature.« less

  18. The hydrogen-bond collective dynamics in liquid methanol

    SciTech Connect

    Bellissima, Stefano; Cunsolo, Alessandro; DePanfilis, Simone; Bafile, Ubaldo; Gonzalez, Miguel Angel; Guarini, Eleonora; Formisano, Ferdinando

    2016-12-20

    The relatively simple molecular structure of hydrogen-bonded (HB) systems is often belied by their exceptionally complex thermodynamic and microscopic behaviour. For this reason, after a thorough experimental, computational and theoretical scrutiny, the dynamics of molecules in HB systems still eludes a comprehensive understanding. Aiming at shedding some insight into this topic, we jointly used neutron Brillouin scattering and molecular dynamics simulations to probe the dynamics of a prototypical hydrogen-bonded alcohol, liquid methanol. The comparison with the most thoroughly investigated HB system, liquid water, pinpoints common behaviours of their THz microscopic dynamics, thereby providing additional information on the role of HB dynamics in these two systems. This study demonstrates that the dynamic behaviour of methanol is much richer than what so far known, and prompts us to establish striking analogies with the features of liquid and supercooled water. In particular, based on the strong differences between the structural properties of the two systems, our results suggest that the assignment of some dynamical properties to the tetrahedral character of water structure should be questioned. We finally highlight the similarities between the characteristic decay times of the time correlation function, as obtained from our data and the mean lifetime of hydrogen bond known in literature.

  19. The hydrogen-bond collective dynamics in liquid methanol

    PubMed Central

    Bellissima, Stefano; De Panfilis, Simone; Bafile, Ubaldo; Cunsolo, Alessandro; González, Miguel Angel; Guarini, Eleonora; Formisano, Ferdinando

    2016-01-01

    The relatively simple molecular structure of hydrogen-bonded (HB) systems is often belied by their exceptionally complex thermodynamic and microscopic behaviour. For this reason, after a thorough experimental, computational and theoretical scrutiny, the dynamics of molecules in HB systems still eludes a comprehensive understanding. Aiming at shedding some insight into this topic, we jointly used neutron Brillouin scattering and molecular dynamics simulations to probe the dynamics of a prototypical hydrogen-bonded alcohol, liquid methanol. The comparison with the most thoroughly investigated HB system, liquid water, pinpoints common behaviours of their THz microscopic dynamics, thereby providing additional information on the role of HB dynamics in these two systems. This study demonstrates that the dynamic behaviour of methanol is much richer than what so far known, and prompts us to establish striking analogies with the features of liquid and supercooled water. In particular, based on the strong differences between the structural properties of the two systems, our results suggest that the assignment of some dynamical properties to the tetrahedral character of water structure should be questioned. We finally highlight the similarities between the characteristic decay times of the time correlation function, as obtained from our data and the mean lifetime of hydrogen bond known in literature. PMID:27996056

  20. Restoration of rhythmicity in diffusively coupled dynamical networks.

    PubMed

    Zou, Wei; Senthilkumar, D V; Nagao, Raphael; Kiss, István Z; Tang, Yang; Koseska, Aneta; Duan, Jinqiao; Kurths, Jürgen

    2015-07-15

    Oscillatory behaviour is essential for proper functioning of various physical and biological processes. However, diffusive coupling is capable of suppressing intrinsic oscillations due to the manifestation of the phenomena of amplitude and oscillation deaths. Here we present a scheme to revoke these quenching states in diffusively coupled dynamical networks, and demonstrate the approach in experiments with an oscillatory chemical reaction. By introducing a simple feedback factor in the diffusive coupling, we show that the stable (in)homogeneous steady states can be effectively destabilized to restore dynamic behaviours of coupled systems. Even a feeble deviation from the normal diffusive coupling drastically shrinks the death regions in the parameter space. The generality of our method is corroborated in diverse non-linear systems of diffusively coupled paradigmatic models with various death scenarios. Our study provides a general framework to strengthen the robustness of dynamic activity in diffusively coupled dynamical networks.

  1. Restoration of rhythmicity in diffusively coupled dynamical networks

    PubMed Central

    Zou, Wei; Senthilkumar, D. V.; Nagao, Raphael; Kiss, István Z.; Tang, Yang; Koseska, Aneta; Duan, Jinqiao; Kurths, Jürgen

    2015-01-01

    Oscillatory behaviour is essential for proper functioning of various physical and biological processes. However, diffusive coupling is capable of suppressing intrinsic oscillations due to the manifestation of the phenomena of amplitude and oscillation deaths. Here we present a scheme to revoke these quenching states in diffusively coupled dynamical networks, and demonstrate the approach in experiments with an oscillatory chemical reaction. By introducing a simple feedback factor in the diffusive coupling, we show that the stable (in)homogeneous steady states can be effectively destabilized to restore dynamic behaviours of coupled systems. Even a feeble deviation from the normal diffusive coupling drastically shrinks the death regions in the parameter space. The generality of our method is corroborated in diverse non-linear systems of diffusively coupled paradigmatic models with various death scenarios. Our study provides a general framework to strengthen the robustness of dynamic activity in diffusively coupled dynamical networks. PMID:26173555

  2. Hydrogen bonding definitions and dynamics in liquid water.

    PubMed

    Kumar, R; Schmidt, J R; Skinner, J L

    2007-05-28

    X-ray and neutron diffractions, vibrational spectroscopy, and x-ray Raman scattering and absorption experiments on water are often interpreted in terms of hydrogen bonding. To this end a number of geometric definitions of hydrogen bonding in water have been developed. While all definitions of hydrogen bonding are to some extent arbitrary, those involving one distance and one angle for a given water dimer are unnecessarily so. In this paper the authors develop a systematic procedure based on two-dimensional potentials of mean force for defining cutoffs for a given pair of distance and angular coordinates. They also develop an electronic structure-based definition of hydrogen bonding in liquid water, related to the electronic occupancy of the antibonding OH orbitals. This definition turns out to be reasonably compatible with one of the distance-angle geometric definitions. These two definitions lead to an estimate of the number of hydrogen bonds per molecule in liquid simple point charge/extended (SPC/E) water of between 3.2 and 3.4. They also used these and other hydrogen-bond definitions to examine the dynamics of local hydrogen-bond number fluctuations, finding an approximate long-time decay constant for SPC/E water of between 0.8 and 0.9 ps, which corresponds to the time scale for local structural relaxation.

  3. Development and analysis of diffusion bonding techniques for LBE-cooled spallation targets

    NASA Astrophysics Data System (ADS)

    Nelson, A. T.; Hosemann, P.; Maloy, S. A.

    2012-12-01

    Spallation sources incorporating solid targets may be driven to utilize liquid metal coolants by neutronics or temperature concerns. If tungsten is chosen as the target material, it will require cladding given its poor performance under irradiation. One option to meet this need are ferritic/martensitic stainless steel alloys. This study investigates possible diffusion bonding techniques suitable to clad tungsten targets with HT9, a high chromium stainless steel familiar to the nuclear industry. A test bonding matrix was performed to identify bonding conditions and process parameters suitable for the three material systems of interest (HT9/Ta, HT9/W, and HT9/HT9). Temperatures of 900 and 1060 °C were investigated along with bonding pressures of 7 and 70 MPa. A nominal soak time of 3 h was used for all tests. Three interlayers were investigated: pure nickel, Ni-6P, and vanadium. Finally, different surface preparation techniques for the tungsten were explored in order to gage their effect on the bond quality. Following joining, the bonds were characterized using an array of microscopy and micromechanical techniques to determine the resulting interface character. The nickel and NiP coatings were found to stabilize austenite at the HT9 surface during bonding, while the vanadium remained generally inert given good solubility in each of the three systems. Intermetallic formation is also a significant concern at elevated bonding temperatures as FeTa, FeW, NiTa, and NiW each rapidly form during interdiffusion. Multiple failures were observed through crack propagation parallel to the interface along the intermetallic phases. Differing contraction rates among the base materials also resulted in brittle fracture within the tungsten during cooling from bonding temperatures. Bonding performed at 900 °C under 70 MPa for 3 h with the inclusion of a vanadium interlayer was found to be superior of the conditions explored in this work.

  4. Shrinkage-Stress Assisted Diffusion Bonds Between Titanium and Stainless Steel: A Novel Technique

    NASA Astrophysics Data System (ADS)

    Mukherjee, A. B.; Laik, A.; Kain, V.; Chakravartty, J. K.

    2016-10-01

    Diffusion bonding of high-strength titanium (Ti) to stainless steel (SS) (i.e., transition joint of lap configuration) is designed and assessed for the possible high-temperature, high-pressure applications for the nuclear power plant and chemical industries. The strength of annular joint is enhanced by providing grooves at the interface ensuring strength of the joint compatible to Ti. The optimized hot forming conditions are utilized to facilitate the flow of Ti to fill the grooves located at the interface on SS sleeve resulting in strong mechanical connection. The shrinkage stress developed due to differential contraction during cooling facilitates the diffusion bonding at the interfaces inside the grooves under relatively lower temperature. The present design concept results in the formation of low level of intermetallic compounds at the interface. The bond width containing the intermetallic compounds toward Ti side has been found to be less than that of the high-strength diffusion bonds as occasionally reported in the open published literatures.

  5. Microstructural Characterization of Diffusion Bonds Assisted by Ni/Ti Nanolayers

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    The microstructure of similar and dissimilar diffusion bonds of metallic materials using reactive Ni/Ti interlayers was studied in this investigation. The base material surfaces were modified by sputter deposition of alternated Ni and Ti nanolayers. These nanolayers increase the diffusivity at the interface, enhancing the bonding process. Bonding experiments were performed at 800 °C under a pressure of 10 MPa with a bonding time of 60 min. The reaction zone was characterized by high-resolution scanning and transmission electron microscopies. Microstructural characterization reveals that similar (NiTi to NiTi and TiAl to TiAl) and dissimilar (NiTi to Ti6Al4V and TiAl to stainless steel) joints can be obtained successfully with Ni/Ti reactive nanolayers. The interfaces are thin (<10 µm) and their microstructure (thickness and number of zones, size and shape of the grains) depends on the elements diffusing from the base materials. For all joints, the interface is mainly composed of equiaxed grains of NiTi and NiTi2.

  6. Structure and dynamics of diffusion flames in microgravity

    NASA Technical Reports Server (NTRS)

    Matalon, Moshe

    1995-01-01

    The objectives of this project are to gain insight into diffusion flames by modeling various configurations related to ongoing experimental investigations in the microgravity combustion science program. The emphasis of the work is to understand the structure and dynamics of diffusion flames. Improving our fundamental understanding of diffusion flames is most relevant to issues related to fire safety and fire prevention because most fires consist of diffusion flames.

  7. Anharmonic dynamics of intramolecular hydrogen bonds driven by DNA breathing

    NASA Astrophysics Data System (ADS)

    Alexandrov, B. S.; Stanev, V. G.; Bishop, A. R.; Rasmussen, K. Ø.

    2012-12-01

    We study the effects of the anharmonic strand-separation dynamics of double-stranded DNA on the infrared spectra of the intramolecular base-pairing hydrogen bonds. Using the extended Peyrard-Bishop-Dauxois model for the DNA breathing dynamics coupled with the Lippincott-Schroeder potential for N-H⋯N and N-H⋯O hydrogen bonding, we identify a high-frequency (˜96 THz) feature in the infrared spectra. We show that this sharp peak arises as a result of the anharmonic base-pair breathing dynamics of DNA. In addition, we study the effects of friction on the infrared spectra. For higher temperatures (˜300 K), where the anharmonicity of DNA dynamics is pronounced, the high-frequency peak is always present irrespective of the friction strength.

  8. Uniaxial diffusion bonding of CLAM/CLAM steels: Microstructure and mechanical performance

    NASA Astrophysics Data System (ADS)

    Zhou, Xiaosheng; Liu, Yongchang; Yu, Liming; Liu, Chenxi; Sui, Guofa; Yang, Jianguo

    2015-06-01

    By performing a two-step uniaxial diffusion bonding, the reliable joining between CLAM/CLAM steels has been attained. The microstructures at the vicinity of the joint region and in base material were respectively investigated through OM, SEM and TEM. The joint interface was integrated, and no microstructural defects were observed. In the base material, small amount of austenite is retained as thin films between martensite laths, which was suggested to be related to the compressive deformation in diffusion bonding. As a candidate structural material for the first wall in fusion energy systems, the radiation resistance of CLAM steel would be deteriorated by the retained austenite. Tensile and impact tests were carried out to assess the reliability of the joints subjected to post bond heat treatment. All the tensile specimens fractured in the base CLAM steel, meaning the good joining between CLAM steels. However, due to the low impact absorbed energy of the joints, efforts should still be made to optimize the bonding technology and the post bond heat treatment further.

  9. Effects of interface bonding and defects on boron diffusion at Si/SiO2 interface

    NASA Astrophysics Data System (ADS)

    Kim, Geun-Myeong; Oh, Young Jun; Chang, K. J.

    2013-12-01

    We perform first-principles density functional calculations to find the migration pathway and barrier for B diffusion at the Si/SiO2 interface. For various interface models, in which crystalline α-quartz or amorphous silica (a-SiO2) is placed on Si, we examine stable and metastable configurations of B-related defects which play a role in B diffusion. While a substitutional B alone is immobile in Si, it tends to diffuse to the interface via an interstitialcy mechanism in the presence of a self-interstitial and then changes into an interstitial B in oxide via a kick-out mechanism, leaving the self-interstitial at the interface. At the defect-free interface, where bridging O atoms are inserted to remove interface dangling bonds, an interstitial B prefers to intervene between the interface Si and bridging O atoms and subsequently diffuses through the hollow space or along the network of the Si-O-Si bonds in oxide. The overall migration barriers are calculated to be 2.02-2.12 eV at the Si/α-quartz interface, while they lie in the range of 2.04 ± 0.44 eV at the Si/a-SiO2 interface, similar to that in α-quartz. The migration pathway and barrier are not significantly affected by interface defects such as suboxide bond and O protrusion, while dangling bonds in the suboxide region can increase the migration barrier by about 1.5 eV. The result that the interface generally does not hinder the B diffusion from Si to SiO2 assists in understanding the underlying mechanism for B segregation which commonly occurs at the Si/SiO2 interface.

  10. 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

  11. Role of Hydration Layer in Dynamical Transition in Proteins: Insights from Translational Self-Diffusivity.

    PubMed

    Nandi, Prithwish K; English, Niall J

    2016-12-01

    Elucidation of the role of hydration water underpinning dynamical crossover in proteins has proven challenging. Indeed, many contradictory findings in the literature seek to establish either causal or correlative links between water and protein behavior. Here, via molecular dynamics, we compute the temperature dependence of mean-square displacement and translational self-diffusivities for both hen egg white lysozyme and its hydration layer from 190 to 300 K. We find that the protein's mobility increases sharply at ∼230 K, indicating dynamical onset; concerted motion with hydration-water molecules is evident up to ∼285 K, confirming dynamical correlation between them. Exploring underlying mechanisms of such concerted motion, we scrutinize the water-protein hydrogen-bonding network as a function of temperature, noting sharp deviation from linearity of the hydrogen bond number's profile with temperature originating near the protein dynamical transition. Our studies reveal a common temperature profile/dependence of self-diffusivity values of the protein, hydration water, and the bulk solvent, originating from a common dependence on the bulk solvent viscosity, ηS. The key mechanistic role adopted by the protein-water hydrogen bond network in relation to the onset of proteins' dynamical transition is also discussed.

  12. Hidden Multiple Bond Effects in Dynamic Force Spectroscopy

    PubMed Central

    Getfert, Sebastian; Reimann, Peter

    2012-01-01

    In dynamic force spectroscopy, a (bio-)molecular complex is subjected to a steadily increasing force until the chemical bond breaks. Repeating the same experiment many times results in a broad distribution of rupture forces, whose quantitative interpretation represents a formidable theoretical challenge. In this study we address the situation that more than a single molecular bond is involved in one experimental run, giving rise to multiple rupture events that are even more difficult to analyze and thus are usually eliminated as far as possible from the further evaluation of the experimental data. We develop and numerically solve a detailed model of a complete dynamic force spectroscopy experiment including a possible clustering of molecules on the substrate surface, the formation of bonds, their dissociation under load, and the postprocessing of the force extension curves. We show that the data, remaining after elimination of obvious multiple rupture events, may still contain a considerable number of hidden multiple bonds, which are experimentally indistinguishable from true single bonds, but which have considerable effects on the resulting rupture force statistics and its consistent theoretical interpretation. PMID:22404941

  13. Imaging Local Diffusive Dynamics Using Diffusion Exchange Spectroscopy MRI

    NASA Astrophysics Data System (ADS)

    Benjamini, Dan; Komlosh, Michal E.; Basser, Peter J.

    2017-04-01

    The movement of water between microenvironments presents a central challenge in the physics of soft matter and porous media. Diffusion exchange spectroscopy (DEXSY) is a powerful 2D nuclear magnetic resonance method for measuring such exchange, yet it is rarely used because of its long scan time requirements. Moreover, it has never been combined with magnetic resonance imaging (MRI). Using probability theory, we vastly reduce the required data, making DEXSY MRI feasible for the first time. Experiments are performed on a composite nerve tissue phantom with restricted and free water-exchanging compartments.

  14. Hydrophobic molecules slow down the hydrogen-bond dynamics of water.

    PubMed

    Bakulin, Artem A; Pshenichnikov, Maxim S; Bakker, Huib J; Petersen, Christian

    2011-03-17

    We study the spectral and orientational dynamics of HDO molecules in solutions of tertiary-butyl-alcohol (TBA), trimethyl-amine-oxide (TMAO), and tetramethylurea (TMU) in isotopically diluted water (HDO:D(2)O and HDO:H(2)O). The spectral dynamics are studied with femtosecond two-dimensional infrared spectroscopy and the orientational dynamics with femtosecond polarization-resolved vibrational pump-probe spectroscopy. We observe a strong slowing down of the spectral diffusion around the central part of the absorption line that increases with increasing solute concentration. At low concentrations, the fraction of water showing slow spectral dynamics is observed to scale with the number of methyl groups, indicating that this effect is due to slow hydrogen-bond dynamics in the hydration shell of the methyl groups of the solute molecules. The slowing down of the vibrational frequency dynamics is strongly correlated with the slowing down of the orientational mobility of the water molecules. This correlation indicates that these effects have a common origin in the effect of hydrophobic molecular groups on the hydrogen-bond dynamics of water.

  15. Fabrication and Design Aspects of High-Temperature Compact Diffusion Bonded Heat Exchangers

    SciTech Connect

    Mylavarapu, Sai K.; Sun, Xiaodong; Christensen, Richard N.; Glosup, Richard E.; Unocic, Raymond R

    2012-01-01

    The very high temperature reactor (VHTR), using gas-cooled reactor technology, is one of the six reactor concepts selected by the Generation IV International Forum and is anticipated to be the reactor type for the next generation nuclear plant (NGNP). In this type of reactor with an indirect power cycle system, a high-temperature and high integrity intermediate heat exchanger (IHX) with high effectiveness is required to efficiently transfer the core thermal output to secondary fluid for electricity production, process heat, or hydrogen cogeneration. The current Technology Readiness Level status issued by NGNP to all components associated with the IHX for reactor core outlet temperatures of 750-800oC is 3 on a scale of 1 to 10 with 10 being the most ready. At present, there is no proven high-temperature IHX concept for VHTRs. Amongst the various potential IHX concepts available, diffusion bonded heat exchangers (henceforth called printed circuit heat exchangers, or PCHEs) appear promising for NGNP applications. The design and fabrication of this key component of NGNP is the primary focus of this paper. In the current study, two PCHEs were fabricated using Alloy 617 plates and will be experimentally investigated for their thermal-hydraulic performance in a high-temperature helium test facility (HTHF). The HTHF was primarily designed and constructed to test the thermal-hydraulic performance of PCHEs The test facility is primarily of Alloy 800H construction and is designed to facilitate experiments at temperatures and pressures up to 800oC and 3 MPa, respectively. The PCHE fabrication related processes, i.e., photochemical machining and diffusion bonding are briefly discussed for Alloy 617 plates. Diffusion bonding of Alloy 617 plates with and without a Ni interlayer is discussed. Furthermore, preliminary microstructural and mechanical characterization studies of representative diffusion bonded Alloy 617 specimens are presented.

  16. Understanding Dynamic Competitive Technology Diffusion in Electronic Markets

    NASA Astrophysics Data System (ADS)

    Zhang, Cheng; Song, Peijian; Xu, Yunjie; Xue, Ling

    The extant literature on information technology (IT) diffusion has largely treated technology diffusion as a generic and independent process. This study, in contrast, examines the diffusion of different IT products with brand differentiation and competition. Drawing upon existing theories of product diffusion, we propose a research model to capture the dynamics of the competitive diffusion of web-based IT products and validate it with longitudinal field data of e-business platforms. Our findings suggest that IT product diffusion can be better predicted by a competitive model than by an independent-diffusion-process model. This research extends IT research to the context of competitive diffusion and provides practitioners an effective model to predict the dissemination of their products. The research also suggests the existence of asymmetric interactions among competing products, prompting scholars and practitioners to pay attention to the influence of competing products when making forecast of their product market.

  17. Influence of silicon dangling bonds on germanium thermal diffusion within SiO{sub 2} glass

    SciTech Connect

    Barba, D.; Martin, F.; Ross, G. G.; Cai, R. S.; Wang, Y. Q.; Demarche, J.; Terwagne, G.; Rosei, F.

    2014-03-17

    We study the influence of silicon dangling bonds on germanium thermal diffusion within silicon oxide and fused silica substrates heated to high temperatures. By using scanning electron microscopy and Rutherford backscattering spectroscopy, we determine that the lower mobility of Ge found within SiO{sub 2}/Si films can be associated with the presence of unsaturated SiO{sub x} chemical bonds. Comparative measurements obtained by x-ray photoelectron spectroscopy show that 10% of silicon dangling bonds can reduce Ge desorption by 80%. Thus, the decrease of the silicon oxidation state yields a greater thermal stability of Ge inside SiO{sub 2} glass, which could enable to considerably extend the performance of Ge-based devices above 1300 K.

  18. 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.

  19. Fluid dynamics of double diffusive systems

    SciTech Connect

    Koseff, J.R.

    1989-04-07

    A study of mixing processes in doubly diffusive systems is being conducted. Continuous gradients of two diffusing components (heat and salinity in our case) are being used as initial conditions, and forcing is introduced by lateral heating and surface shear. The goals of the proposed work include: (1) quantification of the effects of finite amplitude disturbances on stable, double diffusive systems, particularly with respect to lateral heating, (2) development of an improved understanding of the physical phenomena present in wind-driven shear flows in double diffusive stratified environments, (3) increasing our knowledge-base on turbulent flow in stratified environments and how to represent it, and (4) formulation of a numerical code for such flows. The work is being carried out in an experimental facility which is located in the Stanford Environmental Fluid Mechanics Laboratory, and on laboratory minicomputers and CRAY computers. In particular we are focusing on the following key issues: (1) the formation and propagation of double diffusive intrusions away from a heated wall and the effects of lateral heating on the double diffusive system; (2) the interaction between the double diffusively influenced fluxes and the turbulence induced fluxes; (3) the measurement of heat and mass fluxes; and (4) the influence of double diffusive gradients on mixed layer deepening. 1 fig.

  20. Dynamic versus static bond-strength testing of adhesive interfaces.

    PubMed

    Poitevin, André; De Munck, Jan; Cardoso, Marcio Vivan; Mine, Atsushi; Peumans, Marleen; Lambrechts, Paul; Van Meerbeek, Bart

    2010-11-01

    A static bond-strength test is often regarded as clinically less relevant, since such abrupt loading of the adhesive-tooth bond clinically never occurs. Therefore, dynamic fatigue testing is often claimed to better predict the clinical effectiveness of adhesives. To measure the micro-tensile fatigue resistance (μTFR) of adhesives bonded to dentin, and to compare their μTFR to their micro-tensile bond strength (μTBS). The bonding effectiveness (including fracture analysis) of three adhesives (OptiBond FL, Kerr: 3-step etch-and-rinse adhesive or 3-E&Ra; Clearfil SE, Kuraray: 2-step self-etch adhesive or 2-SEa; G-Bond, GC: 1-step self-etch adhesive or 1-SEa) was measured by means of both a dynamic μTFR and a static μTBS approach. Preparation and test set-up of the micro-specimens were identical for both tests. In fatigue, specimens were tested with a wide range of selected loads at 2Hz and at 10Hz until failure, or until 10(4) cycles were reached. At 2Hz, the μTFR was also measured after 3-month water storage. The μTFR was determined using a logistic regression model. Two-way ANOVA and Tukey HSD multiple comparisons test were used to determine statistical differences in μTBS. The 1-SEa recorded significantly lower values in μTFR at 10Hz and in μTBS than the 2-SEa and 3-E&Ra. The 1-SEa and the 2-SEa performed significantly lower in μTFR than the 3-E&Ra, when tested at 2Hz after 3-month water storage. Fatigue testing at 2Hz after 1-week water storage did not reveal any differences in μTFR between the three adhesives. The 3-E&Ra performed best in terms of bonding effectiveness, irrespective of the experimental condition or test used. The μTBS test proved once more to be a reliable laboratory test in ranking contemporary adhesives on their bonding effectiveness. Copyright © 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  1. Reflexion measurements for inverse characterization of steel diffusion bond mechanical properties

    NASA Astrophysics Data System (ADS)

    Le Bourdais, Florian; Cachon, Lionel; Rigal, Emmanuel

    2017-02-01

    The present work describes a non-destructive testing method aimed at securing high manufacturing quality of the innovative compact heat exchanger developed under the framework of the CEA R&D program dedicated to the Advanced Sodium Technological Reactor for Industrial Demonstration (ASTRID). The heat exchanger assembly procedure currently proposed involves high temperature and high pressure diffusion welding of stainless steel plates. The aim of the non-destructive method presented herein is to characterize the quality of the welds obtained through this assembly process. Based on a low-frequency model developed by Baik and Thompson [1], pulse-echo normal incidence measurements are calibrated according to a specific procedure and allow the determination of the welding interface stiffness using a nonlinear fitting procedure in the frequency domain. Performing the characterization of plates after diffusion welding using this method allows a useful assessment of the material state as a function of the diffusion bonding process.

  2. Diffusion bonding of commercially pure titanium to low carbon steel using a silver interlayer

    SciTech Connect

    Atasoy, Evren; Kahraman, Nizamettin

    2008-10-15

    Titanium and low carbon steel plates were joined through diffusion bonding using a silver interlayer at various temperatures for various diffusion times. In order to determine the strength of the resulting joints, tensile-shear tests and hardness tests were applied. Additionally, optical, scanning electron microscopy examinations and energy dispersive spectrometry elemental analyses were carried out to determine the interface properties of the joint. The work showed that the highest interface strength was obtained for the specimens joined at 850 deg. C for 90 min. It was seen from the hardness results that the highest hardness value was obtained for the interlayer material and the hardness values on the both sides of the interlayer decreased gradually as the distance from the joint increased. In energy dispersive spectrometry analyses, it was seen that the amount of silver in the interlayer decreased markedly depending on the temperature rise. In addition, increasing diffusion time also caused some slight decrease in the amount of silver.

  3. Fabrication and Design Aspects of High-Temperature Compact Diffusion Bonded Heat Exchangers

    SciTech Connect

    Sai K. Mylavarapu; Richard N. Christensen; Raymond R. Unocic; Richard E. Glosup; Mike W. Patterson

    2012-08-01

    The Very High Temperature Reactor (VHTR) using gas-cooled reactor technology is anticipated to be the reactor type for the Next Generation Nuclear Plant (NGNP). In this reactor concept with an indirect power cycle system, a high-temperature and high integrity Intermediate Heat Exchanger (IHX) with high effectiveness is required to efficiently transfer the core thermal output to a secondary fluid for electricity generation, hydrogen production, and/or industrial process heat applications. At present, there is no proven IHX concept for VHTRs. The current Technology Readiness Level (TRL) status issued by NGNP to all components associated with the IHX for reduced nominal reactor outlet temperatures of 750–800 degrees C is 3 on a 1–10 scale, with 10 indicating omplete technological maturity. Among the various potential IHX concepts available, diffusion bonded heat exchangers (henceforth called printed circuit heat exchangers, or PCHEs) appear promising for NGNP applications. The design and fabrication of this key component of NGNP with Alloy 617, a candidate high-temperature structural material for NGNP applications, are the primary focus of this paper. In the current study, diffusion bonding of Alloy 617 has been demonstrated, although the optimum diffusion bonding process parameters to engineer a quasi interface-free joint are yet to be determined. The PCHE fabrication related processes, i.e., photochemical etching and diffusion bonding are discussed for Alloy 617 plates. In addition, the authors’ experiences with these non-conventional machining and joining techniques are discussed. Two PCHEs are fabricated using Alloy 617 plates and are being experimentally investigated for their thermal-hydraulic performance in a High-Temperature Helium Facility (HTHF). The HTHF is primarily of Alloy 800H construction and is designed to facilitate experiments at temperatures and pressures up to 800 degrees C and 3 MPa, respectively. Furthermore, some preliminary

  4. Rumor diffusion in an interests-based dynamic social network.

    PubMed

    Tang, Mingsheng; Mao, Xinjun; Guessoum, Zahia; Zhou, Huiping

    2013-01-01

    To research rumor diffusion in social friend network, based on interests, a dynamic friend network is proposed, which has the characteristics of clustering and community, and a diffusion model is also proposed. With this friend network and rumor diffusion model, based on the zombie-city model, some simulation experiments to analyze the characteristics of rumor diffusion in social friend networks have been conducted. The results show some interesting observations: (1) positive information may evolve to become a rumor through the diffusion process that people may modify the information by word of mouth; (2) with the same average degree, a random social network has a smaller clustering coefficient and is more beneficial for rumor diffusion than the dynamic friend network; (3) a rumor is spread more widely in a social network with a smaller global clustering coefficient than in a social network with a larger global clustering coefficient; and (4) a network with a smaller clustering coefficient has a larger efficiency.

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

    SciTech Connect

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

    2014-05-01

    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–10Mo 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

  6. Molecular dynamics study of tracer diffusion of argon adsorbed on amorphous surfaces

    NASA Astrophysics Data System (ADS)

    Riccardo, J. L.; Steele, W. A.

    1996-12-01

    An isokinetic molecular dynamics simulation of argon adsorbed on several model amorphous surfaces of titanium dioxide is carried out. The solid is represented by the Bernal Model in which the surface is taken to be the exposed face of a dense random packing of oxide ions. This surface is roughened by deleting varying numbers of oxides at random from the outer layer of the solid. Surface diffusion in the limit of very low coverage (tracer diffusion) is evaluated by following the dynamics of noninteracting single adatoms. The diffusion coefficient in the zero-density limit is calculated from velocity autocorrelation functions for adatoms at several temperatures ranging from 85 to 300 K. The temperature dependence of the diffusion constants obtained in this way shows nearly Arrhenius behavior in this temperature range. It is shown that surface roughening at the atomic scale give rise to a higher apparent activation energy for diffusion. A statistical characterization of the adsorptive field through distributions of local maxima and minima in the adsorption energy surface along the diffusion paths was performed in order to relate the surface diffusion of monatomic species on amorphous surfaces to the recently proposed Dual Site-Bond Description of Heterogeneous Surfaces (DSBD). Independent evidence supporting the theoretical hypothesis of the DSBD is also obtained.

  7. Bonding dynamics of compliant microbump during ultrasonic bonding investigated by using Si strain gauge

    NASA Astrophysics Data System (ADS)

    Iwanabe, Keiichiro; Nakadozono, Kenichi; Senda, Yousuke; Asano, Tanemasa

    2016-06-01

    The bonding dynamics of a cone-shaped microbump during ultrasonic bonding are investigated by in situ measurements of the strain generated in a substrate using a piezoresistance strain sensor. The strain sensor is composed of a pair of p- and n-type piezoresistance gauges to extract strain components in the ultrasonic vibration along the plane parallel to the substrate surface and along the direction perpendicular to the surface. Flip-chip bonding is performed at room-temperature. The time evolution of the strain generated in the substrate according to the load-up of pressing force and application of ultrasonic vibration is clearly detected. The softening of the bump metal during the application of ultrasonic vibration is clearly observed. Results of a comparative study between the bonding of a cone-shaped microbump and that of a flat-top microbump suggest mechanical stress concentration near the top end of the cone-shaped microbump, which results in the transformation of the crystal texture of the bump from grains to fine crystallites.

  8. Diffusive Dynamics of Nanoparticles in Arrays of Nanoposts

    SciTech Connect

    He, Kai; Korasani, Firoozeh; Thomas, Darrell Keith; Retterer, Scott T; Conrad, Jacinta; Krishnamoorti, Ramanan

    2013-01-01

    The diffusive dynamics of dilute dispersions of nanoparticles of diameter 200 400 nm were studied in microfabricated arrays of nanoposts using differential dynamic microscopy and single particle tracking. Posts of diameter 500 nm and height 10 m were spaced by 1.2 10 m on a square lattice. As the spacing between posts was decreased, the dynamics of the nanoparticles slowed. Moreover, the dynamics at all length scales were best represented by a stretched exponential rather than a simple exponential. Both the relative diffusivity and the stretching exponent decreased linearly with increased confinement and, equivalently, with decreased void volume. The slowing of the overall diffusive dynamics and the broadening distribution of nanoparticle displacements with increased confinement are consistent with the onset of cooperative dynamics.

  9. Gas Diffusion in Polyethylene Terepthalate By Molecular Dynamics

    NASA Astrophysics Data System (ADS)

    Butler, Simon; Adolf, David

    2006-03-01

    Molecular dynamics simulations of the diffusion of small penetrants through PET have been performed utilising the anisotropic united atom model [1] and a virtual liquid technique. [2] The accuracy and reliability of these two approaches has been assessed in terms of the improvement in equation of state behaviour and of diffusion co-efficients and solubilities. The effect of the diffusion of nitrogen, carbon dioxide, and oxygen on the local dynamics of PET have been investigated as a result. Attention has been focused on the dual mode effect [3] observed during mixed gas diffusion. [1] Molecular dynamics calculation of the equation of state of alkanes, J. Chem. Phys. 93, 6 (1990) [2] Kikuchi, Kuwajima, Fukada, Novel method to estimate the solubility of small molecules in cis-polyisoprene by molecular dynamics simulations, J. Chem. Phys, 115, 13 (2001) [3] Lewis, Duckett, Ward, Fairclough, Ryan, The barrier properties of polyethylene terephthalate to mixtures of oxygen, carbon dioxide and nitrogen, Polymer, 1631, 44 (2003)

  10. Verification of the effect of surface preparation on Hot Isostatic Pressing diffusion bonding joints of CLAM steel

    NASA Astrophysics Data System (ADS)

    Zhao, Yanyun; Li, Chunjing; Huang, Bo; Liu, Shaojun; Huang, Qunying

    2014-12-01

    Hot Isostatic Pressing (HIP) diffusion bonding with CLAM steel is the primary candidate fabrication technique for the first wall (FW) of DFLL-TBM. Surface state is one of the key factors for the joints quality. The effect of surface state prepared with grinder and miller on HIP diffusion bonding joints of CLAM steel was investigated. HIP diffusion bonding was performed at 140 MPa and 1373 K within 3 h. The mechanical properties of the joints were investigated with instrumented Charpy V-notch impact tests and the microstructures of the joints were analyzed with scanning electron microscopy (SEM). The results showed that the milled samples with fine surface roughness were more suitable for CLAM steel HIP diffusion bonding.

  11. Molecular dynamics simulations on local structure and diffusion in liquid Ti x Al 1- x alloys

    NASA Astrophysics Data System (ADS)

    Xia, J. H.; Liu, C. S.; Cheng, Z. F.; Shi, D. P.

    2011-10-01

    The microscopic structure and dynamics of liquid Ti xAl 1- x alloys together with pure liquid Ti and Al metals were investigated by means of molecular dynamics simulations. This work gives the structural properties, including pair-correlation function, bond-angle distribution function, HA and Voronoi indices, and their composition dependence. The dynamical properties have also been studied. The calculated pair-correlation function, bond-angle distribution function, and HA and Voronoi indices suggest that the stoichiometric composition Ti 0.75Al 0.25 exhibits a different local structure order compared with other concentrations, which help us understand the appearance of the minimum diffusion coefficient at this composition. These results indicate that the mobility of atoms strongly depends on their atomic local structure.

  12. Diffusion bonding of Al7075 alloy to titanium aluminum vanadate alloy

    NASA Astrophysics Data System (ADS)

    Alhazaa, Abdulaziz Nasser

    The aluminum alloy (Al7075) and titanium alloy (Ti-6Al-4V) are used in a variety of applications in the aerospace industry. However, the high cost of Ti-6Al-4V alloy has been a major factor which has limited its use and therefore, the ability to join Al7075 alloy to Ti-6Al-4V alloy can provide a product that is less costly, but retains the high strength and light weight properties necessary for the transport industry. However, the large difference in the physical properties between these two alloys prevents the use of conventional joining techniques such as fusion welding to join these dissimilar alloys. Therefore, the diffusion bonding technique was used to join Al7075 alloy to Ti-6Al-4V alloy with the objective of minimizing microstructural changes of the two alloys during the bonding process. In this thesis, solid state and liquid phase bonding processes were undertaken. Solid state bonding was employed without interlayers and was successful at 510°C and 7 MPa. The bond interface showed an absence of the oxides due to the dissolution of oxygen into the titanium solution. Bonds made using copper interlayers at a temperature sufficient enough to form eutectic liquid formation between copper and aluminum were produced. The intermetallics theta(Al2Cu), S(Al2CuMg) and T(Al2Mg3Zn3) were identified at the aluminum interface while Cu3Ti2 intermetallic was identified at the titanium interface. Bonds made using tin based alloys interlayers and copper coatings were successful and gave the highest shear strength. The eutectic formation on the Al7075 alloy was responsible for joint formation at the aluminum interface while the formation of Sn3Ti5 intermetallic was responsible for the joint formation at titanium interface. The corrosion rate of the bonds decreased with increasing bonding time for joints made using the tin based interlayer in 3% NaCl solution. However, the presence of copper within the joint increased the corrosion rate of the bonds and this was attributed to

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

    SciTech Connect

    Bhatia, Harsh; Gyulassy, Attila; Ong, Mitchell; Lordi, Vincenzo; Draeger, Erik; Pask, John; Pascucci, Valerio; Bremer, Peer -Timo

    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 to 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.

  14. Diffusion mechanism of hydrogen in amorphous silicon - Ab initio molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Su, Y.-S.; Pantelides, S. T.

    2001-03-01

    Diffusion of hydrogen in hydrogenated amorphous silicon (a-Si:H) is an important process, but the mechanism is still not well understood and even controversial. The observed activation energy is only about 1.5 eV, whereas the energy to dissociate Si-H bonds is much larger ( 2.5 eV). H is generally believed to migrate as an interstitial, perhaps as in crystalline Si. We report first-principles density-functional molecular dynamics simulations and identify a wealth of processes that occur. The main mechanism for the release of H from Si-H bonds is the conversion of the Si atom to fivefold coordination by the arrival of a floating bond, as suggested by one of us (STP, Phys. Rev. Lett. 58, 1344 (1987)) but the H atom is not released in the interstitial regions. Migration occurs by a bond-interconversion process, with the H atom acting as the analog of a floating bond. Estimates of the diffusion constant are in agreement with observations. Work supported in part by NSF.

  15. Extracting the diffusion tensor from molecular dynamics simulation with Milestoning

    NASA Astrophysics Data System (ADS)

    Mugnai, Mauro L.; Elber, Ron

    2015-01-01

    We propose an algorithm to extract the diffusion tensor from Molecular Dynamics simulations with Milestoning. A Kramers-Moyal expansion of a discrete master equation, which is the Markovian limit of the Milestoning theory, determines the diffusion tensor. To test the algorithm, we analyze overdamped Langevin trajectories and recover a multidimensional Fokker-Planck equation. The recovery process determines the flux through a mesh and estimates local kinetic parameters. Rate coefficients are converted to the derivatives of the potential of mean force and to coordinate dependent diffusion tensor. We illustrate the computation on simple models and on an atomically detailed system—the diffusion along the backbone torsions of a solvated alanine dipeptide.

  16. Extracting the diffusion tensor from molecular dynamics simulation with Milestoning

    SciTech Connect

    Mugnai, Mauro L.; Elber, Ron

    2015-01-07

    We propose an algorithm to extract the diffusion tensor from Molecular Dynamics simulations with Milestoning. A Kramers-Moyal expansion of a discrete master equation, which is the Markovian limit of the Milestoning theory, determines the diffusion tensor. To test the algorithm, we analyze overdamped Langevin trajectories and recover a multidimensional Fokker-Planck equation. The recovery process determines the flux through a mesh and estimates local kinetic parameters. Rate coefficients are converted to the derivatives of the potential of mean force and to coordinate dependent diffusion tensor. We illustrate the computation on simple models and on an atomically detailed system—the diffusion along the backbone torsions of a solvated alanine dipeptide.

  17. Extracting the diffusion tensor from molecular dynamics simulation with Milestoning.

    PubMed

    Mugnai, Mauro L; Elber, Ron

    2015-01-07

    We propose an algorithm to extract the diffusion tensor from Molecular Dynamics simulations with Milestoning. A Kramers-Moyal expansion of a discrete master equation, which is the Markovian limit of the Milestoning theory, determines the diffusion tensor. To test the algorithm, we analyze overdamped Langevin trajectories and recover a multidimensional Fokker-Planck equation. The recovery process determines the flux through a mesh and estimates local kinetic parameters. Rate coefficients are converted to the derivatives of the potential of mean force and to coordinate dependent diffusion tensor. We illustrate the computation on simple models and on an atomically detailed system-the diffusion along the backbone torsions of a solvated alanine dipeptide.

  18. Galactic civilizations: Population dynamics and interstellar diffusion

    NASA Technical Reports Server (NTRS)

    Newman, W. I.; Sagan, C.

    1978-01-01

    The interstellar diffusion of galactic civilizations is reexamined by potential theory; both numerical and analytical solutions are derived for the nonlinear partial differential equations which specify a range of relevant models, drawn from blast wave physics, soil science, and, especially, population biology. An essential feature of these models is that, for all civilizations, population growth must be limited by the carrying capacity of the environment. Dispersal is fundamentally a diffusion process; a density-dependent diffusivity describes interstellar emigration. Two models are considered: the first describing zero population growth (ZPG), and the second which also includes local growth and saturation of a planetary population, and for which an asymptotic traveling wave solution is found.

  19. Applying Taguchi methods for solvent-assisted PMMA bonding technique for static and dynamic micro-TAS devices.

    PubMed

    Hsu, Yi-Chu; Chen, Tang-Yuan

    2007-08-01

    This work examines numerous significant process parameters in the solvent-assistant Polymethyl methacrylate (PMMA) bonding scheme and presents two Micro-total-analysis System (micro-TAS) devices generated by adopting the optimal bonding parameters. The process parameters considered were heating temperature, applied loading, duration and solution. The effects of selected process parameters on bonding dimensions loss and strength, and subsequent optimal setting of the parameters were accomplished using Taguchi's scheme. Additionally, two micro-TAS devices were realized using a static paraffin microvalve and a dynamic diffuser micropump. The PMMA chips were carved using a CO2 laser that patterned device microchannels and microchambers. The operation principles, fabrication processes and experimental performance of the devices are discussed. This bonding technique has numerous benefits, including high bonding strength (240 kgf/cm2) and low dimension loss (2-6%). For comparison, this work also demonstrates that the normal stress of this technology is 2-15 times greater than that of other bonding technologies, including hot embossing, anodic bonding, direct bonding and thermal fusion bonding.

  20. Classification of Dynamical Diffusion States in Single Molecule Tracking Microscopy

    PubMed Central

    Bosch, Peter J.; Kanger, Johannes S.; Subramaniam, Vinod

    2014-01-01

    Single molecule tracking of membrane proteins by fluorescence microscopy is a promising method to investigate dynamic processes in live cells. Translating the trajectories of proteins to biological implications, such as protein interactions, requires the classification of protein motion within the trajectories. Spatial information of protein motion may reveal where the protein interacts with cellular structures, because binding of proteins to such structures often alters their diffusion speed. For dynamic diffusion systems, we provide an analytical framework to determine in which diffusion state a molecule is residing during the course of its trajectory. We compare different methods for the quantification of motion to utilize this framework for the classification of two diffusion states (two populations with different diffusion speed). We found that a gyration quantification method and a Bayesian statistics-based method are the most accurate in diffusion-state classification for realistic experimentally obtained datasets, of which the gyration method is much less computationally demanding. After classification of the diffusion, the lifetime of the states can be determined, and images of the diffusion states can be reconstructed at high resolution. Simulations validate these applications. We apply the classification and its applications to experimental data to demonstrate the potential of this approach to obtain further insights into the dynamics of cell membrane proteins. PMID:25099798

  1. Dynamics and pattern formation in a cancer network with diffusion

    NASA Astrophysics Data System (ADS)

    Zheng, Qianqian; Shen, Jianwei

    2015-10-01

    Diffusion is ubiquitous inside cells, and it is capable of inducing spontaneous pattern formation in reaction-diffusion systems on a spatially homogeneous domain. In this paper, we investigate the dynamics of a diffusive cancer network regulated by microRNA and obtain the condition that the network undergoes a Hopf bifurcation and a Turing pattern bifurcation. In addition, we also develop the amplitude equation of the network model by using Taylor series expansion, multi-scaling and further expansion in powers of a small parameter. As a result of these analyses, we obtain the explicit condition on how the dynamics of the diffusive cancer network evolve. These results reveal that this system has rich dynamics, such as spotted stripe and hexagon patterns. The bifurcation diagram helps us understand the biological mechanism in the cancer network. Finally, numerical simulations confirm our analytical results.

  2. Examination of superplastic forming combined with diffusion bonding for titanium: Perspective from experience

    NASA Astrophysics Data System (ADS)

    Sanders, Daniel G.; Ramulu, Mamidala

    2004-12-01

    Superplastic forming (SPF) combined with diffusion bonding (DB) has been used successfully for the fabrication of titanium aerospace hardware. Many of these applications have been for military aircraft, whereby a complex built-up structure has been replaced with monolithic parts. Several methods for applying the two- and four-sheet titanium SPF/DB processes have been devised, including the welding of sheets prior to forming and the use of silk-screened stop-off (yttria) to prevent bonding where it is undesirable. Very little progress has been made in the past few years toward understanding and modeling the SPF/DB process using constitutive equations and data by laboratory testing. Concerns that engineers face in designing for fatigue life, acceptable design loads, and damage tolerance are currently being studied, but the database is very limited. This is a summary of past work found in the literature and forms the foundation for additional research.

  3. Molecular dynamics study of water molecule diffusion in oil-paper insulation materials

    NASA Astrophysics Data System (ADS)

    Liao, Rui-Jin; Zhu, Meng-Zhao; Yang, Li-Jun; Zhou, Xin; Gong, Chun-Yan

    2011-03-01

    Moisture is an important factor that influences the safe operation of transformers. In this study, molecular dynamics was employed to investigate the diffusion behavior of water molecules in the oil-paper insulation materials of transformers. Two oil-cellulose models were built. In the first model, water molecules were initially distributed in oil, and in the second model, water molecules were distributed in cellulose. The non-bonding energies of interaction between water molecules and oil, and between water molecules and cellulose, were calculated by the Dreiding force field. The interaction energy was found to play a dominant role in influencing the equilibrium distribution of water molecules. The radial direction functions of water molecules toward oil and cellulose indicate that the hydrogen bonds between water molecules and cellulose are sufficiently strong to withstand the operating temperature of the transformer. Mean-square displacement analysis of water molecules diffusion suggests that water molecules initially distributed in oil showed anisotropic diffusion; they tended to diffuse toward cellulose. Water molecules initially distributed in cellulose diffused isotropically. This study provides a theoretical contribution for improvements in online monitoring of water in transformers, and for subsequent research on new insulation materials.

  4. Elastic stability of superplastically formed/diffusion-bonded orthogonally corrugated core sandwich plates

    NASA Technical Reports Server (NTRS)

    Ko, W. L.

    1980-01-01

    The paper concerns the elastic buckling behavior of a newly developed superplastically formed/diffusion-bonded (SPF/DB) orthogonally corrugated core sandwich plate. Uniaxial buckling loads were calculated for this type of sandwich plate with simply supported edges by using orthotropic sandwich plate theory. The buckling behavior of this sandwich plate was then compared with that of an SPF/DB unidirectionally corrugated core sandwich plate under conditions of equal structural density. It was found that the buckling load for the former was considerably higher than that of the latter.

  5. 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.

  6. Structural properties of superplastically formed/diffusion-bonded orthogonally corrugated core sandwich plates

    NASA Technical Reports Server (NTRS)

    Ko, W. L.

    1980-01-01

    This paper describes a new superplastically formed/diffusion-bonded (SPF/DB) orthogonally corrugated sandwich structure, and presents formulae and the associated plots for evaluating the effective elastic constants for the core of this new sandwich structure. Comparison of structural properties of this new sandwich structure with the conventional honeycomb core sandwich structure was made under the condition of equal sandwich density. It was found that the SPF/DB orthogonally corrugated sandwich core has higher transverse shear stiffness than the conventional honeycomb sandwich core. However, the former has lower stiffness in the sandwich core thickness direction than the latter.

  7. Superplastic Formed and Diffusion Bonded Titanium Landing Gear Component Feasibility Study.

    DTIC Science & Technology

    1980-07-01

    Gear Superplastic Forming Shock Strut SPF/DB Outer Cylinder Titanium Diffusion Bonding Cylindrical Sandwich Structure Z% ABSTRACT (Continue en ro,eree...lO0 Fighter Aircraft 6 5 F-lO0 Main Landing Gear 6 6 F-lO0 Landing Gear Strut Section Selected for this Program 7 7 SPF/DB Titanium Landing Gear... Assembly with a Diaphram Seal for DB Cycle. 18 15 MLG SPF/DB Titanium Outer Cylinder Segment DB Cycle Using a Diaphram Seal 19 16 Hot Sizing Tool 20 17

  8. Tracer surface diffusion at high pressures: Molecular-dynamics study

    NASA Astrophysics Data System (ADS)

    Zeiri, Yehuda

    2000-09-01

    Molecular-dynamics simulations were employed to investigate the influence of high pressure on tracer surface diffusion. A model potential was used to describe the interaction among the various species in the system. The different binding energy values and masses used in this model simulation correspond to surface diffusion of N2 on Ru(001) surface under pressure of Ar. A pronounced enhancement in the magnitude of the diffusion coefficients was observed when pressure increased from P=0 to P=200 atm. The relationship between diffusion coefficient and three parameters that characterize the system was explored. It was found that the gas temperature and the nature of gas-adsorbate interaction (i.e., attractive or repulsive) have only a negligible influence on the diffusion coefficient. However, a marked variation in the diffusion coefficient was observed when the magnitude of gas-substrate binding energy was altered. The temperature dependence of the surface diffusion coefficient exhibits an Arrhenius behavior for all cases investigated. The relationship between the pressure and both pre-exponential factor and activation energy for surface diffusion was discussed based on a detailed analysis of the diffusion mechanism. The diffusion mechanism was deduced by careful examination of large number of individual trajectories.

  9. Release of polyphenolic drugs from dynamically bonded layer-by-layer films.

    PubMed

    Zhou, Lin; Chen, Mao; Tian, Lili; Guan, Ying; Zhang, Yongjun

    2013-05-01

    Layer-by-layer (LbL) assembled films have been exploited for surface-mediated drug delivery. The drugs loaded in the films were usually released via diffusion or the degradation of one of the film components. Here we demonstrate that drug release can also be achieved by exploiting the dynamic nature of hydrogen-bonded LbL films. The films were fabricated from tannic acid (TA), a model polyphenolic drug, and poly(vinyl pyrrolidone) (PVPON). The driving force for the film buildup is the hydrogen bonding between the two components, which was confirmed by Fourier transform infrared (FTIR) spectra. The film growth is linear, and the growth rate of the film decreases with increasing assembly temperature. Because of the reversible/dynamic nature of hydrogen bonding, when soaked in aqueous solutions, the PVPON/TA films disassemble gradually and thus release TA to the media. The release rate of TA increases with increasing pH and temperature but decreases with increasing ionic strength. Scanning electron microscopy (SEM) studies on the surface morphology of the film during TA release reveal that the film surface becomes smoother and then rougher again because of the dewetting of the film. The released TA can scavenge ABTS(+•) cation radicals, indicating it retains its antioxidant activity, a major biological activity of polyphenols.

  10. 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.

  11. Diffusion Bonding of Ti-6Al-4V Sheet with Ti-6Al-4V Foam for Biomedical Implant Applications

    NASA Astrophysics Data System (ADS)

    Hamilton, Brittany; Oppenheimer, Scott; Dunand, David C.; Lewis, Daniel

    2013-12-01

    Advanced metallic bone implants are designed to have a porous surface to improve osseointegration and reduce risks of loosening. An alternative approach to existing surface treatments to create a porous surface is to bond separately produced metallic foams onto the implant. To assess the feasibility of this approach, a Ti-6Al-4V foam was diffusion bonded onto bulk Ti-6Al-4V in an argon atmosphere at temperatures between 1173 K and 1223 K (900 °C and 950 °C) for times between 45 and 75 minutes. These specimens were tested in tension to determine bond quality: failures occurred in the foam, indicating a strong diffusion-bonded interface. The quality of the bond was confirmed by metallographic studies, indicating that this approach, which can also be applied to creating of sandwich with porous cores, is successful.

  12. Microstructure and mechanical strength of diffusion bonded joints between silicon carbide and F82H steel

    NASA Astrophysics Data System (ADS)

    Zhong, Zhihong; Hinoki, Tatsuya; Kohyama, Akira

    2011-10-01

    The combination of SiC and reduced activation ferritic/martensitic steels is attractive for fusion applications because it is expected to offer high thermal efficiency, high reliability and superior safety characteristic under a neutron irradiation environment. In this paper, diffusion bonding of SiC to F82H steel has been investigated. Direct joining of SiC to F82H was unsuccessful due to a large residual stress generated in the joint. A double W/Cu and a multiple W/Ni/Cu/Ni interlayer were used to reduce the residual stress, and encouraging results were obtained. The interfacial microstructure examination revealed that the various interfaces were bonded well. Diffusion products in the reaction zones were identified. The shear strength of the SiC/F82H joints measured by knife-edge tests at room temperature was found to increase with the increase in the joining temperature, and reached a maximum of 41.3 MPa. The fracture surfaces of the joints were also analyzed.

  13. Detailed analysis of surface asperity deformation mechanism in diffusion bonding of steel hollow structural components

    NASA Astrophysics Data System (ADS)

    Zhang, C.; Li, H.; Li, M. Q.

    2016-05-01

    This study focused on the detailed analysis of surface asperity deformation mechanism in similar diffusion bonding as well as on the fabrication of high quality martensitic stainless steel hollow structural components. A special surface with regular patterns was processed to be joined so as to observe the extent of surface asperity deformation under different bonding pressures. Results showed that an undamaged hollow structural component has been obtained with full interfacial contact and the same shear strength to that of base material. Fracture surface characteristic combined with surface roughness profiles distinctly revealed the enhanced surface asperity deformation as the applied pressure increases. The influence of surface asperity deformation mechanism on joint formation was analyzed: (a) surface asperity deformation not only directly expanded the interfacial contact areas, but also released deformation heat and caused defects, indirectly accelerating atomic diffusion, then benefits to void shrinkage; (b) surface asperity deformation readily introduced stored energy difference between two opposite sides of interface grain boundary, resulting in strain induced interface grain boundary migration. In addition, the influence of void on interface grain boundary migration was analyzed in detail.

  14. Dynamic Fracture Behavior of Plastic-Bonded Explosives

    NASA Astrophysics Data System (ADS)

    Fu, Hua; Li, Jun-Ling; Tan, Duo-Wang; Ifp, Caep Team

    2011-06-01

    Plastic-Bonded Explosives (PBX) are used as important energetic materials in nuclear or conventional weapons. Arms Warhead in the service process and the ballistic phase, may experience complex process such as long pulse and higher loading, compresson, tension and reciprocating compression - tension, friction with the projectile shell, which would lead to explosive deformation and fracture.And the dynamic deformation and fracture behavior of PBX subsequently affect reaction characteristics and initiation mechanism in explosives, then having influence on explosives safety. The dynamic fracure behavior of PBX are generally complex and not well studied or understood. In this paper, the dynamic fracture of explosives are conducted using a Kolsky bar. The Brazilian test, also known as a indirect tensile test or splitting test, is chosen as the test method. Tensile strength under different strain rates are obtained using quartz crystal embedded in rod end. The dynamic deformation and fracture process are captured in real-time by high-speed digital camera, and the displacement and strain fields distribution before specimen fracture are obtained by digital correlation method. Considering the non-uniform microstructure of explosives,the dynamic fracture behavior of explosive are simulated by discrete element method, the simulation results can reproduce the deformation and fracture process in Brazilian test using a maximum tensile strain criterion.

  15. Multiparticle collision dynamics for diffusion-influenced signaling pathways

    NASA Astrophysics Data System (ADS)

    Strehl, R.; Rohlf, K.

    2016-08-01

    An efficient yet accurate simulation method for modeling diffusion-influenced reaction networks is presented. The method extends existing reactive multiparticle collision dynamics by incorporating species-dependent diffusion coefficients, and developing theoretical expressions for the reactant-dependent diffusion control. This off-lattice particle-based mesoscopic simulation tool is particularly suited for problems in which detailed descriptions of particle trajectories and local reactions are required. Numerical simulations of an intracellular signaling pathway for bacterial chemotaxis are carried out to validate our approach, and to demonstrate its efficiency.

  16. Diffusive dynamics of nanoparticles in ultra-confined media

    DOE PAGES

    Jacob, Jack Deodato; Conrad, Jacinta; Krishnamoorti, Ramanan; ...

    2015-08-10

    Differential dynamic microscopy (DDM) was used to investigate the diffusive dynamics of nanoparticles of diameter 200 400 nm that were strongly confined in a periodic square array of cylindrical nanoposts. The minimum distance between posts was 1.3 5 times the diameter of the nanoparticles. The image structure functions obtained from the DDM analysis were isotropic and could be fit by a stretched exponential function. The relaxation time scaled diffusively across the range of wave vectors studied, and the corresponding scalar diffusivities decreased monotonically with increased confinement. The decrease in diffusivity could be described by models for hindered diffusion that accountedmore » for steric restrictions and hydrodynamic interactions. The stretching exponent decreased linearly as the nanoparticles were increasingly confined by the posts. Altogether, these results are consistent with a picture in which strongly confined nanoparticles experience a heterogeneous spatial environment arising from hydrodynamics and volume exclusion on time scales comparable to cage escape, leading to multiple relaxation processes and Fickian but non-Gaussian diffusive dynamics.« less

  17. Diffusive dynamics of nanoparticles in ultra-confined media

    SciTech Connect

    Jacob, Jack Deodato; Conrad, Jacinta; Krishnamoorti, Ramanan; Retterer, Scott T.; He, Kai

    2015-08-10

    Differential dynamic microscopy (DDM) was used to investigate the diffusive dynamics of nanoparticles of diameter 200 400 nm that were strongly confined in a periodic square array of cylindrical nanoposts. The minimum distance between posts was 1.3 5 times the diameter of the nanoparticles. The image structure functions obtained from the DDM analysis were isotropic and could be fit by a stretched exponential function. The relaxation time scaled diffusively across the range of wave vectors studied, and the corresponding scalar diffusivities decreased monotonically with increased confinement. The decrease in diffusivity could be described by models for hindered diffusion that accounted for steric restrictions and hydrodynamic interactions. The stretching exponent decreased linearly as the nanoparticles were increasingly confined by the posts. Altogether, these results are consistent with a picture in which strongly confined nanoparticles experience a heterogeneous spatial environment arising from hydrodynamics and volume exclusion on time scales comparable to cage escape, leading to multiple relaxation processes and Fickian but non-Gaussian diffusive dynamics.

  18. Inferring Diffusion Dynamics from FCS in Heterogeneous Nuclear Environments

    PubMed Central

    Tsekouras, Konstantinos; Siegel, Amanda P.; Day, Richard N.; Pressé, Steve

    2015-01-01

    Fluorescence correlation spectroscopy (FCS) is a noninvasive technique that probes the diffusion dynamics of proteins down to single-molecule sensitivity in living cells. Critical mechanistic insight is often drawn from FCS experiments by fitting the resulting time-intensity correlation function, G(t), to known diffusion models. When simple models fail, the complex diffusion dynamics of proteins within heterogeneous cellular environments can be fit to anomalous diffusion models with adjustable anomalous exponents. Here, we take a different approach. We use the maximum entropy method to show—first using synthetic data—that a model for proteins diffusing while stochastically binding/unbinding to various affinity sites in living cells gives rise to a G(t) that could otherwise be equally well fit using anomalous diffusion models. We explain the mechanistic insight derived from our method. In particular, using real FCS data, we describe how the effects of cell crowding and binding to affinity sites manifest themselves in the behavior of G(t). Our focus is on the diffusive behavior of an engineered protein in 1) the heterochromatin region of the cell’s nucleus as well as 2) in the cell’s cytoplasm and 3) in solution. The protein consists of the basic region-leucine zipper (BZip) domain of the CCAAT/enhancer-binding protein (C/EBP) fused to fluorescent proteins. PMID:26153697

  19. Specific Ions Modulate Diffusion Dynamics of Hydration Water on Lipid Membrane Surfaces

    PubMed Central

    2015-01-01

    Effects of specific ions on the local translational diffusion of water near large hydrophilic lipid vesicle surfaces were measured by Overhauser dynamic nuclear polarization (ODNP). ODNP relies on an unpaired electron spin-containing probe located at molecular or surface sites to report on the dynamics of water protons within ∼10 Å from the spin probe, which give rise to spectral densities for electron–proton cross-relaxation processes in the 10 GHz regime. This pushes nuclear magnetic resonance relaxometry to more than an order of magnitude higher frequencies than conventionally feasible, permitting the measurement of water moving with picosecond to subnanosecond correlation times. Diffusion of water within ∼10 Å of, i.e., up to ∼3 water layers around the spin probes located on hydrophilic lipid vesicle surfaces is ∼5 times retarded compared to the bulk water translational diffusion. This directly reflects on the activation barrier for surface water diffusion, i.e., how tightly water is bound to the hydrophilic surface and surrounding waters. We find this value to be modulated by the presence of specific ions in solution, with its order following the known Hofmeister series. While a molecular description of how ions affect the hydration structure at the hydrophilic surface remains to be answered, the finding that Hofmeister ions directly modulate the surface water diffusivity implies that the strength of the hydrogen bond network of surface hydration water is directly modulated on hydrophilic surfaces. PMID:24456096

  20. The interstitialcy diffusion in FCC copper: A molecular dynamics study

    SciTech Connect

    Bukkuru, S. Rao, A. D. P.; Warrier, M.

    2015-06-24

    Damage of materials due to neutron irradiation occurs via energetic cascades caused by energetic primary knock-on atoms (PKA) created by the energetic neutron as it passes through the material. These cascades result in creation of Frenkel Pairs (interstitials and vacancies). The interstitials and vacancies diffuse and recombine to (I) nullify the damage when an interstitial recombines with a vacancy, (II) form interstitial clusters when two or more interstitials recombine, and (III) form vacancy clusters when several vacancies come together. The latter two processes result in change of material properties. Interstitial diffusion has reported time-scales of microseconds and vacancy diffusion has diffusion time-scales of the order of seconds. We have carried out molecular dynamics (MD) simulations of interstitial diffusion in crystal Cu to study the mechanism of diffusion. It is found that interstitialcy diffusion – wherein an interstitial displaces a lattice atom thereby making the lattice atom an interstitial – has time-scales of a few tens of pico-seconds. Therefore we propose that the “interstitialcy diffusion” mechanism could play a major part in the diffusive-recombinations of the Frenkel Pairs created during the cascade.

  1. Equilibrium and dynamic pleating of a crystalline bonded network

    NASA Astrophysics Data System (ADS)

    Ganguly, Saswati; Nath, Parswa; Horbach, Jürgen; Sollich, Peter; Karmakar, Smarajit; Sengupta, Surajit

    2017-03-01

    We describe a phase transition that gives rise to structurally non-trivial states in a two-dimensional ordered network of particles connected by harmonic bonds. Monte Carlo simulations reveal that the network supports, apart from the homogeneous phase, a number of heterogeneous "pleated" phases, which can be stabilised by an external field. This field is conjugate to a global collective variable quantifying "non-affineness," i.e., the deviation of local particle displacements from local affine deformation. In the pleated phase, stress is localised in ordered rows of pleats and eliminated from the rest of the lattice. The kinetics of the phase transition is unobservably slow in molecular dynamics simulation near coexistence, due to very large free energy barriers. When the external field is increased further to lower these barriers, the network exhibits rich dynamic behaviour: it transforms into a metastable phase with the stress now localised in a disordered arrangement of pleats. The pattern of pleats shows ageing dynamics and slow relaxation to equilibrium. Our predictions may be checked by experiments on tethered colloidal solids in dynamic laser traps.

  2. Recovering position-dependent diffusion from biased molecular dynamics simulations

    SciTech Connect

    Ljubetič, Ajasja; Urbančič, Iztok; Štrancar, Janez

    2014-02-28

    All atom molecular dynamics (MD) models provide valuable insight into the dynamics of biophysical systems, but are limited in size or length by the high computational demands. The latter can be reduced by simulating long term diffusive dynamics (also known as Langevin dynamics or Brownian motion) of the most interesting and important user-defined parts of the studied system, termed collective variables (colvars). A few hundred nanosecond-long biased MD trajectory can therefore be extended to millisecond lengths in the colvars subspace at a very small additional computational cost. In this work, we develop a method for determining multidimensional anisotropic position- and timescale-dependent diffusion coefficients (D) by analysing the changes of colvars in an existing MD trajectory. As a test case, we obtained D for dihedral angles of the alanine dipeptide. An open source Mathematica{sup ®} package, capable of determining and visualizing D in one or two dimensions, is available at https://github.com/lbf-ijs/DiffusiveDynamics . Given known free energy and D, the package can also generate diffusive trajectories.

  3. Recovering position-dependent diffusion from biased molecular dynamics simulations.

    PubMed

    Ljubetič, Ajasja; Urbančič, Iztok; Štrancar, Janez

    2014-02-28

    All atom molecular dynamics (MD) models provide valuable insight into the dynamics of biophysical systems, but are limited in size or length by the high computational demands. The latter can be reduced by simulating long term diffusive dynamics (also known as Langevin dynamics or Brownian motion) of the most interesting and important user-defined parts of the studied system, termed collective variables (colvars). A few hundred nanosecond-long biased MD trajectory can therefore be extended to millisecond lengths in the colvars subspace at a very small additional computational cost. In this work, we develop a method for determining multidimensional anisotropic position- and timescale-dependent diffusion coefficients (D) by analysing the changes of colvars in an existing MD trajectory. As a test case, we obtained D for dihedral angles of the alanine dipeptide. An open source Mathematica(®) package, capable of determining and visualizing D in one or two dimensions, is available at https://github.com/lbf-ijs/DiffusiveDynamics. Given known free energy and D, the package can also generate diffusive trajectories.

  4. Quantum diffusive dynamics of macromolecular transitions

    NASA Astrophysics Data System (ADS)

    Beccara, S. a.; Garberoglio, G.; Faccioli, P.

    2011-07-01

    We study the role of quantum fluctuations of atomic nuclei in the real-time dynamics of non-equilibrium macro-molecular transitions. To this goal we introduce an extension of the dominant reaction pathways formalism, in which the quantum corrections to the classical overdamped Langevin dynamics are rigorously taken into account to order ℏ2. We first illustrate our approach in simple cases, and compare with the results of the instanton theory. Then we apply our method to study the C7eq → C7ax transition of alanine dipeptide. We find that the inclusion of quantum fluctuations can significantly modify the reaction mechanism for peptides. For example, the energy difference which is overcome along the most probable pathway is reduced by as much as 50%.

  5. A Comparison Between Cold-Welded and Diffusion-Bonded Al/Cu Bimetallic Rods Produced by ECAE Process

    NASA Astrophysics Data System (ADS)

    Eslami, P.; Karimi Taheri, A.; Zebardast, M.

    2013-10-01

    In this research, the application of equal channel angular extrusion process to produce both the cold-welded and diffusion-bonded Al/Cu bimetallic rods is assessed. The joints shear strength for both of the methods are measured and compared. The microstructure examinations were also carried out using scanning electron microscope equipped with EDX system and x-ray diffraction analysis. The results exhibit that the strength of the bond in cold-welded specimens is dependent on the amount of stretch and pressure at the materials interface. But in the diffusion-bonded specimens, it is depended on the struggle between the oxidation rate of the mating surfaces accompanied by inter-metallic compounds formation and the aluminum and copper atoms ability to diffuse in the joint interface.

  6. Extracting the diffusion tensor from molecular dynamics simulation with Milestoning

    PubMed Central

    Mugnai, Mauro L.; Elber, Ron

    2015-01-01

    We propose an algorithm to extract the diffusion tensor from Molecular Dynamics simulations with Milestoning. A Kramers-Moyal expansion of a discrete master equation, which is the Markovian limit of the Milestoning theory, determines the diffusion tensor. To test the algorithm, we analyze overdamped Langevin trajectories and recover a multidimensional Fokker-Planck equation. The recovery process determines the flux through a mesh and estimates local kinetic parameters. Rate coefficients are converted to the derivatives of the potential of mean force and to coordinate dependent diffusion tensor. We illustrate the computation on simple models and on an atomically detailed system—the diffusion along the backbone torsions of a solvated alanine dipeptide. PMID:25573551

  7. 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.

  8. Dynamic heterogeneity controls diffusion and viscosity near biological interfaces.

    PubMed

    Pronk, Sander; Lindahl, Erik; Kasson, Peter M

    2014-01-01

    At a nanometre scale, the behaviour of biological fluids is largely governed by interfacial physical chemistry. This may manifest as slowed or anomalous diffusion. Here we describe how measures developed for studying glassy systems allow quantitative measurement of interfacial effects on water dynamics, showing that correlated motions of particles near a surface result in a viscosity greater than anticipated from individual particle motions. This effect arises as a fundamental consequence of spatial heterogeneity on nanometre length scales and applies to any fluid near any surface. Increased interfacial viscosity also causes the classic finding that large solutes such as proteins diffuse much more slowly than predicted in bulk water. This has previously been treated via an empirical correction to the solute size: the hydrodynamic radius. Using measurements of quantities from theories of glass dynamics, we can now calculate diffusion constants from molecular details alone, eliminating the empirical correction factor.

  9. Dynamic heterogeneity controls diffusion and viscosity near biological interfaces

    NASA Astrophysics Data System (ADS)

    Pronk, Sander; Lindahl, Erik; Kasson, Peter M.

    2014-01-01

    At a nanometre scale, the behaviour of biological fluids is largely governed by interfacial physical chemistry. This may manifest as slowed or anomalous diffusion. Here we describe how measures developed for studying glassy systems allow quantitative measurement of interfacial effects on water dynamics, showing that correlated motions of particles near a surface result in a viscosity greater than anticipated from individual particle motions. This effect arises as a fundamental consequence of spatial heterogeneity on nanometre length scales and applies to any fluid near any surface. Increased interfacial viscosity also causes the classic finding that large solutes such as proteins diffuse much more slowly than predicted in bulk water. This has previously been treated via an empirical correction to the solute size: the hydrodynamic radius. Using measurements of quantities from theories of glass dynamics, we can now calculate diffusion constants from molecular details alone, eliminating the empirical correction factor.

  10. The quantum nature of the hydrogen bond: insight from path-integral molecular dynamics

    NASA Astrophysics Data System (ADS)

    Walker, Brent; Li, Xin-Zheng; Michaelides, Angelos

    2011-03-01

    Hydrogen (H) bonds are weak, generally intermolecular bonds, that hold together much of soft matter, the condensed phases of water, network liquids, and many ferroelectric crystals. The small mass of H means H-bonds are inherently quantum mechanical; effects such as zero point motion and tunneling should be considered, although often are not. In particular, a consistent picture of quantum nuclear effects on the strength of H-bonds and consequently the structure of H-bonded systems is still absent. Here, we report ab initio path-integral molecular dynamics studies on the quantum nature of the H-bond. Systematic examination of a range of H-bonded systems shows that quantum nuclei weaken weak H-bonds but strengthen relatively strong ones. This correlation arises from a competition between anharmonic intermolecular bond bending and intramolecular bond stretching. A simple rule of thumb enables predictions to be made for H-bonded bonded materials in general with merely classical knowledge (e.g. H-bond strength or H-bond length). Our work rationalizes the contrasting influence of quantum nuclear dynamics on a wide variety of materials, including liquid water and HF, and highlights the need for flexible molecules in force-field based studies of quantum nuclear dynamics.

  11. Dynamic force spectroscopy of parallel individual mucin1-antibody bonds

    SciTech Connect

    Sulchek, T A; Friddle, R W; Langry, K; Lau, E; Albrecht, H; Ratto, T; DeNardo, S; Colvin, M E; Noy, A

    2005-05-02

    We used atomic force microscopy (AFM) to measure the binding forces between Mucin1 (MUC1) peptide and a single chain antibody fragment (scFv) selected from a scFv library screened against MUC1. This binding interaction is central to the design of the molecules for targeted delivery of radioimmunotherapeutic agents for prostate and breast cancer treatment. Our experiments separated the specific binding interaction from non-specific interactions by tethering the antibody and MUC1 molecules to the AFM tip and sample surface with flexible polymer spacers. Rupture force magnitude and elastic characteristics of the spacers allowed identification of the bond rupture events corresponding to different number of interacting proteins. We used dynamic force spectroscopy to estimate the intermolecular potential widths and equivalent thermodynamic off rates for mono-, bi-, and tri-valent interactions. Measured interaction potential parameters agree with the results of molecular docking simulation. Our results demonstrate that an increase of the interaction valency leads to a precipitous decline in the dissociation rate. Binding forces measured for mono and multivalent interactions match the predictions of a Markovian model for the strength of multiple uncorrelated bonds in parallel configuration. Our approach is promising for comparison of the specific effects of molecular modifications as well as for determination of the best configuration of antibody-based multivalent targeting agents.

  12. Towards a unified description of the hydrogen bond network of liquid water: A dynamics based approach

    SciTech Connect

    Ozkanlar, Abdullah Zhou, Tiecheng; Clark, Aurora E.

    2014-12-07

    The definition of a hydrogen bond (H-bond) is intimately related to the topological and dynamic properties of the hydrogen bond network within liquid water. The development of a universal H-bond definition for water is an active area of research as it would remove many ambiguities in the network properties that derive from the fixed definition employed to assign whether a water dimer is hydrogen bonded. This work investigates the impact that an electronic-structure based definition, an energetic, and a geometric definition of the H-bond has upon both topological and dynamic network behavior of simulated water. In each definition, the use of a cutoff (either geometric or energetic) to assign the presence of a H-bond leads to the formation of transiently bonded or broken dimers, which have been quantified within the simulation data. The relative concentration of transient species, and their duration, results in two of the three definitions sharing similarities in either topological or dynamic features (H-bond distribution, H-bond lifetime, etc.), however no two definitions exhibit similar behavior for both classes of network properties. In fact, two networks with similar local network topology (as indicated by similar average H-bonds) can have dramatically different global network topology (as indicated by the defect state distributions) and altered H-bond lifetimes. A dynamics based correction scheme is then used to remove artificially transient H-bonds and to repair artificially broken bonds within the network such that the corrected network exhibits the same structural and dynamic properties for two H-bond definitions (the properties of the third definition being significantly improved). The algorithm described represents a significant step forward in the development of a unified hydrogen bond network whose properties are independent of the original hydrogen bond definition that is employed.

  13. Towards a unified description of the hydrogen bond network of liquid water: a dynamics based approach.

    PubMed

    Ozkanlar, Abdullah; Zhou, Tiecheng; Clark, Aurora E

    2014-12-07

    The definition of a hydrogen bond (H-bond) is intimately related to the topological and dynamic properties of the hydrogen bond network within liquid water. The development of a universal H-bond definition for water is an active area of research as it would remove many ambiguities in the network properties that derive from the fixed definition employed to assign whether a water dimer is hydrogen bonded. This work investigates the impact that an electronic-structure based definition, an energetic, and a geometric definition of the H-bond has upon both topological and dynamic network behavior of simulated water. In each definition, the use of a cutoff (either geometric or energetic) to assign the presence of a H-bond leads to the formation of transiently bonded or broken dimers, which have been quantified within the simulation data. The relative concentration of transient species, and their duration, results in two of the three definitions sharing similarities in either topological or dynamic features (H-bond distribution, H-bond lifetime, etc.), however no two definitions exhibit similar behavior for both classes of network properties. In fact, two networks with similar local network topology (as indicated by similar average H-bonds) can have dramatically different global network topology (as indicated by the defect state distributions) and altered H-bond lifetimes. A dynamics based correction scheme is then used to remove artificially transient H-bonds and to repair artificially broken bonds within the network such that the corrected network exhibits the same structural and dynamic properties for two H-bond definitions (the properties of the third definition being significantly improved). The algorithm described represents a significant step forward in the development of a unified hydrogen bond network whose properties are independent of the original hydrogen bond definition that is employed.

  14. Dynamic Characterization of Crystalline Supramolecular Rotors Assembled through Halogen Bonding.

    PubMed

    Catalano, Luca; Pérez-Estrada, Salvador; Terraneo, Giancarlo; Pilati, Tullio; Resnati, Giuseppe; Metrangolo, Pierangelo; Garcia-Garibay, Miguel A

    2015-12-16

    A modular molecular kit for the preparation of crystalline molecular rotors was devised from a set of stators and rotators to gain simple access to a large number of structures with different dynamic performance and physical properties. In this work, we have accomplished this with crystalline molecular rotors self-assembled by halogen bonding of diazabicyclo[2.2.2]octane, acting as a rotator, and a set of five fluorine-substituted iodobenzenes that take the role of the stator. Using variable-temperature (1)H T1 spin-lattice relaxation measurements, we have shown that all structures display ultrafast Brownian rotation with activation energies of 2.4-4.9 kcal/mol and pre-exponential factors of the order of (1-9) × 10(12) s(-1). Line shape analysis of quadrupolar echo (2)H NMR measurements in selected examples indicated rotational trajectories consistent with the 3-fold or 6-fold symmetric potential of the rotator.

  15. Reactive diffusion bonding of Si3N4 to MA6000

    NASA Astrophysics Data System (ADS)

    Kaysser, W. A.; Frisch, A.; Zhang, W.; Petzow, G.

    The procedure for joining Si3N4 to the MA6000 superalloy by diffusion bonding during HIP is described. Due to the large thermal mismatch between both components, it was necessary to introduce multiphase interlayers to allow relaxation of thermal stresses. Calculations of the stress development and the results of experiments showed that stress relaxation by thin soft interlayers in Si3N4/MA6000 is very limited: during bonding of Si3N4 to metals suitable as interlayers, brittle reaction products often form at the metal/ceramic interfaces. Experiments were then performed with iron-based alloys with small thermal expansion coefficients at low temperatures, combined with V, Nb, and Hf-based layers, and the reactions at the layer interfaces and the fracture surfaces were investigated by SEM, EDX, and WDX. It was found that, in systems with low deformability of the stiff reaction layers, stress relaxation by controlled microcrack formation reduced the interfacial damage and improved the mechanical stability of the joints.

  16. Lasing and thermal characteristics of Yb:YAG/YAG composite with atomic diffusion bonding

    NASA Astrophysics Data System (ADS)

    Sankar Nagisetty, Siva; Severova, Patricie; Miura, Taisuke; Smrž, Martin; Kon, Hitoe; Uomoto, Miyuki; Shimatsu, Takehito; Kawasaki, Masato; Higashiguchi, Takeshi; Endo, Akira; Mocek, Tomáš

    2017-01-01

    We demonstrated the laser performance of an Yb:YAG/YAG composite ceramic laser medium mounted on an aluminium heatsink via atomic diffusion bonding (ADB) technique using nanocrystalline metal films at room temperature in air. The surface temperature rise of the ADB bonded laser medium was linear with 57 °C lower than that of the commercially available soldered Yb:YAG thin disk at the pump power of 280 W. Moreover, the ADB disk was pumped 1.5 times higher (7.3 kW cm-2) than the typical damage threshold of the soldered disk without any sign of damage. The undoped capping may be effective for the suppression of ASE heating; however, according to the in situ OPD measurement it induces strong thermal lensing. The CW laser output power of 177 W was obtained at the pump power of 450 W with the optical-to-optical efficiency of 40% using V-shape cavity.

  17. FRET Fluctuation Spectroscopy of Diffusing Biopolymers: Contributions of Conformational Dynamics and Translational Diffusion

    PubMed Central

    Gurunathan, Kaushik; Levitus, Marcia

    2009-01-01

    The use of Fluorescence Correlation Spectroscopy (FCS) to study conformational dynamics in diffusing biopolymers requires that the contributions to the signal due to translational diffusion are separated from those due to conformational dynamics. A simple approach that has been proposed to achieve this goal involves the analysis of fluctuations in Fluorescence Resonance Energy Transfer (FRET) efficiency. In this work, we investigate the applicability of this methodology by combining Monte Carlo simulations and experiments. Results show that diffusion does not contribute to the measured fluctuations in FRET efficiency in conditions where the relaxation time of the kinetic process is much shorter than the mean transit time of the molecules in the optical observation volume. However, in contrast to what has been suggested in previous work, the contributions of diffusion are otherwise significant. Neglecting the contributions of diffusion can potentially lead to an erroneous interpretation of the kinetic mechanisms. As an example, we demonstrate that the analysis of FRET fluctuations in terms of a purely kinetic model would generally lead to the conclusion that the system presents complex kinetic behavior even for an idealized two-state system PMID:20030305

  18. Memristors with diffusive dynamics as synaptic emulators for neuromorphic computing

    NASA Astrophysics Data System (ADS)

    Wang, Zhongrui; Joshi, Saumil; Savel'Ev, Sergey E.; Jiang, Hao; Midya, Rivu; Lin, Peng; Hu, Miao; Ge, Ning; Strachan, John Paul; Li, Zhiyong; Wu, Qing; Barnell, Mark; Li, Geng-Lin; Xin, Huolin L.; Williams, R. Stanley; Xia, Qiangfei; Yang, J. Joshua

    2017-01-01

    The accumulation and extrusion of Ca2+ in the pre- and postsynaptic compartments play a critical role in initiating plastic changes in biological synapses. To emulate this fundamental process in electronic devices, we developed diffusive Ag-in-oxide memristors with a temporal response during and after stimulation similar to that of the synaptic Ca2+ dynamics. In situ high-resolution transmission electron microscopy and nanoparticle dynamics simulations both demonstrate that Ag atoms disperse under electrical bias and regroup spontaneously under zero bias because of interfacial energy minimization, closely resembling synaptic influx and extrusion of Ca2+, respectively. The diffusive memristor and its dynamics enable a direct emulation of both short- and long-term plasticity of biological synapses, representing an advance in hardware implementation of neuromorphic functionalities.

  19. Memristors with diffusive dynamics as synaptic emulators for neuromorphic computing

    SciTech Connect

    Wang, Zhongrui; Joshi, Saumil; Savel’ev, Sergey E.; Jiang, Hao; Midya, Rivu; Lin, Peng; Hu, Miao; Ge, Ning; Strachan, John Paul; Li, Zhiyong; Wu, Qing; Barnell, Mark; Li, Geng-Lin; Xin, Huolin L.; Williams, R. Stanley; Xia, Qiangfei; Yang, J. Joshua

    2016-09-26

    The accumulation and extrusion of Ca2+ in the pre- and postsynaptic compartments play a critical role in initiating plastic changes in biological synapses. In order to emulate this fundamental process in electronic devices, we developed diffusive Ag-in-oxide memristors with a temporal response during and after stimulation similar to that of the synaptic Ca2+ dynamics. In situ high-resolution transmission electron microscopy and nanoparticle dynamics simulations both demonstrate that Ag atoms disperse under electrical bias and regroup spontaneously under zero bias because of interfacial energy minimization, closely resembling synaptic influx and extrusion of Ca2+, respectively. Furthermore, the diffusive memristor and its dynamics enable a direct emulation of both short- and long-term plasticity of biological synapses, representing an advance in hardware implementation of neuromorphic functionalities.

  20. Memristors with diffusive dynamics as synaptic emulators for neuromorphic computing

    SciTech Connect

    Wang, Zhongrui; Joshi, Saumil; Savel’ev, Sergey E.; Jiang, Hao; Midya, Rivu; Lin, Peng; Hu, Miao; Ge, Ning; Strachan, John Paul; Li, Zhiyong; Wu, Qing; Barnell, Mark; Li, Geng-Lin; Xin, Huolin L.; Williams, R. Stanley; Xia, Qiangfei; Yang, J. Joshua

    2016-09-26

    The accumulation and extrusion of Ca2+ in the pre- and postsynaptic compartments play a critical role in initiating plastic changes in biological synapses. In order to emulate this fundamental process in electronic devices, we developed diffusive Ag-in-oxide memristors with a temporal response during and after stimulation similar to that of the synaptic Ca2+ dynamics. In situ high-resolution transmission electron microscopy and nanoparticle dynamics simulations both demonstrate that Ag atoms disperse under electrical bias and regroup spontaneously under zero bias because of interfacial energy minimization, closely resembling synaptic influx and extrusion of Ca2+, respectively. Furthermore, the diffusive memristor and its dynamics enable a direct emulation of both short- and long-term plasticity of biological synapses, representing an advance in hardware implementation of neuromorphic functionalities.

  1. Configurational Disorder of Water Hydrogen-Bond Network at the Protein Dynamical Transition.

    PubMed

    Rahaman, Obaidur; Kalimeri, Maria; Katava, Marina; Paciaroni, Alessandro; Sterpone, Fabio

    2017-07-20

    We introduce a novel strategy to quantify the disorder of extended water-water hydrogen-bond (HB) networks sampled in particle-based computer simulations. The method relies on the conformational clustering of the HB connectivity states. We successfully applied it to unveil the fine relationship among the protein dynamical transition in hydrated powder, which marks the activation of protein flexibility at Td ≈ 240 K, and the sudden increase in the configurational disorder of the water HB network enveloping the proteins. Our finding links, in the spirit of the Adam-Gibbs relationship, the diffusivity of protein atoms, as quantified by the hydrogen mean-square displacements, and the thermodynamic solvent configurational entropy.

  2. Decoupling of surface diffusion and relaxation dynamics of molecular glasses.

    PubMed

    Zhang, Yue; Fakhraai, Zahra

    2017-04-03

    Tobacco mosaic virus is used as a probe to measure surface diffusion of ultrathin films of N,N'-Bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD) (12 nm [Formula: see text] 53 nm, where [Formula: see text] is the film thickness) at various temperatures below the glass transition temperature, [Formula: see text], of all films. As the film thickness is decreased, [Formula: see text] decreases rapidly and the average film dynamics are enhanced by 6-14 orders of magnitude. We show that the surface diffusion is invariant of the film thickness decrease and the resulting enhanced overall mobility. The values of the surface diffusion coefficient and its temperature dependence are invariant of film thickness and are the same as the corresponding bulk values ([Formula: see text]400 nm). For the thinnest films ([Formula: see text]20 nm), the effective activation energy for rearrangement (temperature dependence of relaxation times) becomes smaller than the activation energy for surface diffusion. These results suggest that the fast surface diffusion is decoupled from film relaxation dynamics and is a solely free surface property.

  3. Molecular dynamics simulations of hydrogen diffusion in aluminum

    SciTech Connect

    Zhou, X. W.; El Gabaly, F.; Stavila, V.; Allendorf, M. D.

    2016-03-23

    In this study, hydrogen diffusion impacts the performance of solid-state hydrogen storage materials and contributes to the embrittlement of structural materials under hydrogen-containing environments. In atomistic simulations, the diffusion energy barriers are usually calculated using molecular statics simulations where a nudged elastic band method is used to constrain a path connecting the two end points of an atomic jump. This approach requires prior knowledge of the “end points”. For alloy and defective systems, the number of possible atomic jumps with respect to local atomic configurations is tremendous. Even when these jumps can be exhaustively studied, it is still unclear how they can be combined to give an overall diffusion behavior seen in experiments. Here we describe the use of molecular dynamics simulations to determine the overall diffusion energy barrier from the Arrhenius equation. This method does not require information about atomic jumps, and it has additional advantages, such as the ability to incorporate finite temperature effects and to determine the pre-exponential factor. As a test case for a generic method, we focus on hydrogen diffusion in bulk aluminum. We find that the challenge of this method is the statistical variation of the results. However, highly converged energy barriers can be achieved by an appropriate set of temperatures, output time intervals (for tracking hydrogen positions), and a long total simulation time. Our results help elucidate the inconsistencies of the experimental diffusion data published in the literature. The robust approach developed here may also open up future molecular dynamics simulations to rapidly study diffusion properties of complex material systems in multidimensional spaces involving composition and defects.

  4. Molecular dynamics simulations of hydrogen diffusion in aluminum

    DOE PAGES

    Zhou, X. W.; El Gabaly, F.; Stavila, V.; ...

    2016-03-23

    In this study, hydrogen diffusion impacts the performance of solid-state hydrogen storage materials and contributes to the embrittlement of structural materials under hydrogen-containing environments. In atomistic simulations, the diffusion energy barriers are usually calculated using molecular statics simulations where a nudged elastic band method is used to constrain a path connecting the two end points of an atomic jump. This approach requires prior knowledge of the “end points”. For alloy and defective systems, the number of possible atomic jumps with respect to local atomic configurations is tremendous. Even when these jumps can be exhaustively studied, it is still unclear howmore » they can be combined to give an overall diffusion behavior seen in experiments. Here we describe the use of molecular dynamics simulations to determine the overall diffusion energy barrier from the Arrhenius equation. This method does not require information about atomic jumps, and it has additional advantages, such as the ability to incorporate finite temperature effects and to determine the pre-exponential factor. As a test case for a generic method, we focus on hydrogen diffusion in bulk aluminum. We find that the challenge of this method is the statistical variation of the results. However, highly converged energy barriers can be achieved by an appropriate set of temperatures, output time intervals (for tracking hydrogen positions), and a long total simulation time. Our results help elucidate the inconsistencies of the experimental diffusion data published in the literature. The robust approach developed here may also open up future molecular dynamics simulations to rapidly study diffusion properties of complex material systems in multidimensional spaces involving composition and defects.« less

  5. Post-processing interstitialcy diffusion from molecular dynamics simulations

    SciTech Connect

    Bhardwaj, U.; Bukkuru, S.; Warrier, M.

    2016-01-15

    An algorithm to rigorously trace the interstitialcy diffusion trajectory in crystals is developed. The algorithm incorporates unsupervised learning and graph optimization which obviate the need to input extra domain specific information depending on crystal or temperature of the simulation. The algorithm is implemented in a flexible framework as a post-processor to molecular dynamics (MD) simulations. We describe in detail the reduction of interstitialcy diffusion into known computational problems of unsupervised clustering and graph optimization. We also discuss the steps, computational efficiency and key components of the algorithm. Using the algorithm, thermal interstitialcy diffusion from low to near-melting point temperatures is studied. We encapsulate the algorithms in a modular framework with functionality to calculate diffusion coefficients, migration energies and other trajectory properties. The study validates the algorithm by establishing the conformity of output parameters with experimental values and provides detailed insights for the interstitialcy diffusion mechanism. The algorithm along with the help of supporting visualizations and analysis gives convincing details and a new approach to quantifying diffusion jumps, jump-lengths, time between jumps and to identify interstitials from lattice atoms. -- Graphical abstract:.

  6. Diffusion Dynamics and Creative Destruction in a Simple Classical Model

    PubMed Central

    2015-01-01

    ABSTRACT The article explores the impact of the diffusion of new methods of production on output and employment growth and income distribution within a Classical one‐sector framework. Disequilibrium paths are studied analytically and in terms of simulations. Diffusion by differential growth affects aggregate dynamics through several channels. The analysis reveals the non‐steady nature of economic change and shows that the adaptation pattern depends both on the innovation's factor‐saving bias and on the extent of the bias, which determines the strength of the selection pressure on non‐innovators. The typology of different cases developed shows various aspects of Schumpeter's concept of creative destruction. PMID:27642192

  7. Dynamic covalent bond from first principles: Diarylbibenzofuranone structural, electronic, and oxidation studies.

    PubMed

    Schleder, Gabriel R; Fazzio, Adalberto; Arantes, Jeverson T

    2017-07-27

    A structure that can self-heal under standard conditions is a challenge faced nowadays and is one of the most promising areas in smart materials science. This can be achieved by dynamic bonds, of which diarylbibenzofuranone (DABBF) dynamic covalent bond is an appealing solution. In this report, we studied the DABBF bond formation against arylbenzofuranone (ABF) and O2 reaction (autoxidation). Our results show that the barrierless DABBF bond formation is preferred over autoxidation due to the charge transfer process that results in the weakly bonded superoxide. We calculated the electronic and structural properties using total energy density functional theory. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  8. Protonation Dynamics and Hydrogen Bonding in Aqueous Sulfuric Acid.

    PubMed

    Niskanen, Johannes; Sahle, Christoph J; Juurinen, Iina; Koskelo, Jaakko; Lehtola, Susi; Verbeni, Roberto; Müller, Harald; Hakala, Mikko; Huotari, Simo

    2015-09-03

    Hydration of sulfuric acid plays a key role in new-particle formation in the atmosphere. It has been recently proposed that proton dynamics is crucial in the stabilization of these clusters. One key question is how water molecules mediate proton transfer from sulfuric acid, and hence how the deprotonation state of the acid molecule behaves as a function concentration. We address the proton transfer in aqueous sulfuric acid with O K edge and S L edge core-excitation spectra recorded using inelastic X-ray scattering and with ab initio molecular dynamics simulations in the concentration range of 0-18.0 M. Throughout this range, we quantify the acid-water interaction with atomic resolution. Our simulations show that the number of donated hydrogen bonds per Owater increases from 1.9 to 2.5 when concentration increases from 0 to 18.0 M, in agreement with a rapid disappearance of the pre-edge feature in the O K edge spectrum. The simulations also suggest that for 1.5 M sulfuric acid SO4(2-) is most abundant and that its concentration falls monotonously with increasing concentration. Moreover, the fraction of HSO4(-) peaks at ∼12 M.

  9. Dynamic urea bond for the design of reversible and self-healing polymers.

    PubMed

    Ying, Hanze; Zhang, Yanfeng; Cheng, Jianjun

    2014-01-01

    Polymers bearing dynamic covalent bonds may exhibit dynamic properties, such as self-healing, shape memory and environmental adaptation. However, most dynamic covalent chemistries developed so far require either catalyst or change of environmental conditions to facilitate bond reversion and dynamic property change in bulk materials. Here we report the rational design of hindered urea bonds (urea with bulky substituent attached to its nitrogen) and the use of them to make polyureas and poly(urethane-urea)s capable of catalyst-free dynamic property change and autonomous repairing at low temperature. Given the simplicity of the hindered urea bond chemistry (reaction of a bulky amine with an isocyanate), incorporation of the catalyst-free dynamic covalent urea bonds to conventional polyurea or urea-containing polymers that typically have stable bulk properties may further broaden the scope of applications of these widely used materials.

  10. Dynamic urea bond for the design of reversible and self-healing polymers

    NASA Astrophysics Data System (ADS)

    Ying, Hanze; Zhang, Yanfeng; Cheng, Jianjun

    2014-02-01

    Polymers bearing dynamic covalent bonds may exhibit dynamic properties, such as self-healing, shape memory and environmental adaptation. However, most dynamic covalent chemistries developed so far require either catalyst or change of environmental conditions to facilitate bond reversion and dynamic property change in bulk materials. Here we report the rational design of hindered urea bonds (urea with bulky substituent attached to its nitrogen) and the use of them to make polyureas and poly(urethane-urea)s capable of catalyst-free dynamic property change and autonomous repairing at low temperature. Given the simplicity of the hindered urea bond chemistry (reaction of a bulky amine with an isocyanate), incorporation of the catalyst-free dynamic covalent urea bonds to conventional polyurea or urea-containing polymers that typically have stable bulk properties may further broaden the scope of applications of these widely used materials.

  11. Dynamic urea bond for the design of reversible and self-healing polymers

    PubMed Central

    Ying, Hanze; Zhang, Yanfeng; Cheng, Jianjun

    2014-01-01

    Polymers bearing dynamic covalent bonds may exhibit dynamic properties, such as self-healing, shape memory and environmental adaptation. However, most dynamic covalent chemistries developed so far require either catalyst or change of environmental conditions to facilitate bond reversion and dynamic property change in bulk materials. Here we report the rational design of hindered urea bonds (urea with bulky substituent attached to its nitrogen) and the use of them to make polyureas and poly(urethane-ureas) capable of catalyst-free dynamic property change and autonomous repairing at low temperature. Given the simplicity of the hindered urea bond chemistry (reaction of a bulky amine with an isocyanate), incorporation of the catalyst-free dynamic covalent urea bonds to conventional polyurea or urea-containing polymers that typically have stable bulk properties may further broaden the scope of applications of these widely used materials. PMID:24492620

  12. Low cycle fatigue strength of diffusion bonded joints of alumina dispersion-strengthened copper to stainless steel

    NASA Astrophysics Data System (ADS)

    Nishi, H.; Araki, T.

    2000-12-01

    It is proposed that the first wall and divertor components of ITER employ alumina dispersion-strengthened copper (DS Cu) joined to austenitic stainless steel. In this work, low cycle fatigue tests were performed on a direct diffusion bonded joint, a diffusion bonded joint with a Au interlayer, stainless steel and DS Cu in order to investigate their fatigue strength and fracture behavior. For the direct diffusion bonded joint, the fatigue strength in the small strain range was considerably lower than that of the DS Cu, while in the large strain range the fatigue strength was similar to that of the DS Cu. The low cycle fatigue strength of the Au interlayer joint increased compared with the direct diffusion bonded joint, and was the same as that of the DS Cu. The strain distribution in joint specimens was not uniform, because the deformation stress was different between the 316 stainless steel and the DS Cu. The fracture locations for the joint specimens varied depending on their strain distribution.

  13. Slow diffusive dynamics in a chaotic balanced neural network.

    PubMed

    Shaham, Nimrod; Burak, Yoram

    2017-05-01

    It has been proposed that neural noise in the cortex arises from chaotic dynamics in the balanced state: in this model of cortical dynamics, the excitatory and inhibitory inputs to each neuron approximately cancel, and activity is driven by fluctuations of the synaptic inputs around their mean. It remains unclear whether neural networks in the balanced state can perform tasks that are highly sensitive to noise, such as storage of continuous parameters in working memory, while also accounting for the irregular behavior of single neurons. Here we show that continuous parameter working memory can be maintained in the balanced state, in a neural circuit with a simple network architecture. We show analytically that in the limit of an infinite network, the dynamics generated by this architecture are characterized by a continuous set of steady balanced states, allowing for the indefinite storage of a continuous parameter. In finite networks, we show that the chaotic noise drives diffusive motion along the approximate attractor, which gradually degrades the stored memory. We analyze the dynamics and show that the slow diffusive motion induces slowly decaying temporal cross correlations in the activity, which differ substantially from those previously described in the balanced state. We calculate the diffusivity, and show that it is inversely proportional to the system size. For large enough (but realistic) neural population sizes, and with suitable tuning of the network connections, the proposed balanced network can sustain continuous parameter values in memory over time scales larger by several orders of magnitude than the single neuron time scale.

  14. Molecular dynamics evaluation of self-diffusion in Yukawa systems

    NASA Astrophysics Data System (ADS)

    Ohta, H.; Hamaguchi, S.

    2000-11-01

    Self-diffusion coefficients of Yukawa systems in the fluid phase are obtained from molecular dynamics simulations in a wide range of the thermodynamical parameters. The Yukawa system is a collection of particles interacting through Yukawa (i.e., screened Coulomb) potentials, which may serve as a model for charged dust particles in a plasma or colloidal particles in electrolytes. The self-diffusion coefficients are found to follow a simple scaling law with respect to the system temperature, which is consistent with the universal scaling (i.e., temperature scaling independent of the ratio of interparticle distance to screening length) observed by Robbins et al. [J. Chem. Phys. 88, 3286 (1988)] if the fluid system is near solidification. Also discussed is the velocity autocorrelation function, which is in part used to determine the self-diffusion coefficients through the Green-Kubo formula.

  15. Pattern dynamics and optimization by reaction diffusion systems

    SciTech Connect

    Ebeling, W.

    1986-12-01

    Reaction-diffusion systems show a fast and rather complex response on patterns produced by external space- and/or time-dependent perturbations. For example, one-component autocatalytic reactions rapidly find the loci where the given space-dependent reaction rates have relatively high values by following a kind of Darwinian strategy (combining self-reproduction and diffusion). It is shown that a simulation of this strategy in combination with annealing (decreasing the diffusion rates in time) may be used as an alternative to thermodynamic annealing strategies. Many-component reactions, such as the light-sensitive Belousov-Zhabotinsky reaction, show a more complex response to patterns impressed by illumination, for example. The response behavior and possible applications to dynamic information processing are discussed.

  16. Single-file dynamics with different diffusion constants.

    PubMed

    Ambjörnsson, Tobias; Lizana, Ludvig; Lomholt, Michael A; Silbey, Robert J

    2008-11-14

    We investigate the single-file dynamics of a tagged particle in a system consisting of N hardcore interacting particles (the particles cannot pass each other) which are diffusing in a one-dimensional system where the particles have different diffusion constants. For the two-particle case an exact result for the conditional probability density function (PDF) is obtained for arbitrary initial particle positions and all times. The two-particle PDF is used to obtain the tagged particle PDF. For the general N-particle case (N large) we perform stochastic simulations using our new computationally efficient stochastic simulation technique based on the Gillespie algorithm. We find that the mean square displacement for a tagged particle scales as the square root of time (as for identical particles) for long times, with a prefactor which depends on the diffusion constants for the particles; these results are in excellent agreement with very recent analytic predictions in the mathematics literature.

  17. Intramolecular Hydrogen Bonding Restricts Gd-Aqua-Ligand Dynamics [The Day the Water Stood Still: Intramolecular Hydrogen Bonding to Restrict Gd-Aqua Ligand Dynamics

    DOE PAGES

    Boros, Eszter; Srinivas, Raja; Kim, Hee -Kyung; ...

    2017-04-11

    Aqua ligands can undergo rapid internal rotation about the M-O bond. For magnetic resonance contrast agents, this rotation results in diminished relaxivity. Herein, we show that an intramolecular hydrogen bond to the aqua ligand can reduce this internal rotation and increase relaxivity. Molecular modeling was used to design a series of four Gd complexes capable of forming an intramolecular H-bond to the coordinated water ligand, and these complexes had anomalously high relaxivities compared to similar complexes lacking a H-bond acceptor. Molecular dynamics simulations supported the formation of a stable intramolecular H-bond, while alternative hypotheses that could explain the higher relaxivitymore » were systematically ruled out. Finally, intramolecular H-bonding represents a useful strategy to limit internal water rotational motion and increase relaxivity of Gd complexes.« less

  18. Diffuse Reflectance Infrared Spectroscopic Identification of Dispersant/Particle Bonding Mechanisms in Functional Inks

    PubMed Central

    Deiner, L. Jay; Farjami, Elaheh

    2015-01-01

    In additive manufacturing, or 3D printing, material is deposited drop by drop, to create micron to macroscale layers. A typical inkjet ink is a colloidal dispersion containing approximately ten components including solvent, the nano to micron scale particles which will comprise the printed layer, polymeric dispersants to stabilize the particles, and polymers to tune layer strength, surface tension and viscosity. To rationally and efficiently formulate such an ink, it is crucial to know how the components interact. Specifically, which polymers bond to the particle surfaces and how are they attached? Answering this question requires an experimental procedure that discriminates between polymer adsorbed on the particles and free polymer. Further, the method must provide details about how the functional groups of the polymer interact with the particle. In this protocol, we show how to employ centrifugation to separate particles with adsorbed polymer from the rest of the ink, prepare the separated samples for spectroscopic measurement, and use Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS) for accurate determination of dispersant/particle bonding mechanisms. A significant advantage of this methodology is that it provides high level mechanistic detail using only simple, commonly available laboratory equipment. This makes crucial data available to almost any formulation laboratory. The method is most useful for inks composed of metal, ceramic, and metal oxide particles in the range of 100 nm or greater. Because of the density and particle size of these inks, they are readily separable with centrifugation. Further, the spectroscopic signatures of such particles are easy to distinguish from absorbed polymer. The primary limitation of this technique is that the spectroscopy is performed ex-situ on the separated and dried particles as opposed to the particles in dispersion. However, results from attenuated total reflectance spectra of the wet separated

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

    SciTech Connect

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

    1999-07-01

    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 4 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.

  20. Memristors with diffusive dynamics as synaptic emulators for neuromorphic computing

    DOE PAGES

    Wang, Zhongrui; Joshi, Saumil; Savel’ev, Sergey E.; ...

    2016-09-26

    The accumulation and extrusion of Ca2+ in the pre- and postsynaptic compartments play a critical role in initiating plastic changes in biological synapses. In order to emulate this fundamental process in electronic devices, we developed diffusive Ag-in-oxide memristors with a temporal response during and after stimulation similar to that of the synaptic Ca2+ dynamics. In situ high-resolution transmission electron microscopy and nanoparticle dynamics simulations both demonstrate that Ag atoms disperse under electrical bias and regroup spontaneously under zero bias because of interfacial energy minimization, closely resembling synaptic influx and extrusion of Ca2+, respectively. Furthermore, the diffusive memristor and its dynamicsmore » enable a direct emulation of both short- and long-term plasticity of biological synapses, representing an advance in hardware implementation of neuromorphic functionalities.« less

  1. Untangling Knots Via Reaction-Diffusion Dynamics of Vortex Strings

    NASA Astrophysics Data System (ADS)

    Maucher, Fabian; Sutcliffe, Paul

    2016-04-01

    We introduce and illustrate a new approach to the unknotting problem via the dynamics of vortex strings in a nonlinear partial differential equation of reaction-diffusion type. To untangle a given knot, a Biot-Savart construction is used to initialize the knot as a vortex string in the FitzHugh-Nagumo equation. Remarkably, we find that the subsequent evolution preserves the topology of the knot and can untangle an unknot into a circle. Illustrative test case examples are presented, including the untangling of a hard unknot known as the culprit. Our approach to the unknotting problem has two novel features, in that it applies field theory rather than particle mechanics and uses reaction-diffusion dynamics in place of energy minimization.

  2. Mesoscopic dynamics of diffusion-influenced enzyme kinetics

    NASA Astrophysics Data System (ADS)

    Chen, Jiang-Xing; Kapral, Raymond

    2011-01-01

    A particle-based mesoscopic model for enzyme kinetics is constructed and used to investigate the influence of diffusion on the reactive dynamics. Enzymes and enzyme-substrate complexes are modeled as finite-size soft spherical particles, while substrate, product, and solvent molecules are point particles. The system is evolved using a hybrid molecular dynamics-multiparticle collision dynamics scheme. Both the nonreactive and reactive dynamics are constructed to satisfy mass, momentum, and energy conservation laws, and reversible reaction steps satisfy detailed balance. Hydrodynamic interactions among the enzymes and complexes are automatically accounted for in the dynamics. Diffusion manifests itself in various ways, notably in power-law behavior in the evolution of the species concentrations. In accord with earlier investigations, regimes where the product production rate exhibits either monotonic or nonmonotonic behavior as a function of time are found. In addition, the species concentrations display both t^{-1/2} and t^{-3/2} power-law behavior, depending on the dynamical regime under investigation. For high enzyme volume fractions, cooperative effects influence the enzyme kinetics. The time dependent rate coefficient determined from the mass action rate law is computed and shown to depend on the enzyme concentration. Lifetime distributions of substrate molecules newly released in complex dissociation events are determined and shown to have either a power-law form for rebinding to the same enzyme from which they were released or an exponential form for rebinding to different enzymes. The model can be used and extended to explore a variety of issues related concentration effects and diffusion on enzyme kinetics.

  3. Mesoscopic dynamics of diffusion-influenced enzyme kinetics.

    PubMed

    Chen, Jiang-Xing; Kapral, Raymond

    2011-01-28

    A particle-based mesoscopic model for enzyme kinetics is constructed and used to investigate the influence of diffusion on the reactive dynamics. Enzymes and enzyme-substrate complexes are modeled as finite-size soft spherical particles, while substrate, product, and solvent molecules are point particles. The system is evolved using a hybrid molecular dynamics-multiparticle collision dynamics scheme. Both the nonreactive and reactive dynamics are constructed to satisfy mass, momentum, and energy conservation laws, and reversible reaction steps satisfy detailed balance. Hydrodynamic interactions among the enzymes and complexes are automatically accounted for in the dynamics. Diffusion manifests itself in various ways, notably in power-law behavior in the evolution of the species concentrations. In accord with earlier investigations, regimes where the product production rate exhibits either monotonic or nonmonotonic behavior as a function of time are found. In addition, the species concentrations display both t(-1/2) and t(-3/2) power-law behavior, depending on the dynamical regime under investigation. For high enzyme volume fractions, cooperative effects influence the enzyme kinetics. The time dependent rate coefficient determined from the mass action rate law is computed and shown to depend on the enzyme concentration. Lifetime distributions of substrate molecules newly released in complex dissociation events are determined and shown to have either a power-law form for rebinding to the same enzyme from which they were released or an exponential form for rebinding to different enzymes. The model can be used and extended to explore a variety of issues related concentration effects and diffusion on enzyme kinetics.

  4. Spatiotemporal mapping of diffusion dynamics and organization in plasma membranes

    NASA Astrophysics Data System (ADS)

    Bag, Nirmalya; Ng, Xue Wen; Sankaran, Jagadish; Wohland, Thorsten

    2016-09-01

    Imaging fluorescence correlation spectroscopy (FCS) and the related FCS diffusion law have been applied in recent years to investigate the diffusion modes of lipids and proteins in membranes. These efforts have provided new insights into the membrane structure below the optical diffraction limit, new information on the existence of lipid domains, and on the influence of the cytoskeleton on membrane dynamics. However, there has been no systematic study to evaluate how domain size, domain density, and the probe partition coefficient affect the resulting imaging FCS diffusion law parameters. Here, we characterize the effects of these factors on the FCS diffusion law through simulations and experiments on lipid bilayers and live cells. By segmenting images into smaller 7  ×  7 pixel areas, we can evaluate the FCS diffusion law on areas smaller than 2 µm and thus provide detailed maps of information on the membrane structure and heterogeneity at this length scale. We support and extend this analysis by deriving a mathematical expression to calculate the mean squared displacement (MSDACF) from the autocorrelation function of imaging FCS, and demonstrate that the MSDACF plots depend on the existence of nanoscopic domains. Based on the results, we derive limits for the detection of domains depending on their size, density, and relative viscosity in comparison to the surroundings. Finally, we apply these measurements to bilayers and live cells using imaging total internal reflection FCS and single plane illumination microscopy FCS.

  5. Spatiotemporal mapping of diffusion dynamics and organization in plasma membranes.

    PubMed

    Bag, Nirmalya; Ng, Xue Wen; Sankaran, Jagadish; Wohland, Thorsten

    2016-07-26

    Imaging fluorescence correlation spectroscopy (FCS) and the related FCS diffusion law have been applied in recent years to investigate the diffusion modes of lipids and proteins in membranes. These efforts have provided new insights into the membrane structure below the optical diffraction limit, new information on the existence of lipid domains, and on the influence of the cytoskeleton on membrane dynamics. However, there has been no systematic study to evaluate how domain size, domain density, and the probe partition coefficient affect the resulting imaging FCS diffusion law parameters. Here, we characterize the effects of these factors on the FCS diffusion law through simulations and experiments on lipid bilayers and live cells. By segmenting images into smaller 7  ×  7 pixel areas, we can evaluate the FCS diffusion law on areas smaller than 2 µm and thus provide detailed maps of information on the membrane structure and heterogeneity at this length scale. We support and extend this analysis by deriving a mathematical expression to calculate the mean squared displacement (MSDACF) from the autocorrelation function of imaging FCS, and demonstrate that the MSDACF plots depend on the existence of nanoscopic domains. Based on the results, we derive limits for the detection of domains depending on their size, density, and relative viscosity in comparison to the surroundings. Finally, we apply these measurements to bilayers and live cells using imaging total internal reflection FCS and single plane illumination microscopy FCS.

  6. Sodium diffusion through amorphous silica surfaces: a molecular dynamics study.

    PubMed

    Rarivomanantsoa, Michaël; Jund, Philippe; Jullien, Rémi

    2004-03-08

    We have studied the diffusion inside the silica network of sodium atoms initially located outside the surfaces of an amorphous silica film. We have focused our attention on structural and dynamical quantities, and we have found that the local environment of the sodium atoms is close to the local environment of the sodium atoms inside bulk sodo-silicate glasses obtained by quench. This is in agreement with recent experimental results.

  7. Dynamics of Robertson–Walker spacetimes with diffusion

    SciTech Connect

    Alho, A.; Calogero, S.; Machado Ramos, M.P.; Soares, A.J.

    2015-03-15

    We study the dynamics of spatially homogeneous and isotropic spacetimes containing a fluid undergoing microscopic velocity diffusion in a cosmological scalar field. After deriving a few exact solutions of the equations, we continue by analyzing the qualitative behavior of general solutions. To this purpose we recast the equations in the form of a two dimensional dynamical system and perform a global analysis of the flow. Among the admissible behaviors, we find solutions that are asymptotically de-Sitter both in the past and future time directions and which undergo accelerated expansion at all times.

  8. Collective sub-diffusive dynamics in bacterial carpet microfluidic channel

    NASA Astrophysics Data System (ADS)

    Hsiao, Yi-Teng; Wang, Jing-Hui; Hsu, Yi-Chun; Chiu, Chien-Chun; Lo, Chien-Jung; Tsao, Chia-Wen; Yen Woon, Wei

    2012-05-01

    We experimentally investigate the collective dynamics in bacterial carpet microfluidic channel. The microfluidic channel is composed of single polar flagellated Vibrio alginolyticus deposited glass substrates. The individual flagellum swimming speed is tuned by varying buffer sodium concentration. Hydrodynamic coupling strength is tuned by varying buffer viscosity. The attached bacteria constantly perform two major modes in flagellum motion, namely, the local rotation and large angle flick. Particle tracking statistics shows high flagellum rotational rate and strong hydrodynamic coupling strength lead to collective sub-diffusive dynamics. The observed effect is strongly correlated to hydrodynamic coupling of flick motions between nearby bacteria.

  9. A Dynamic Pathway for Stone-Wales Bond Rotation on Carbon Nanotubes through Diamond-Like Bonds

    NASA Technical Reports Server (NTRS)

    Wei, Chen-Yu; Srivastava, Deepak; Cho, Kyeong-Jae; Menon, Madhu

    2003-01-01

    A new lower energy barrier with a two-step pathway of Stone-Wales (SW) ,ond rotation on carbon nanotubes (CNTs) is found through molecular dynamics (MD) simulations of CNTs under tension. The first step involves going over to a stable sp3-like metastable configuration with half rotated and partially tilted C-C bond. The second step involves going over to the fully rotated C-C bond with the formation of a SW defect in the nanotube. The energy barrier for this two-step dynamic pathway is significantly lower than the previously known static barrier for in-plane rotation of the C-C bond on a tensile strained (> 4%) CNT.

  10. Convection-diffusion effects in marathon race dynamics

    NASA Astrophysics Data System (ADS)

    Rodriguez, E.; Espinosa-Paredes, G.; Alvarez-Ramirez, J.

    2014-01-01

    In the face of the recent terrorist attack event on the 2013 Boston Marathon, the increasing participation of recreational runners in large marathon races has imposed important logistical and safety issues for organizers and city authorities. An accurate understanding of the dynamics of the marathon pack along the race course can provide important insights for improving safety and performance of these events. On the other hand, marathon races can be seen as a model of pedestrian movement under confined conditions. This work used data of the 2011 Chicago Marathon event for modeling the dynamics of the marathon pack from the corral zone to the finish line. By considering the marathon pack as a set of particles moving along the race course, the dynamics are modeled as a convection-diffusion partial differential equation with position-dependent mean velocity and diffusion coefficient. A least-squares problem is posed and solved with optimization techniques for fitting field data from the 2011 Chicago Marathon. It was obtained that the mean pack velocity decreases while the diffusion coefficient increases with distance. This means that the dispersion rate of the initially compact marathon pack increases as the marathon race evolves along the race course.

  11. Method for producing components with internal architectures, such as micro-channel reactors, via diffusion bonding sheets

    DOEpatents

    Alman, David E.; Wilson, Rick D.; Davis, Daniel L.

    2011-03-08

    This invention relates to a method for producing components with internal architectures, and more particularly, this invention relates to a method for producing structures with microchannels via the use of diffusion bonding of stacked laminates. Specifically, the method involves weakly bonding a stack of laminates forming internal voids and channels with a first generally low uniaxial pressure and first temperature such that bonding at least between the asperites of opposing laminates occurs and pores are isolated in interfacial contact areas, followed by a second generally higher isostatic pressure and second temperature for final bonding. The method thereby allows fabrication of micro-channel devices such as heat exchangers, recuperators, heat-pumps, chemical separators, chemical reactors, fuel processing units, and combustors without limitation on the fin aspect ratio.

  12. 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.

  13. Evaluation of Cu as an interlayer in Be/F82H diffusion bonds for ITER TBM

    NASA Astrophysics Data System (ADS)

    Hunt, R. M.; Goods, S. H.; Ying, A.; Dorn, C. K.; Abdou, M.

    2011-10-01

    Copper has been investigated as a potential interlayer material for diffusion bonds between beryllium and Reduced Activation Ferritic/Martensitic (RAFM) steel. Utilizing Hot Isostatic Pressing (HIP), copper was directly bonded to a RAFM steel, F82H, at 650 °C, 700 °C, 750 °C, 800 °C and 850 °C, under 103 MPa for 2 h. Interdiffusion across the bonded interface was limited to 1 μm or less, even at the highest HIP'ing temperature. Through mechanical testing it was found that samples HIP'ed at 750 °C and above remain bonded up to 211 MPa under tensile loading, at which point ductile failure occurred in the bulk copper. As titanium will be used as a barrier layer to prevent the formation of brittle Be/Cu intermetallics, additional annealing studies were performed on copper samples coated with a titanium thin film to study Ti/Cu interdiffusion characteristics. Samples were heated to temperatures between 650 °C and 850 °C for 2 h in order to mimic the range of likely HIP temperatures. A correlation was drawn between HIP temperature and diffusion depth for use in determining the minimum Ti film thickness necessary to block diffusion in the Be/F82H joint.

  14. Coupling between inter-helical hydrogen bonding and water dynamics in a proton transporter.

    PubMed

    del Val, Coral; Bondar, Luiza; Bondar, Ana-Nicoleta

    2014-04-01

    Long-distance proton transfers by proton pumps occurs in discrete steps that may involve the direct participation of protein sidechains and water molecules, and coupling of protonation changes to structural rearrangements of the protein matrix. Here we explore the role of inter-helical hydrogen bonding in long-distance protein conformational coupling and dynamics of internal water molecules. From molecular dynamics simulations of wild type and nine different bacteriorhodopsin mutants we find that both intra- and inter-helical hydrogen bonds are important determinants of the local protein structure, dynamics, and water interactions. Based on molecular dynamics and bioinformatics analyses, we identify an aspartate/threonine inter-helical hydrogen-bonding motif involved in controlling the local conformational dynamics. Perturbation of inter-helical hydrogen bonds can couple to rapid changes in water dynamics.

  15. Brownian Dynamics Simulation of Macromolecule Diffusion in a Protocell

    NASA Astrophysics Data System (ADS)

    Ando, Tadashi; Skolnick, Jeffrey

    2011-01-01

    The interiors of all living cells are highly crowded with macro molecules, which differs considerably the thermodynamics and kinetics of biological reactions between in vivo and in vitro. For example, the diffusion of green fluorescent protein (GFP) in E. coli is ~10-fold slower than in dilute conditions. In this study, we performed Brownian dynamics (BD) simulations of rigid macromolecules in a crowded environment mimicking the cytosol of E. coli to study the motions of macromolecules. The simulation systems contained 35 70S ribosomes, 750 glycolytic enzymes, 75 GFPs, and 392 tRNAs in a 100 nm × 100 nm × 100 nm simulation box, where the macromolecules were represented by rigid-objects of one bead per amino acid or four beads per nucleotide models. Diffusion tensors of these molecules in dilute solutions were estimated by using a hydrodynamic theory to take into account the diffusion anisotropy of arbitrary shaped objects in the BD simulations. BD simulations of the system where each macromolecule is represented by its Stokes radius were also performed for comparison. Excluded volume effects greatly reduce the mobility of molecules in crowded environments for both molecular-shaped and equivalent sphere systems. Additionally, there were no significant differences in the reduction of diffusivity over the entire range of molecular size between two systems. However, the reduction in diffusion of GFP in these systems was still 4-5 times larger than for the in vivo experiment. We will discuss other plausible factors that might cause the large reduction in diffusion in vivo.

  16. Effects of interface bonding and defects on boron diffusion at Si/SiO{sub 2} interface

    SciTech Connect

    Kim, Geun-Myeong; Oh, Young Jun; Chang, K. J.

    2013-12-14

    We perform first-principles density functional calculations to find the migration pathway and barrier for B diffusion at the Si/SiO{sub 2} interface. For various interface models, in which crystalline α-quartz or amorphous silica (a-SiO{sub 2}) is placed on Si, we examine stable and metastable configurations of B-related defects which play a role in B diffusion. While a substitutional B alone is immobile in Si, it tends to diffuse to the interface via an interstitialcy mechanism in the presence of a self-interstitial and then changes into an interstitial B in oxide via a kick-out mechanism, leaving the self-interstitial at the interface. At the defect-free interface, where bridging O atoms are inserted to remove interface dangling bonds, an interstitial B prefers to intervene between the interface Si and bridging O atoms and subsequently diffuses through the hollow space or along the network of the Si-O-Si bonds in oxide. The overall migration barriers are calculated to be 2.02–2.12 eV at the Si/α-quartz interface, while they lie in the range of 2.04 ± 0.44 eV at the Si/a-SiO{sub 2} interface, similar to that in α-quartz. The migration pathway and barrier are not significantly affected by interface defects such as suboxide bond and O protrusion, while dangling bonds in the suboxide region can increase the migration barrier by about 1.5 eV. The result that the interface generally does not hinder the B diffusion from Si to SiO{sub 2} assists in understanding the underlying mechanism for B segregation which commonly occurs at the Si/SiO{sub 2} interface.

  17. An investigation on microstructure evolution and mechanical properties during liquid state diffusion bonding of Al2024 to Ti–6Al–4V

    SciTech Connect

    Samavatian, Majid; Halvaee, Ayoub; Amadeh, Ahmad Ali; Khodabandeh, Alireza

    2014-12-15

    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 process 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.

  18. Molecular dynamics simulation of water at mineral surfaces: Structure, dynamics, energetics and hydrogen bonding

    NASA Astrophysics Data System (ADS)

    Kalinichev, A. G.; Wang, J.; Kirkpatrick, R.

    2006-05-01

    Fundamental molecular-level understanding of the properties of aqueous mineral interfaces is of great importance for many geochemical and environmental systems. Interaction between water and mineral surfaces substantially affects the properties of both phases, including the reactivity and functionality of the substrate surface, and the structure, dynamics, and energetics of the near surface aqueous phase. Experimental studies of interfacial water structure and dynamics using surface-sensitive techniques such as sum-frequency vibrational spectroscopy or X-ray and neutron reflectivity are not always possible for many practically important substrates, and their results often require interpretation concerning the atomistic mechanisms responsible for the observed behavior. Molecular computer simulations can provide new insight into the underlying molecular- level relationships between the inorganic substrate structure and composition and the structure, ordering, and dynamics of interfacial water. We have performed a series of molecular dynamics (MD) computer simulations of aqueous interfaces with several silicates (quartz, muscovite, and talc) and hydroxides (brucite, portlandite, gibbsite, Ca/Al and Mg/Al double hydroxides) to quantify the effects of the substrate mineral structure and composition on the structural, transport, and thermodynamic properties of water on these mineral surfaces. Due to the prevalent effects of the development of well-interconnected H-bonding networks across the mineral- water interfaces, all the hydroxide surfaces (including a fully hydroxylated quartz surface) show very similar H2O density profiles perpendicular to the interface. However, the predominant orientations of the interfacial H2O molecules and their detailed 2-dimensional near-surface structure and dynamics parallel to the interface are quite different reflecting the differences in the substrate structural charge distribution and the density and orientations of the surface OH

  19. A new dynamic covalent bond of Se-N: towards controlled self-assembly and disassembly.

    PubMed

    Yi, Yu; Xu, Huaping; Wang, Lu; Cao, Wei; Zhang, Xi

    2013-07-15

    A new kind of Se-N dynamic covalent bond has been found that can form between the Se atom of a phenylselenyl halogen species and the N atom of a pyridine derivative, such as polystyrene-b-poly(4-vinylpyridine). This Se-N dynamic covalent bond can be reversibly and rapidly formed or cleaved under acidic or basic conditions, respectively. Furthermore, the bond can be dynamically cleaved by heating or treatment with stronger electron-donating pyridine derivatives. The multiple responses of Se-N bond to external stimuli has enriched the existing family of dynamic covalent bonds. It can be used for controlled and reversible self-assembly and disassembly, which may find potential applications in a number of areas, including self-healing materials and responsive assemblies. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Reaction Diffusion Modeling of Calcium Dynamics with Realistic ER Geometry

    PubMed Central

    Means, Shawn; Smith, Alexander J.; Shepherd, Jason; Shadid, John; Fowler, John; Wojcikiewicz, Richard J. H.; Mazel, Tomas; Smith, Gregory D.; Wilson, Bridget S.

    2006-01-01

    We describe a finite-element model of mast cell calcium dynamics that incorporates the endoplasmic reticulum's complex geometry. The model is built upon a three-dimensional reconstruction of the endoplasmic reticulum (ER) from an electron tomographic tilt series. Tetrahedral meshes provide volumetric representations of the ER lumen, ER membrane, cytoplasm, and plasma membrane. The reaction-diffusion model simultaneously tracks changes in cytoplasmic and ER intraluminal calcium concentrations and includes luminal and cytoplasmic protein buffers. Transport fluxes via PMCA, SERCA, ER leakage, and Type II IP3 receptors are also represented. Unique features of the model include stochastic behavior of IP3 receptor calcium channels and comparisons of channel open times when diffusely distributed or aggregated in clusters on the ER surface. Simulations show that IP3R channels in close proximity modulate activity of their neighbors through local Ca2+ feedback effects. Cytoplasmic calcium levels rise higher, and ER luminal calcium concentrations drop lower, after IP3-mediated release from receptors in the diffuse configuration. Simulation results also suggest that the buffering capacity of the ER, and not restricted diffusion, is the predominant factor influencing average luminal calcium concentrations. PMID:16617072

  1. Spatial dynamics of a population with stage-dependent diffusion

    NASA Astrophysics Data System (ADS)

    Azevedo, F.; Coutinho, R. M.; Kraenkel, R. A.

    2015-05-01

    We explore the spatial dynamics of a population whose individuals go through life stages with very different dispersal capacities. We model it through a system of partial differential equations of the reaction-diffusion kind, with nonlinear diffusion terms that may depend on population density and on the stage. This model includes a few key biological ingredients: growth and saturation, life stage structure, small population effects, and diffusion dependent on the stage. In particular, we consider that adults exhibit two distinct classes: one highly mobile and the other less mobile but with higher fecundity rate, and the development of juveniles into one or the other depends on population density. We parametrize the model with estimated parameters of an insect species, the brown planthopper. We focus on a situation akin to an invasion of the species in a new habitat and find that the front of invasion is led by the most mobile adult class. We also show that the trade-off between dispersal and fecundity leads to invasion speed attaining its maximum at an intermediate value of the diffusion coefficient of the most mobile class.

  2. Diffusion in liquid Germanium using ab initio molecular dynamics

    NASA Astrophysics Data System (ADS)

    Kulkarni, R. V.; Aulbur, W. G.; Stroud, D.

    1996-03-01

    We describe the results of calculations of the self-diffusion constant of liquid Ge over a range of temperatures. The calculations are carried out using an ab initio molecular dynamics scheme which combines an LDA model for the electronic structure with the Bachelet-Hamann-Schlüter norm-conserving pseudopotentials^1. The energies associated with electronic degrees of freedom are minimized using the Williams-Soler algorithm, and ionic moves are carried out using the Verlet algorithm. We use an energy cutoff of 10 Ry, which is sufficient to give results for the lattice constant and bulk modulus of crystalline Ge to within 1% and 12% of experiment. The program output includes not only the self-diffusion constant but also the structure factor, electronic density of states, and low-frequency electrical conductivity. We will compare our results with other ab initio and semi-empirical calculations, and discuss extension to impurity diffusion. ^1 We use the ab initio molecular dynamics code fhi94md, developed at 1cm the Fritz-Haber Institute, Berlin. ^2 Work supported by NASA, Grant NAG3-1437.

  3. Dynamic cross-correlations between entangled biofilaments as they diffuse

    PubMed Central

    Tsang, Boyce; Dell, Zachary E.; Jiang, Lingxiang; Schweizer, Kenneth S.; Granick, Steve

    2017-01-01

    Entanglement in polymer and biological physics involves a state in which linear interthreaded macromolecules in isotropic liquids diffuse in a spatially anisotropic manner beyond a characteristic mesoscopic time and length scale (tube diameter). The physical reason is that linear macromolecules become transiently localized in directions transverse to their backbone but diffuse with relative ease parallel to it. Within the resulting broad spectrum of relaxation times there is an extended period before the longest relaxation time when filaments occupy a time-averaged cylindrical space of near-constant density. Here we show its implication with experiments based on fluorescence tracking of dilutely labeled macromolecules. The entangled pairs of aqueous F-actin biofilaments diffuse with separation-dependent dynamic cross-correlations that exceed those expected from continuum hydrodynamics up to strikingly large spatial distances of ≈15 µm, which is more than 104 times the size of the solvent water molecules in which they are dissolved, and is more than 50 times the dynamic tube diameter, but is almost equal to the filament length. Modeling this entangled system as a collection of rigid rods, we present a statistical mechanical theory that predicts these long-range dynamic correlations as an emergent consequence of an effective long-range interpolymer repulsion due to the de Gennes correlation hole, which is a combined consequence of chain connectivity and uncrossability. The key physical assumption needed to make theory and experiment agree is that solutions of entangled biofilaments localized in tubes that are effectively dynamically incompressible over the relevant intermediate time and length scales. PMID:28283664

  4. Dynamic cross-correlations between entangled biofilaments as they diffuse.

    PubMed

    Tsang, Boyce; Dell, Zachary E; Jiang, Lingxiang; Schweizer, Kenneth S; Granick, Steve

    2017-03-10

    Entanglement in polymer and biological physics involves a state in which linear interthreaded macromolecules in isotropic liquids diffuse in a spatially anisotropic manner beyond a characteristic mesoscopic time and length scale (tube diameter). The physical reason is that linear macromolecules become transiently localized in directions transverse to their backbone but diffuse with relative ease parallel to it. Within the resulting broad spectrum of relaxation times there is an extended period before the longest relaxation time when filaments occupy a time-averaged cylindrical space of near-constant density. Here we show its implication with experiments based on fluorescence tracking of dilutely labeled macromolecules. The entangled pairs of aqueous F-actin biofilaments diffuse with separation-dependent dynamic cross-correlations that exceed those expected from continuum hydrodynamics up to strikingly large spatial distances of ≈15 µm, which is more than 10(4) times the size of the solvent water molecules in which they are dissolved, and is more than 50 times the dynamic tube diameter, but is almost equal to the filament length. Modeling this entangled system as a collection of rigid rods, we present a statistical mechanical theory that predicts these long-range dynamic correlations as an emergent consequence of an effective long-range interpolymer repulsion due to the de Gennes correlation hole, which is a combined consequence of chain connectivity and uncrossability. The key physical assumption needed to make theory and experiment agree is that solutions of entangled biofilaments localized in tubes that are effectively dynamically incompressible over the relevant intermediate time and length scales.

  5. Slow diffusive dynamics in a chaotic balanced neural network

    PubMed Central

    Shaham, Nimrod

    2017-01-01

    It has been proposed that neural noise in the cortex arises from chaotic dynamics in the balanced state: in this model of cortical dynamics, the excitatory and inhibitory inputs to each neuron approximately cancel, and activity is driven by fluctuations of the synaptic inputs around their mean. It remains unclear whether neural networks in the balanced state can perform tasks that are highly sensitive to noise, such as storage of continuous parameters in working memory, while also accounting for the irregular behavior of single neurons. Here we show that continuous parameter working memory can be maintained in the balanced state, in a neural circuit with a simple network architecture. We show analytically that in the limit of an infinite network, the dynamics generated by this architecture are characterized by a continuous set of steady balanced states, allowing for the indefinite storage of a continuous parameter. In finite networks, we show that the chaotic noise drives diffusive motion along the approximate attractor, which gradually degrades the stored memory. We analyze the dynamics and show that the slow diffusive motion induces slowly decaying temporal cross correlations in the activity, which differ substantially from those previously described in the balanced state. We calculate the diffusivity, and show that it is inversely proportional to the system size. For large enough (but realistic) neural population sizes, and with suitable tuning of the network connections, the proposed balanced network can sustain continuous parameter values in memory over time scales larger by several orders of magnitude than the single neuron time scale. PMID:28459813

  6. Diffusive and Arrestedlike Dynamics in Currency Exchange Markets

    NASA Astrophysics Data System (ADS)

    Clara-Rahola, J.; Puertas, A. M.; Sánchez-Granero, M. A.; Trinidad-Segovia, J. E.; de las Nieves, F. J.

    2017-02-01

    This work studies the symmetry between colloidal dynamics and the dynamics of the Euro-U.S. dollar currency exchange market (EURUSD). We consider the EURUSD price in the time range between 2001 and 2015, where we find significant qualitative symmetry between fluctuation distributions from this market and the ones belonging to colloidal particles in supercooled or arrested states. In particular, we find that models used for arrested physical systems are suitable for describing the EURUSD fluctuation distributions. Whereas the corresponding mean-squared price displacement (MSPD) to the EURUSD is diffusive for all years, when focusing in selected time frames within a day, we find a two-step MSPD when the New York Stock Exchange market closes, comparable to the dynamics in supercooled systems. This is corroborated by looking at the price correlation functions and non-Gaussian parameters and can be described by the theoretical model. We discuss the origin and implications of this analogy.

  7. Diffusive and Arrestedlike Dynamics in Currency Exchange Markets.

    PubMed

    Clara-Rahola, J; Puertas, A M; Sánchez-Granero, M A; Trinidad-Segovia, J E; de Las Nieves, F J

    2017-02-10

    This work studies the symmetry between colloidal dynamics and the dynamics of the Euro-U.S. dollar currency exchange market (EURUSD). We consider the EURUSD price in the time range between 2001 and 2015, where we find significant qualitative symmetry between fluctuation distributions from this market and the ones belonging to colloidal particles in supercooled or arrested states. In particular, we find that models used for arrested physical systems are suitable for describing the EURUSD fluctuation distributions. Whereas the corresponding mean-squared price displacement (MSPD) to the EURUSD is diffusive for all years, when focusing in selected time frames within a day, we find a two-step MSPD when the New York Stock Exchange market closes, comparable to the dynamics in supercooled systems. This is corroborated by looking at the price correlation functions and non-Gaussian parameters and can be described by the theoretical model. We discuss the origin and implications of this analogy.

  8. Hydrogen Bonding and Related Properties in Liquid Water: A Car-Parrinello Molecular Dynamics Simulation Study.

    PubMed

    Guardia, Elvira; Skarmoutsos, Ioannis; Masia, Marco

    2015-07-23

    The local hydrogen-bonding structure and dynamics of liquid water have been investigated using the Car-Parrinello molecular dynamics simulation technique. The radial distribution functions and coordination numbers around water molecules have been found to be strongly dependent on the number of hydrogen bonds formed by each molecule, revealing also the existence of local structural heterogeneities in the structure of the liquid. The results obtained have also revealed the strong effect of the local hydrogen-bonding network on the local tetrahedral structure and entropy. The investigation of the dynamics of the local hydrogen-bonding network in liquid water has shown that this network is very labile, and the hydrogen bonds break and reform very rapidly. Nevertheless, it has been found that the hydrogen-bonding states associated with the formation of four hydrogen bonds by a water molecule exhibit the largest survival probability and corresponding lifetime. The reorientational motions of water molecules have also been found to be strongly dependent on their initial hydrogen-bonding state. Finally, the dependence of the librational and vibrational modes of water molecules on the local hydrogen-bonding network has been carefully examined, revealing a significant effect upon the libration and bond-stretching peak frequencies. The calculated low frequency peaks come in agreement with previously reported interpretations of the experimental low-frequency Raman spectrum of liquid water.

  9. 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.

  10. Diffusion and structure in silica liquid: a molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Hung, P. K.; Hong, N. V.; Vinh, L. T.

    2007-11-01

    Diffusion and structure in liquid silica under pressure have been investigated by a molecular dynamics model of 999 atoms with the inter-atomic potentials of van Beest, Kramer and van Santen. The simulation reveals that silica liquid is composed of the species SiO4, SiO5 and SiO6 with a fraction dependent on pressure. The density as well as volume of voids can be expressed as a linear function of the fraction of those species. Low-density liquid is mainly constructed of SiO4 and has a large number of O- and Si-voids and a large void tube. This tube contains most O-voids and is spread over the whole system. The anomalous diffusion behavior is observed and discussed.

  11. Diffusion in crowded biological environments: applications of Brownian dynamics

    PubMed Central

    2011-01-01

    Biochemical reactions in living systems occur in complex, heterogeneous media with total concentrations of macromolecules in the range of 50 - 400 mgml. Molecular species occupy a significant fraction of the immersing medium, up to 40% of volume. Such complex and volume-occupied environments are generally termed 'crowded' and/or 'confined'. In crowded conditions non-specific interactions between macromolecules may hinder diffusion - a major process determining metabolism, transport, and signaling. Also, the crowded media can alter, both qualitatively and quantitatively, the reactions in vivo in comparison with their in vitro counterparts. This review focuses on recent developments in particle-based Brownian dynamics algorithms, their applications to model diffusive transport in crowded systems, and their abilities to reproduce and predict the behavior of macromolecules under in vivo conditions. PMID:21595998

  12. Diffusion Bonding Behavior and Characterization of Joints Made Between 316L Stainless Steel Alloy and AZ31 Magnesium Alloy

    NASA Astrophysics Data System (ADS)

    Elthalabawy, Waled Mohamed

    The 316L austenitic stainless steel and AZ31 magnesium alloy have physical and mechanical properties which makes these alloys suitable in a number of high technology based industries such as the aerospace and automotive sectors. However, for these alloys to be used in engineering applications, components must be fabricated and joined successfully. The differences in the physical and metallurgical properties between these two alloys prevents the use of conventional fusion welding processes commonly employed in aerospace and transport industry. Therefore, alternative techniques need to be developed and diffusion bonding technology is a process that has considerable potential to join these two dissimilar alloys. In this research work both solid-state and transient liquid phase (TLP) bonding processes were applied. The solid-state bonding of 316L steel to AZ31 magnesium alloy was possible at a bonding temperature of 550°C for 120 minutes using a pressure of 1.3 MPa. The interface characterization of the joint showed a thin intermetallic zone rich in Fe-Al was responsible for providing a metallurgical bond. However, low joint shear strengths were recorded and this was attributed to the poor surface to surface contact. The macro-deformation of the AZ31 alloy prevented the use of higher bonding pressures and longer bonding times. In order to overcome these problems, the TLP bonding process was implemented using pure Cu and Ni foils as interlayers which produced a eutectic phase at the bonding temperature. This research identified the bonding mechanism through microstructural and differential scanning calorimetry investigations. The microstructural characterization of the TLP joints identified intermetallics which became concentrated along the 316L steel/AZ31 bond interface due to the "pushing effect" of the solid/liquid interface during isothermal solidification stage of bonding. The size and concentration of the intermetallics had a noticeable effect on the final joint

  13. A Mathematical Model of Diffusion-Limited Gas Bubble Dynamics in Tissue with Varying Diffusion Region Thickness

    NASA Technical Reports Server (NTRS)

    Srinivasan, R. Srini; Gerth, Wayne A.; Powell, Michael R.; Paloski, William H. (Technical Monitor)

    2000-01-01

    A three-region mathematical model of gas bubble dynamics has been shown suitable for describing diffusion-limited dynamics of more than one bubble in a given volume of extravascular tissue. The model is based on the dynamics of gas exchange between a bubble and a well-stirred tissue region through an intervening unperfused diffusion region previously assumed to have constant thickness and uniform gas diffusivity. As a result, the gas content of the diffusion region remains constant as the volume of the region increases with bubble growth, causing dissolved gas in the region to violate Henry's law. Earlier work also neglected the relationship between the varying diffusion region volume and the fixed total tissue volume, because only cases in which the diffusion region volume is a small fraction of the overall tissue volume were considered. We herein extend the three-region model to correct these theoretical inconsistencies by allowing both the thickness and gas content of the diffusion region to vary during bubble evolution. A postulated difference in gas diffusivity between an infinitesimally thin layer at the bubble surface and the remainder of the diffusion region leads to variation in diffusion region gas content and thickness during bubble growth and resolution. This variable thickness, differential diffusivity (VTDD) model can yield bubble lifetimes considerably longer than those yielded by earlier three-region models for given model and decompression parameters, and meets a need for theoretically consistent but relatively simple bubble dynamics models for use in studies of decompression sickness (DCS) in human subjects, Keywords: decompression sickness, gas diffusion in tissue, diffusivity

  14. Molecular Dynamics Simulations of Diffusion in a Silica Melt

    NASA Astrophysics Data System (ADS)

    Gemmell, A.; Fraser, D.; Refson, K.

    2003-12-01

    Computer modelling of silicate melts enables the study of pressure-temperature conditions not easily obtainable by traditional experimentation (e.g. 1). Diffusion in melts under various conditions is critical to our understanding of a variety of processes such as melt crystallisation, magma mixing and the behaviour of trace elements during magma ascent that underpins the field of igneous petrogenesis. It can also provide information on melt structure via diffusion mechanisms and their activation energies. In the present paper, the magnitude and mechanism of diffusion of silicon and oxygen in molten silica has been investigated by molecular dynamics using a modified BKS potential (2). A range of melt temperatures and pressures were studied with a view to understanding the relationship between temperature, pressure, diffusion and melt structure. At each P-T point studied, the system was equilibrated for between 1 million and 40 million 1fs steps depending on the conditions, with data collection over the same time range. The potential was adjusted to overcome problems with instability in the particle velocities at high temperature. The simulations were run at the Oxford University Supercomputing centre, UK. Systems of 144, 288, 576 and 1152 particles were investigated. In addition, two different sets of periodic boundary conditions were used - cubic and truncated octahedral. The latter was found to provide a better ratio of simulated time to compute time. The present data extend the range of data available and indicate a pronounced non-linearity in the temperature dependence of diffusion, as shown by plots of log10D with 1/T. The second derivative is greatest around 3500K. At least two different diffusion mechanisms may operate at lower and higher temperatures with differing activation energies. Comparison with previous molecular dynamics data shows broad agreement with most studies. Although the data presented do include some low temperature runs, comparison with

  15. Testing and modeling of diffusion bonded prototype optical windows under ITER conditions

    SciTech Connect

    Jacobs, M.; Van Oost, G.; Degrieck, J.; De Baere, I.; Gusarov, A.; Gubbels, F.; Massaut, V.

    2011-07-01

    Glass-metal joints are a part of ITER optical diagnostics windows. These joints must be leak tight for the safety (presence of tritium in ITER) and to preserve the vacuum. They must also withstand the ITER environment: temperatures up to 220 deg.C and fast neutron fluxes of {approx}3.10{sup 9} n/cm{sup 2}.s. At the moment, little information is available about glass-metal joints suitable for ITER. Therefore, we performed mechanical and thermal tests on some prototypes of an aluminium diffusion bonded optical window. Finite element modeling with Abaqus code was used to understand the experimental results. The prototypes were helium leaking probably due to very tiny cracks in the interaction layer between the steel and the aluminium. However, they were all able to withstand a thermal cycling test up to 200 deg. C; no damage could be seen after the tests by visual inspection. The prototypes successfully passed push-out test with a 500 N load. During the destructive push-out tests the prototypes broke at a 6-12 kN load between the aluminium layer and the steel or the glass, depending on the surface quality of the glass. The microanalysis of the joints has also been performed. The finite element modeling of the push-out tests is in a reasonable agreement with the experiments. According to the model, the highest thermal stress is created in the aluminium layer. Thus, the aluminium joint seems to be the weakest part of the prototypes. If this layer is improved, it will probably make the prototype helium leak tight and as such, a good ITER window candidate. (authors)

  16. 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.

  17. Topological hydrogen-bond definition to characterize the structure and dynamics of liquid water.

    PubMed

    Henchman, Richard H; Irudayam, Sheeba Jem

    2010-12-23

    A definition that equates a hydrogen bond topologically with a local energy well in the potential energy surface is used to study the structure and dynamics of liquid water. We demonstrate the robustness of this hydrogen-bond definition versus the many other definitions which use fixed, arbitrary parameters, do not account for variable molecular environments, and cannot effectively resolve transition states. Our topology definition unambiguously shows that most water molecules are double acceptors but sizable proportions are single or triple acceptors. Almost all hydrogens are found to take part in hydrogen bonds. Broken hydrogen bonds only form when two molecules try to form two hydrogen bonds between them. The double acceptors have tetrahedral geometry, lower potential energy, entropy, and density, and slower dynamics. The single and triple acceptors have trigonal and trigonal bipyramidal geometry and when considered together have higher density, potential energy, and entropy, faster dynamics, and a tendency to cluster. These calculations use an extended theory for the entropy of liquid water that takes into account the variable number of hydrogen bonds. Hydrogen-bond switching is shown to depend explicitly on the variable number of hydrogen bonds accepted and the presence of interstitial water molecules. Transition state theory indicates that the switching of hydrogen bonds is a mildly activated process, requiring only a moderate distortion of hydrogen bonds. Three main types of switching events are observed depending on whether the donor and acceptor are already sharing a hydrogen bond. The switch may proceed with no intermediate or via a bifurcated-oxygen or cyclic dimer, both of which have a broken hydrogen bond and symmetric and asymmetric forms. Switching is found to be strongly coupled to whole-molecule vibration, particularly for the more mobile single and triple acceptors. Our analysis suggests that even though water is heterogeneous in terms of the

  18. Dynamic hysteresis modeling including skin effect using diffusion equation model

    NASA Astrophysics Data System (ADS)

    Hamada, Souad; Louai, Fatima Zohra; Nait-Said, Nasreddine; Benabou, Abdelkader

    2016-07-01

    An improved dynamic hysteresis model is proposed for the prediction of hysteresis loop of electrical steel up to mean frequencies, taking into account the skin effect. In previous works, the analytical solution of the diffusion equation for low frequency (DELF) was coupled with the inverse static Jiles-Atherton (JA) model in order to represent the hysteresis behavior for a lamination. In the present paper, this approach is improved to ensure the reproducibility of measured hysteresis loops at mean frequency. The results of simulation are compared with the experimental ones. The selected results for frequencies 50 Hz, 100 Hz, 200 Hz and 400 Hz are presented and discussed.

  19. Stochastic actions for diffusive dynamics: reweighting, sampling, and minimization.

    PubMed

    Adib, Artur B

    2008-05-15

    In numerical studies of diffusive dynamics, two different action functionals are often used to specify the probability distribution of trajectories, one of which requires the evaluation of the second derivative of the potential in addition to the force. Here it is argued that both actions are equivalent prescriptions for the purposes of reweighting and sampling trajectories, whereas the most probable path is more generally given by the global minimum of the action involving the second derivative term. The answer to this apparent paradox lies in the nondifferentiable character of Brownian paths, as well as in the "entropy" associated with a given trajectory.

  20. Radial propagation in population dynamics with density-dependent diffusion

    NASA Astrophysics Data System (ADS)

    Ngamsaad, Waipot

    2014-01-01

    Population dynamics that evolve in a radial symmetric geometry are investigated. The nonlinear reaction-diffusion model, which depends on population density, is employed as the governing equation for this system. The approximate analytical solution to this equation is found. It shows that the population density evolves from the initial state and propagates in a traveling-wave-like manner for a long-time scale. If the distance is insufficiently long, the curvature has an ineluctable influence on the density profile and front speed. In comparison, the analytical solution is in agreement with the numerical solution.

  1. Interface science of controlled metal/metal and metal/ceramic interfaces prepared using ultrahigh vacuum diffusion bonding

    SciTech Connect

    King, W.E.; Campbell, G.H.; Coombs, A.W.; Johnson, G.W.; Kelly, B.E.; Reitz, T.C.; Stoner, S.L.; Wien, W.L.; Wilson, D.M.

    1993-04-01

    We have designed, constructed, and are operating a capability for production of controlled homophase and heterophase interfaces: an ultrahigh vacuum diffusion bonding machine. This machine is based on a previous design which is operating at the Max Planck Institut fuer Metallforschung, Institut fuer Werkstoffwissenschaft, Stuttgart, FRG. In this method, flat-polished single or polycrystals of materials with controlled surfaced topography can be heat treated up to 1500C in ultrahigh vacuum. Surfaces of annealed samples can be sputter cleaned and characterized prior to bonding. Samples can then be precisely aligned crystallographically to obtain desired grain boundary misorientations. Material couples can then be bonded at temperatures up to 1500C and pressures up to 10 MPa. Results are presented from initial work on Mo grain boundaries and Cu/Al{sub 2}A{sub 3} interfaces.

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

    SciTech Connect

    Youchison, D.L.; Guiniiatouline, R.; Watson, R.D.

    1994-12-31

    Thermal response and thermal fatigue tests of four 5 mm thick beryllium tiles on a Russian divertor mock-up were completed on the Electron Beam Test System at Sandia National Laboratories. The beryllium tiles were diffusion bonded onto an OFHC copper saddleblock and a DSCu (MAGT) tube containing a porous coating. Thermal response tests were performed on the tiles to an absorbed heat flux of 5 MW/m{sup 2} and surface temperatures near 300{degrees}C using 1.4 MPa water at 5.0 m/s flow velocity and an inlet temperature of 8-15{degrees}C. One tile was exposed to incrementally increasing heat fluxes up to 9.5 MW/m{sup 2} and surface temperatures up to 690{degrees}C before debonding at 10 MW/m{sup 2}. A third tile debonded after 9200 thermal fatigue cycles at 5 MW/m{sup 2}, while another debonded after 6800 cycles. In all cases, fatigue failure occurred in the intermetallic layers between the beryllium and copper. No fatigue cracking of the bulk beryllium was observed. During thermal cycling, a gradual loss of porous coating produced increasing sample temperatures. These experiments indicate that diffusion-bonded beryllium tiles can survive several thousand thermal cycles under ITER relevant conditions without failure. However, the reliability of the diffusion bonded Joint remains a serious issue.

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

    SciTech Connect

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

    1996-07-01

    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 second 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.

  4. 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.

  5. Valence-bond description of chemical reactions on Born-Oppenheimer molecular dynamics trajectories

    NASA Astrophysics Data System (ADS)

    Noguchi, Nao; Nakano, Haruyuki

    2009-04-01

    The nature of chemical bonds on dynamic paths was investigated using the complete active space valence-bond (CASVB) method and the Born-Oppenheimer dynamics. To extract the chemical bond picture during reactions, a scheme to collect contributions from several VB (resonance) structures into a small numbers of indices was introduced. In this scheme, a tree diagram for the VB structures is constructed with the numbers of the ionic bonds treated as generation. A pair of VB structures is related to each other if one VB structure is transferred into the other by changing a covalent bond to an ionic bond. The former and latter VB structures are named parent and child structures, respectively. The weights of the bond pictures are computed as the sum of the CASVB occupation numbers running from the top generation to the bottom along the descent of the VB structures. Thus, a number of CASVB occupation numbers are collected into a small number of indices, and a clear bond picture may be obtained from the CASVB wave function. The scheme was applied to the hydrogen exchange reaction H2+F→H+HF and the Diels-Alder reaction C5H6(cyclopentadiene)+CH2=CH2(ethylene)→C7H10(norbornene). In both the reactions, the scheme gave a clear picture for the Born-Oppenheimer dynamics trajectories. The reconstruction of the bonds during reactions was well described by following the temporal changes in weight.

  6. Valence-bond description of chemical reactions on Born-Oppenheimer molecular dynamics trajectories.

    PubMed

    Noguchi, Nao; Nakano, Haruyuki

    2009-04-21

    The nature of chemical bonds on dynamic paths was investigated using the complete active space valence-bond (CASVB) method and the Born-Oppenheimer dynamics. To extract the chemical bond picture during reactions, a scheme to collect contributions from several VB (resonance) structures into a small numbers of indices was introduced. In this scheme, a tree diagram for the VB structures is constructed with the numbers of the ionic bonds treated as generation. A pair of VB structures is related to each other if one VB structure is transferred into the other by changing a covalent bond to an ionic bond. The former and latter VB structures are named parent and child structures, respectively. The weights of the bond pictures are computed as the sum of the CASVB occupation numbers running from the top generation to the bottom along the descent of the VB structures. Thus, a number of CASVB occupation numbers are collected into a small number of indices, and a clear bond picture may be obtained from the CASVB wave function. The scheme was applied to the hydrogen exchange reaction H(2)+F-->H+HF and the Diels-Alder reaction C(5)H(6)(cyclopentadiene)+CH(2)=CH(2)(ethylene)-->C(7)H(10)(norbornene). In both the reactions, the scheme gave a clear picture for the Born-Oppenheimer dynamics trajectories. The reconstruction of the bonds during reactions was well described by following the temporal changes in weight.

  7. Cooperative dynamic and diffusion behavior above and below the dynamical crossover of supercooled water

    NASA Astrophysics Data System (ADS)

    Picasso, Germán C.; Malaspina, David C.; Carignano, Marcelo A.; Szleifer, Igal

    2013-07-01

    Using extensive molecular dynamics simulations combined with a novel approach to analyze the molecular displacements we analyzed the change in the dynamics above and below the crossover temperature Tx for supercooled water. Our findings suggest that the crossover from fragile to strong glass former occurring at Tx is related with a change in the diffusion mechanism evidencing the presence of jump-like diffusion at lower temperatures. Also we observe that fluctuations of the local environments are intimately connected with fluctuations in the size and the amount of cooperative cluster of mobile molecules, and in particular we find a highly cooperative nature of the motion at low temperatures.

  8. 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.

  9. Hydrogen Bonding Controls the Dynamics of Catechol Adsorbed on a TiO2(110) Surface

    NASA Astrophysics Data System (ADS)

    Diebold, Ulrike; Li, Shao-Chun; Chu, Li-Na; Gong, Xue-Qing

    2011-03-01

    Direct studies of how organic molecules diffuse on metal oxide surfaces can provide insights into catalysis and molecular assembly processes. We studied individual catechol molecules, C6 H4 (OH)2 , on a rutile Ti O2 (110) surface with scanning tunnelingmicroscopy. Surface hydroxyls enhanced the diffusivity of adsorbed catecholates. The capture and release of a proton caused individual molecules to switch between mobile and immobile states within a measurement period of minutes. Density functional theory calculations showed that the transfer of hydrogen from surface hydroxyls to the molecule and its interaction with surface hydroxyls substantially lowered the activation barrier for rotational motion across the surface. Hydrogen bonding can play an essential role in the initial stages of the dynamics of molecular assembly.

  10. Dynamic diffusion tensor measurements in muscle tissue using Single Line Multiple Echo Diffusion Tensor Acquisition Technique at 3T

    PubMed Central

    Baete, Steven H.; Cho, Gene; Sigmund, Eric E.

    2015-01-01

    When diffusion biomarkers display transient changes, i.e. in muscle following exercise, traditional diffusion tensor imaging (DTI) methods lack temporal resolution to resolve the dynamics. This paper presents an MRI method for dynamic diffusion tensor acquisitions on a clinical 3T scanner. This method, SL-MEDITATE (Single Line Multiple Echo Diffusion Tensor Acquisition Technique) achieves a high temporal resolution (4s) (1) by rapid diffusion encoding through the acquisition of multiple echoes with unique diffusion sensitization and (2) by limiting the readout to a single line volume. The method is demonstrated in a rotating anisotropic phantom, in a flow phantom with adjustable flow speed, and in in vivo skeletal calf muscle of healthy volunteers following a plantar flexion exercise. The rotating and flow-varying phantom experiments show that SL-MEDITATE correctly identifies the rotation of the first diffusion eigenvector and the changes in diffusion tensor parameter magnitudes, respectively. Immediately following exercise, the in vivo mean diffusivity (MD) time-courses show, before the well-known increase, an initial decrease which is not typically observed in traditional DTI. In conclusion, SL-MEDITATE can be used to capture transient changes in tissue anisotropy in a single line. Future progress might allow for dynamic DTI when combined with appropriate k-space trajectories and compressed sensing reconstruction. PMID:25900166

  11. Knowledge diffusion of dynamical network in terms of interaction frequency.

    PubMed

    Liu, Jian-Guo; Zhou, Qing; Guo, Qiang; Yang, Zhen-Hua; Xie, Fei; Han, Jing-Ti

    2017-09-07

    In this paper, we present a knowledge diffusion (SKD) model for dynamic networks by taking into account the interaction frequency which always used to measure the social closeness. A set of agents, which are initially interconnected to form a random network, either exchange knowledge with their neighbors or move toward a new location through an edge-rewiring procedure. The activity of knowledge exchange between agents is determined by a knowledge transfer rule that the target node would preferentially select one neighbor node to transfer knowledge with probability p according to their interaction frequency instead of the knowledge distance, otherwise, the target node would build a new link with its second-order neighbor preferentially or select one node in the system randomly with probability 1 - p. The simulation results show that, comparing with the Null model defined by the random selection mechanism and the traditional knowledge diffusion (TKD) model driven by knowledge distance, the knowledge would spread more fast based on SKD driven by interaction frequency. In particular, the network structure of SKD would evolve as an assortative one, which is a fundamental feature of social networks. This work would be helpful for deeply understanding the coevolution of the knowledge diffusion and network structure.

  12. Diffusion dynamics in the disordered Bose Hubbard model

    NASA Astrophysics Data System (ADS)

    Wadleigh, Laura; Russ, Philip; Demarco, Brian

    2016-05-01

    We explore the dynamics of diffusion for out-of-equilibrium superfluid, Mott insulator, and Bose glass states using an atomic realization of the disordered Bose Hubbard (DBH) model. Dynamics in strongly correlated systems, especially far from equilibrium, are not well understood. The introduction of disorder further complicates these systems. We realize the DBH model--which has been central to our understanding of quantum phase transitions in disordered systems--using ultracold Rubidium-87 atoms trapped in a cubic disordered optical lattice. By tightly focusing a beam into the center of the gas, we create a hole in the atomic density profile. We achieve Mott insulator, superfluid, or Bose glass states by varying the interaction and disorder strength, and measure the time evolution of the density profile after removing the central barrier. This allows us to infer diffusion rates from the velocities at the edge of the hole and to look for signatures of superfluid puddles in the Bose glass state. We acknowledge funding from NSF Grant PHY 15-05468, NSF Grant DGE-1144245, and ARO Grant W911NF-12-1-0462.

  13. Diffusive and dynamical radiating stars with realistic equations of state

    NASA Astrophysics Data System (ADS)

    Brassel, Byron P.; Maharaj, Sunil D.; Goswami, Rituparno

    2017-03-01

    We model the dynamics of a spherically symmetric radiating dynamical star with three spacetime regions. The local internal atmosphere is a two-component system consisting of standard pressure-free, null radiation and an additional string fluid with energy density and nonzero pressure obeying all physically realistic energy conditions. The middle region is purely radiative which matches to a third region which is the Schwarzschild exterior. A large family of solutions to the field equations are presented for various realistic equations of state. We demonstrate that it is possible to obtain solutions via a direct integration of the second order equations resulting from the assumption of an equation of state. A comparison of our solutions with earlier well known results is undertaken and we show that all these solutions, including those of Husain, are contained in our family. We then generalise our class of solutions to higher dimensions. Finally we consider the effects of diffusive transport and transparently derive the specific equations of state for which this diffusive behaviour is possible.

  14. Dynamics of Diffusion Flames in von Karman Swirling Flows Studied

    NASA Technical Reports Server (NTRS)

    Nayagam, Vedha; Williams, Forman A.

    2002-01-01

    Von Karman swirling flow is generated by the viscous pumping action of a solid disk spinning in a quiescent fluid media. When this spinning disk is ignited in an oxidizing environment, a flat diffusion flame is established adjacent to the disk, embedded in the boundary layer (see the preceding illustration). For this geometry, the conservation equations reduce to a system of ordinary differential equations, enabling researchers to carry out detailed theoretical models to study the effects of varying strain on the dynamics of diffusion flames. Experimentally, the spinning disk burner provides an ideal configuration to precisely control the strain rates over a wide range. Our original motivation at the NASA Glenn Research Center to study these flames arose from a need to understand the flammability characteristics of solid fuels in microgravity where slow, subbuoyant flows can exist, producing very small strain rates. In a recent work (ref. 1), we showed that the flammability boundaries are wider and the minimum oxygen index (below which flames cannot be sustained) is lower for the von Karman flow configuration in comparison to a stagnation-point flow. Adding a small forced convection to the swirling flow pushes the flame into regions of higher strain and, thereby, decreases the range of flammable strain rates. Experiments using downward facing, polymethylmethacrylate (PMMA) disks spinning in air revealed that, close to the extinction boundaries, the flat diffusion flame breaks up into rotating spiral flames (refs. 2 and 3). Remarkably, the dynamics of these spiral flame edges exhibit a number of similarities to spirals observed in biological systems, such as the electric pulses in cardiac muscles and the aggregation of slime-mold amoeba. The tail of the spiral rotates rigidly while the tip executes a compound, meandering motion sometimes observed in Belousov-Zhabotinskii reactions.

  15. Chaotic dynamics and diffusion in a piecewise linear equation

    NASA Astrophysics Data System (ADS)

    Shahrear, Pabel; Glass, Leon; Edwards, Rod

    2015-03-01

    Genetic interactions are often modeled by logical networks in which time is discrete and all gene activity states update simultaneously. However, there is no synchronizing clock in organisms. An alternative model assumes that the logical network is preserved and plays a key role in driving the dynamics in piecewise nonlinear differential equations. We examine dynamics in a particular 4-dimensional equation of this class. In the equation, two of the variables form a negative feedback loop that drives a second negative feedback loop. By modifying the original equations by eliminating exponential decay, we generate a modified system that is amenable to detailed analysis. In the modified system, we can determine in detail the Poincaré (return) map on a cross section to the flow. By analyzing the eigenvalues of the map for the different trajectories, we are able to show that except for a set of measure 0, the flow must necessarily have an eigenvalue greater than 1 and hence there is sensitive dependence on initial conditions. Further, there is an irregular oscillation whose amplitude is described by a diffusive process that is well-modeled by the Irwin-Hall distribution. There is a large class of other piecewise-linear networks that might be analyzed using similar methods. The analysis gives insight into possible origins of chaotic dynamics in periodically forced dynamical systems.

  16. Chaotic dynamics and diffusion in a piecewise linear equation

    SciTech Connect

    Shahrear, Pabel; Glass, Leon; Edwards, Rod

    2015-03-15

    Genetic interactions are often modeled by logical networks in which time is discrete and all gene activity states update simultaneously. However, there is no synchronizing clock in organisms. An alternative model assumes that the logical network is preserved and plays a key role in driving the dynamics in piecewise nonlinear differential equations. We examine dynamics in a particular 4-dimensional equation of this class. In the equation, two of the variables form a negative feedback loop that drives a second negative feedback loop. By modifying the original equations by eliminating exponential decay, we generate a modified system that is amenable to detailed analysis. In the modified system, we can determine in detail the Poincaré (return) map on a cross section to the flow. By analyzing the eigenvalues of the map for the different trajectories, we are able to show that except for a set of measure 0, the flow must necessarily have an eigenvalue greater than 1 and hence there is sensitive dependence on initial conditions. Further, there is an irregular oscillation whose amplitude is described by a diffusive process that is well-modeled by the Irwin-Hall distribution. There is a large class of other piecewise-linear networks that might be analyzed using similar methods. The analysis gives insight into possible origins of chaotic dynamics in periodically forced dynamical systems.

  17. Chaotic dynamics and diffusion in a piecewise linear equation.

    PubMed

    Shahrear, Pabel; Glass, Leon; Edwards, Rod

    2015-03-01

    Genetic interactions are often modeled by logical networks in which time is discrete and all gene activity states update simultaneously. However, there is no synchronizing clock in organisms. An alternative model assumes that the logical network is preserved and plays a key role in driving the dynamics in piecewise nonlinear differential equations. We examine dynamics in a particular 4-dimensional equation of this class. In the equation, two of the variables form a negative feedback loop that drives a second negative feedback loop. By modifying the original equations by eliminating exponential decay, we generate a modified system that is amenable to detailed analysis. In the modified system, we can determine in detail the Poincaré (return) map on a cross section to the flow. By analyzing the eigenvalues of the map for the different trajectories, we are able to show that except for a set of measure 0, the flow must necessarily have an eigenvalue greater than 1 and hence there is sensitive dependence on initial conditions. Further, there is an irregular oscillation whose amplitude is described by a diffusive process that is well-modeled by the Irwin-Hall distribution. There is a large class of other piecewise-linear networks that might be analyzed using similar methods. The analysis gives insight into possible origins of chaotic dynamics in periodically forced dynamical systems.

  18. Hydrogen bond lifetime for water in classic and quantum molecular dynamics

    NASA Astrophysics Data System (ADS)

    Antipova, M. L.; Petrenko, V. E.

    2013-07-01

    The lifetime of hydrogen bonds in water at T = 298 K and p = 0.1 MPa is computed by means of classic molecular dynamics with eight different potentials of pair lifetime interaction and Car-Parinello molecular dynamics. The results obtained using various computational techniques for hydrogen bond life-times are compared. It is shown that they can differ from one another by several times. The dependence for the hydrogen bond lifetime computed in our numerical experiment upon the method of its determination is found.

  19. The effect of hydrogen bonding propensity and enantiomeric composition on the dynamics of supercooled ketoprofen - dielectric, rheological and NMR studies.

    PubMed

    Adrjanowicz, K; Kaminski, K; Tarnacka, M; Szutkowski, K; Popenda, L; Bartkowiak, G; Paluch, M

    2016-04-21

    The aim of this work is to analyze in detail the effect of small hydrogen bonding (HB) structures and enantiomeric composition on the dynamics of glass-forming liquid ketoprofen. For that purpose dielectric relaxation, rheological and NMR studies were performed. Investigated samples are racemic ketoprofen, a single enantiomer of ketoprofen and a racemic ketoprofen methyl ester with no tendency to form HB dimers. The combination of complementary experimental techniques enables us to show that macroscopic viscosity η and α-relaxation time τα have nearly the same temperature dependencies, whereas the relation between the viscosity (or molecular reorientation) and the translational self-diffusion coefficient violates Stokes-Einstein law already at high temperature. Additionally, based on dielectric relaxation studies performed on increased pressure we were able to identify similarities and key differences in the supercooled liquid dynamics of investigated materials affected by their tendency to form intermolecular hydrogen bonds. This includes the effect of pressure on the glass transition temperature Tg, changes in the fragility parameter m and activation volume ΔV, the role of thermal energy and density fluctuations in governing the viscous liquid dynamics (Ev/Ep ratio). Finally, we have also demonstrated that the dynamic behaviour of a single enantiomer and the racemic mixture of the same compound are very much alike. Nevertheless, some slight differences were observed, particularly in the τα(T) dependencies measured in the vicinity of glass transition both at ambient and elevated pressure.

  20. An investigation on diffusion bonding of aluminum to copper using equal channel angular extrusion process

    PubMed Central

    Eslami, P.; Taheri, A. Karimi

    2011-01-01

    A new method for production of bimetallic rods, utilizing the equal channel angular extrusion (ECAE) process has been introduced before by previous researchers, but no attempt has been made to assess the effect of different temperatures and holding times in order to achieve a diffusional bond between the mating surfaces. In present research copper sheathed aluminum rods have been ECAEed at room temperature and subsequently held at a constant ECAE pressure, at different temperatures and holding times to produce a diffusional bond between the copper sheath and the aluminum core. The bonding quality of the joints was examined by shear strength test and a sound bonding interface was achieved. Based on the results, a bonding temperature of 200 °C and holding time of 60–80 min yielded the highest shear strength value. PMID:21760654

  1. Anomalously Rapid Hydration Water Diffusion Dynamics Near DNA Surfaces.

    PubMed

    Franck, John M; Ding, Yuan; Stone, Katherine; Qin, Peter Z; Han, Songi

    2015-09-23

    The emerging Overhauser effect dynamic nuclear polarization (ODNP) technique measures the translational mobility of water within the vicinity (5-15 Å) of preselected sites. The work presented here expands the capabilities of the ODNP technique and illuminates an important, previously unseen, property of the translational diffusion dynamics of water at the surface of DNA duplexes. We attach nitroxide radicals (i.e., spin labels) to multiple phosphate backbone positions of DNA duplexes, allowing ODNP to measure the hydration dynamics at select positions along the DNA surface. With a novel approach to ODNP analysis, we isolate the contributions of water molecules at these sites that undergo free translational diffusion from water molecules that either loosely bind to or exchange protons with the DNA. The results reveal that a significant population of water in a localized volume adjacent to the DNA surface exhibits fast, bulk-like characteristics and moves unusually rapidly compared to water found in similar probe volumes near protein and membrane surfaces. Control studies show that the observation of these characteristics are upheld even when the DNA duplex is tethered to streptavidin or the mobility of the nitroxides is altered. This implies that, as compared to protein or lipid surfaces, it is an intrinsic feature of the DNA duplex surface that it interacts only weakly with a significant fraction of the surface hydration water network. The displacement of this translationally mobile water is energetically less costly than that of more strongly bound water by up to several kBT and thus can lower the activation barrier for interactions involving the DNA surface.

  2. Multicomponent diffusion in molten salt NaF-ZrF4: Dynamical correlations and Maxwell-Stefan diffusivities

    NASA Astrophysics Data System (ADS)

    Baig, Mohammad Saad; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

    2016-05-01

    NaF-ZrF4 is used as a waste incinerator and as a coolant in Generation IV reactors.Structural and dynamical properties of molten NaF-ZrF4 system were studied along with Onsagercoefficients and Maxwell-Stefan (MS) Diffusivities applying Green-Kubo formalism and molecular dynamics (MD) simulations. The zirconium ions are found to be 8 fold coordinated with fluoride ions for all temperatures and concentrations. All the diffusive flux correlations show back-scattering. Even though the MS diffusivities are expected to depend very lightly on the composition because of decoupling of thermodynamic factor, the diffusivity ĐNa-F shows interesting behavior with the increase in concentration of ZrF4. This is because of network formation in NaF-ZrF4. Positive entropy constraints have been plotted to authenticate negative diffusivities observed.

  3. Multicomponent diffusion in molten salt NaF-ZrF{sub 4}: Dynamical correlations and Maxwell–Stefan diffusivities

    SciTech Connect

    Baig, Mohammad Saad Chakraborty, Brahmananda; Ramaniah, Lavanya M.

    2016-05-23

    NaF-ZrF{sub 4} is used as a waste incinerator and as a coolant in Generation IV reactors.Structural and dynamical properties of molten NaF-ZrF{sub 4} system were studied along with Onsagercoefficients and Maxwell–Stefan (MS) Diffusivities applying Green–Kubo formalism and molecular dynamics (MD) simulations. The zirconium ions are found to be 8 fold coordinated with fluoride ions for all temperatures and concentrations. All the diffusive flux correlations show back-scattering. Even though the MS diffusivities are expected to depend very lightly on the composition because of decoupling of thermodynamic factor, the diffusivity Đ{sub Na-F} shows interesting behavior with the increase in concentration of ZrF{sub 4}. This is because of network formation in NaF-ZrF{sub 4}. Positive entropy constraints have been plotted to authenticate negative diffusivities observed.

  4. Effect of ultrasonic capillary dynamics on the mechanics of thermosonic ball bonding.

    PubMed

    Huang, Yan; Shah, Aashish; Mayer, Michael; Zhou, Norman Y; Persic, John

    2010-01-01

    Microelectronic wire bonding is an essential step in today's microchip production. It is used to weld (bond) microwires to metallized pads of integrated circuits using ultrasound with hundreds of thousands of vibration cycles. Thermosonic ball bonding is the most popular variant of the wire bonding process and frequently investigated using finite element (FE) models that simplify the ultrasonic dynamics of the process with static or quasistatic boundary conditions. In this study, the ultrasonic dynamics of the bonding tool (capillary), made from Al(2)O(3), is included in a FE model. For more accuracy of the FE model, the main material parameters are measured. The density of the capillary was measured to be rho(cap) = 3552 +/- 100 kg/m(3). The elastic modulus of the capillary, E(cap) = 389 +/- 11 GPa, is found by comparing an auxiliary FE model of the free vibrating capillary with measured values. A capillary "nodding effect" is identified and found to be essential when describing the ultrasonic vibration shape. A main FE model builds on these results and adds bonded ball, pad, chip, and die attach components. There is excellent agreement between the main model and the ultrasonic force measured at the interface on a test chip with stress microsensors. Bonded ball and underpad stress results are reported. When adjusted to the same ultrasonic force, a simplified model without ultrasonic dynamics and with an infinitely stiff capillary tip is substantially off target by -40% for the maximum underpad stress. The compliance of the capillary causes a substantial inclination effect at the bonding interface between wire and pad. This oscillating inclination effect massively influences the stress fields under the pad and is studied in more detail. For more accurate results, it is therefore recommended to include ultrasonic dynamics of the bonding tool in mechanical FE models of wire bonding.

  5. High-Strength, Tough, and Self-Healing Nanocomposite Physical Hydrogels Based on the Synergistic Effects of Dynamic Hydrogen Bond and Dual Coordination Bonds.

    PubMed

    Shao, Changyou; Chang, Huanliang; Wang, Meng; Xu, Feng; Yang, Jun

    2017-08-30

    Dynamic noncovalent interactions with reversible nature are critical for the integral synthesis of self-healing biological materials. In this work, we developed a simple one-pot strategy to prepare a fully physically cross-linked nanocomposite hydrogel through the formation of the hydrogen bonds and dual metal-carboxylate coordination bonds within supramolecular networks, in which iron ions (Fe(3+)) and TEMPO oxidized cellulose nanofibrils (CNFs) acted as cross-linkers and led to the improved mechanical strength, toughness, time-dependent self-recovery capability and self-healing property. The spectroscopic analysis and rheological measurements corroborated the existence of hydrogen bonds and dual coordination bonds. The mechanical tests and microscopic morphology were explored to elucidate the recovery properties and toughening mechanisms. The hydrogen bonds tend to preferentially break prior to the coordination bonds associated complexes that act as skeleton to maintain primary structure integrity, and the survived coordination bonds with dynamic feature also serve as sacrificial bonds to dissipate another amount of energy after the rupture of hydrogen bonds, which collectively maximize the contribution of sacrificial bonds to energy dissipation while affording elasticity. Additionally, the multiple noncovalent interactions in diverse types synergistically serve as dynamic but highly stable associations, leading to the effective self-healing efficiency over 90% after damage. We expect that this facile strategy of incorporating the biocompatible and biodegradable CNFs as building blocks may enrich the avenue in exploration of dynamic and tunable cellulosic hydrogels to expand their potential applications in the biomedical field.

  6. Molecular dynamics simulation of imidazolium-based ionic liquids. I. Dynamics and diffusion coefficient

    NASA Astrophysics Data System (ADS)

    Kowsari, M. H.; Alavi, Saman; Ashrafizaadeh, Mahmud; Najafi, Bijan

    2008-12-01

    Molecular dynamics simulations are used to study the dynamics and transport properties of 12 room-temperature ionic liquids of the 1-alkyl-3-methylimidazolium [amim]+ (alkyl=methyl, ethyl, propyl, and butyl) family with PF6-, NO3-, and Cl- counterions. The explicit atom transferable force field of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] is used in the simulations. In this first part, the dynamics of the ionic liquids are characterized by studying the mean-square displacement (MSD) and the velocity autocorrelation function (VACF) for the centers of mass of the ions at 400 K. Trajectory averaging was employed to evaluate the diffusion coefficients at two temperatures from the linear slope of MSD(t) functions in the range of 150-300 ps and from the integration of the VACF(t) functions at 400 K. Detailed comparisons are made between the diffusion results from the MSD and VACF methods. The diffusion coefficients from the integration of the VACFs are closer to experimental values than the diffusion coefficients calculated from the slope of MSDs. Both methods can show good agreement with experiment in predicting relative trends in the diffusion coefficients and determining the role of the cation and anion structures on the dynamical behavior of this family of ionic liquids. The MSD and self-diffusion of relatively heavier imidazolium cations are larger than those of the lighter anions from the Einstein results, except for the case of [bmim][Cl]. The cationic transference number generally decreases with temperature, in good agreement with experiments. For the same anion, the cationic transference numbers decrease with increasing length of the alkyl chain, and for the same cation, the trends in the cationic transference numbers are [NO3]-<[Cl]-<[PF6]-. The trends in the diffusion coefficient in the series of cations with identical anions are [emim]+>[pmim]+>[bmim]+ and those for anions with identical cations are [NO3]->[PF6]->[Cl]-. The [dmim]+ has a

  7. Hydrogen bonding in a mixture of protic ionic liquids: a molecular dynamics simulation study.

    PubMed

    Paschek, Dietmar; Golub, Benjamin; Ludwig, Ralf

    2015-04-07

    We report results of molecular dynamics (MD) simulations characterising the hydrogen bonding in mixtures of two different protic ionic liquids sharing the same cation: triethylammonium-methylsulfonate (TEAMS) and triethylammonium-triflate (TEATF). The triethylammonium-cation acts as a hydrogen-bond donor, being able to donate a single hydrogen-bond. Both, the methylsulfonate- and the triflate-anions can act as hydrogen-bond acceptors, which can accept multiple hydrogen bonds via their respective SO3-groups. In addition, replacing a methyl-group in the methylsulfonate by a trifluoromethyl-group in the triflate significantly weakens the strength of a hydrogen bond from an adjacent triethylammonium cation to the oxygen-site in the SO3-group of the anion. Our MD simulations show that these subtle differences in hydrogen bond strength significantly affect the formation of differently-sized hydrogen-bonded aggregates in these mixtures as a function of the mixture-composition. Moreover, the reported hydrogen-bonded cluster sizes can be predicted and explained by a simple combinatorial lattice model, based on the approximate coordination number of the ions, and using statistical weights that mostly account for the fact that each anion can only accept three hydrogen bonds.

  8. Study of diffusion bond development in 6061 aluminum and its relationship to future high density fuels fabrication.

    SciTech Connect

    Prokofiev, I.; Wiencek, T.; McGann, D.

    1997-10-07

    Powder metallurgy dispersions of uranium alloys and silicides in an aluminum matrix have been developed by the RERTR program as a new generation of proliferation-resistant fuels. Testing is done with miniplate-type fuel plates to simulate standard fuel with cladding and matrix in plate-type configurations. In order to seal the dispersion fuel plates, a diffusion bond must exist between the aluminum coverplates surrounding the fuel meat. Four different variations in the standard method for roll-bonding 6061 aluminum were studied. They included mechanical cleaning, addition of a getter material, modifications to the standard chemical etching, and welding methods. Aluminum test pieces were subjected to a bend test after each rolling pass. Results, based on 400 samples, indicate that at least a 70% reduction in thickness is required to produce a diffusion bond using the standard rollbonding method versus a 60% reduction using the Type II method in which the assembly was welded 100% and contained open 9mm holes at frame corners.

  9. Tensile and creep properties of diffusion bonded titanium alloy IMI 834 to gamma titanium aluminide IHI alloy 01A

    SciTech Connect

    Holmquist, M.; Recina, V.; Pettersson, B.

    1999-04-23

    Diffusion bonding of the Ti-alloy Ti-5.8Al-4.0Sn-3.5Zr-0.7Nb-0.5Mo-0.35Se-0.06C (wt%) to the intermetallic {gamma}-based alloy Ti-33Al-2Fe-1.8V-0.1B (wt%) using hot isostatic pressing at 900 C, 200 MPa held for 1 h was studied. Sound joints without any pores or cracks with a width of approximately 5--7 {micro}m could be produced. Tensile testing showed that the strengths of the joints are similar to the strength of the {gamma}-TiAl base material at temperatures between room temperature and 600 C. The fracture occurs either at the joint or in the {gamma}-TiAl material. The fracture initiation process is a competition between initiation in the {gamma}-TiAl base material and initiation at the {gamma}-TiAl/diffusion bond interface. Creep testing showed that most of the creep elongation occurs in the Ti-alloy, but failure is initiated in the joint bond line. Creep causes degradation and pore formation in this line. Interlinkage of these pores creates a crack which grows slowly until the fracture toughness of the {gamma}-TiAl is exceeded and the crack starts to propagate in the {gamma}-TiAl material and terminates creep life.

  10. Finite-temperature dynamics of the spin- (1)/(2) bond alternating Heisenberg antiferromagnetic chain

    NASA Astrophysics Data System (ADS)

    Mikeska, H. J.; Luckmann, C.

    2006-05-01

    We present results for the dynamic structure factor of the S=1/2 bond alternating Heisenberg chain over a large range of frequencies and temperatures. Data are obtained from a numerical evaluation of thermal averages based on the calculation of all eigenvalues and eigenfunctions for chains of up to 20 spins. Interpretation is guided by the exact temperature dependence in the noninteracting dimer limit which remains qualitatively valid up to an interdimer exchange λ≈0.5 . The temperature induced central peak around zero frequency is clearly identified and aspects of the crossover to spin diffusion in its variation from low to high temperatures are discussed. The one-magnon peak acquires an asymmetric shape with increasing temperature. The two-magnon peak is dominated by the S=1 bound state which remains well defined up to temperatures of the order of J . The variation with temperature and wave vector of the integrated intensity for one-magnon and two-magnon scattering and of the central peak are discussed.

  11. Cosolvent Effects on Solute-Solvent Hydrogen-Bond Dynamics: Ultrafast 2D IR Investigations.

    PubMed

    Kashid, Somnath M; Jin, Geun Young; Bagchi, Sayan; Kim, Yung Sam

    2015-12-10

    Cosolvents strongly influence the solute-solvent interactions of biomolecules in aqueous environments and have profound effects on the stability and activity of several proteins and enzymes. Experimental studies have previously reported on the hydrogen-bond dynamics of water molecules in the presence of a cosolvent, but understanding the effects from a solute's perspective could provide greater insight into protein stability. Because carbonyl groups are abundant in biomolecules, the current study used 2D IR spectroscopy and molecular dynamics simulations to compare the hydrogen-bond dynamics of the solute's carbonyl group in aqueous solution, with and without the presence of DMSO as a cosolvent. 2D IR spectroscopy was used to quantitatively estimate the time scales of the hydrogen-bond dynamics of the carbonyl group in neat water and 1:1 DMSO/water solution. The 2D IR results show spectral signatures of a chemical exchange process: The presence of the cosolvent was found to lower the hydrogen-bond exchange rate by a factor of 5. The measured exchange rates were 7.50 × 10(11) and 1.48 × 10(11) s(-1) in neat water and 1:1 DMSO/water, respectively. Molecular dynamics simulations predict a significantly shorter carbonyl hydrogen-bond lifetime in neat water than in 1:1 DMSO/water and provide molecular insights into the exchange mechanism. The binding of the cosolvent to the solute was found to be accompanied by the release of hydrogen-bonded water molecules to the bulk. The widely different hydrogen-bond lifetimes and exchange rates with and without DMSO indicate a significant change in the ultrafast hydrogen-bond dynamics in the presence of a cosolvent, which, in turn, might play an important role in the stability and activity of biomolecules.

  12. Hydrogen-bonding structure and dynamics of aqueous carbonate species from car-parrinello molecular dynamics simulations.

    PubMed

    Kumar, P Padma; Kalinichev, Andrey G; Kirkpatrick, R James

    2009-01-22

    A comprehensive Car-Parrinello molecular dynamics (CP-MD) study of aqueous solutions of carbonic acid (H(2)CO(3)), bicarbonate (HCO(3)(-)), carbonate (CO(3)(2-)), and carbon dioxide (CO(2)) provides new quantitative insight into the structural and dynamic aspects of the hydrogen-bonding environments for these important aqueous species and their effects on the structure, H-bonding, and dynamical behavior of the surrounding water molecules. The hydration structures of the different carbonate species depend on their ability to accept and donate H-bonds with H(2)O. The H-bonds donated by the C-O-H sites of the carbonate species to water molecules are generally stronger and longer-lived than those accepted by these sites from water molecules. The structural relaxation among the water molecules is dominated by diffusional (translational) motion of H(2)O, whereas the H-bond reorganization is dominated by the librational motion of the water molecules and the carbonate species. The rates of structural relaxation of the H(2)O molecules and the rates of H-bond reorganization among them are slower in systems containing carbonate species, consistent with previous studies of simple salt solutions. The strengths and lifetimes of H-bonds involving the carbonate species positively correlate with the total negative charge on the species. H-bond donation from H(2)O to CO(2) is weak, but the presence of CO(2) noticeably affects the structure and structural relaxation of the surrounding H-bonding network leading to generally stronger H-bonds and slower relaxation rates, the behavior typical of a hydrophobic solute.

  13. Diffusion within α-CuI studied using ab initio molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Mohn, Chris E.; Stølen, Svein; Hull, Stephen

    2009-08-01

    The structure and dynamics of superionic α-CuI are studied in detail by means of ab initio Born-Oppenheimer molecular dynamics simulations. The extreme cation disorder and a soft immobile face centred cubic sublattice are evident from the highly diffuse atomic density profiles. The Cu-Cu pair distribution function and distribution of Cu-I-Cu bond angles possess distinct peaks at 2.6 Å and 60° respectively, which are markedly lower than the values expected from the average cationic density, pointing to the presence of pronounced short-range copper-copper correlations. Comparison with lattice static calculations shows that these correlations and the marked shift in the cationic density profile in the lang111rang directions are associated with a locally distorted cation sublattice, and that the movements within the tetrahedral cavities involve rapid jumps into and out of shallow basins on the system potential energy surface. On average, the iodines are surrounded by three coppers within their first coordination shell, with the fourth copper being located in a transition zone between two neighbouring iodine cavities. However, time-resolved analysis reveals that the local structure actually involves a mixture of threefold-, fourfold- and fivefold-coordinated iodines. Examination of the ionic trajectories shows that the copper ions jump rapidly to nearest neighbouring tetrahedral cavities (aligned in the lang100rang directions) following a markedly curved trajectory and often involving short-lived (~1 ps) interstitial positions. The nature of the correlated diffusion underlying the unusually high fraction of coppers with short residence time can be attributed to the presence of a large number of 'unsuccessful' jumps and the likelihood of cooperative motion of pairs of coppers. The calculated diffusion coefficient at 750 K, DCu = 2.8 × 10-5 cm2 s-1, is in excellent agreement with that found experimentally.

  14. Solvent dynamical behavior in an organogel phase as studied by NMR relaxation and diffusion experiments.

    PubMed

    Yemloul, Mehdi; Steiner, Emilie; Robert, Anthony; Bouguet-Bonnet, Sabine; Allix, Florent; Jamart-Grégoire, Brigitte; Canet, Daniel

    2011-03-24

    An organogelation process depends on the gelator-solvent pair. This study deals with the solvent dynamics once the gelation process is completed. The first approach used is relaxometry, i.e., the measurement of toluene proton longitudinal relaxation time T(1) as a function of the proton NMR resonance frequency (here in the 5 kHz to 400 MHz range). Pure toluene exhibits an unexpected T(1) variation, which has been identified as paramagnetic relaxation resulting from an interaction of toluene with dissolved oxygen. In the gel phase, this contribution is retrieved with, in addition, a strong decay at low frequencies assigned to toluene molecules within the gel fibers. Comparison of dispersion curves of pure toluene and toluene in the gel phase leads to an estimate of the proportion of toluene embedded within the organogel (found around 40%). The second approach is based on carbon-13 T(1) and nuclear Overhauser effect measurements, the combination of these two parameters providing direct information about the reorientation of C-H bonds. It appears clearly that reorientation of toluene is the same in pure liquid and in the gel phase. The only noticeable changes in carbon-13 longitudinal relaxation times are due to the so-called chemical shift anisotropy (csa) mechanism and reflect slight modifications of the toluene electronic distribution in the gel phase. NMR diffusion measurements by the pulse gradient spin-echo (PGSE) method allow us to determine the diffusion coefficient of toluene inside the organogel. It is roughly two-thirds of the one in pure toluene, thus indicating that self-diffusion is the only dynamical parameter to be slightly affected when the solvent is inside the gel structure. The whole set of experimental observations leads to the conclusion that, once the gel is formed, the solvent becomes essentially passive, although an important fraction is located within the gel structure.

  15. Diffusion of innovations dynamics, biological growth and catenary function

    NASA Astrophysics Data System (ADS)

    Guseo, Renato

    2016-12-01

    The catenary function has a well-known role in determining the shape of chains and cables supported at their ends under the force of gravity. This enables design using a specific static equilibrium over space. Its reflected version, the catenary arch, allows the construction of bridges and arches exploiting the dual equilibrium property under uniform compression. In this paper, we emphasize a further connection with well-known aggregate biological growth models over time and the related diffusion of innovation key paradigms (e.g., logistic and Bass distributions over time) that determine self-sustaining evolutionary growth dynamics in naturalistic and socio-economic contexts. Moreover, we prove that the 'local entropy function', related to a logistic distribution, is a catenary and vice versa. This special invariance may be explained, at a deeper level, through the Verlinde's conjecture on the origin of gravity as an effect of the entropic force.

  16. Rates of diffusion in dynamical systems with random jumps

    NASA Astrophysics Data System (ADS)

    Kobre, Elisha J.

    2005-12-01

    This dissertation explores the diffusion properties of a large class of measures under a dynamical system on bigcup i=0infinity S1i with randomly occurring jumps that behave according to a particular probability distribution. The drift rate for the center of mass of the system is then defined and is shown to be well defined Lebesgue almost everywhere. Properties of the drift rate are then explored. In particular the drift rate is shown to be continuous as a function of the probability "jump" distribution and, in a special case, it is shown that the drift rate increases with the probability of jumping. Finally, a central limit theorem for fluctuations about the drift rate is proved. The results are obtained by modeling the system as a random map on a compact space, and using the ergodic properties of the random map.

  17. Non-Gaussian Brownian Diffusion in Dynamically Disordered Thermal Environments.

    PubMed

    Tyagi, Neha; Cherayil, Binny J

    2017-07-27

    In this article, we suggest simple alternatives to the methods recently used by Jain and Sebastian [ J. Phys. Chem. B 2016 , 120 , 3988 ] and Chechkin et al. [ Phys. Rev. X 2017 , 7 , 021002 ] to treat a model of non-Gaussian Brownian diffusion based on the dynamics of a particle governed by Ornstein-Uhlenbeck modulated white noise. In addition to substantiating these authors' earlier findings (which show that a particle can execute a simple random walk even when the distribution of its displacements deviates from Gaussianity), our approach identifies another process, two-state white noise, that exhibits the same "anomalous" Brownian behavior. Indeed, we find that the modulation of white noise by any stochastic process whose time correlation function decays exponentially is likely to behave similarly, suggesting that the occurrence of such behavior can be widespread and commonplace.

  18. Dynamic diffuse optical tomography imaging of peripheral arterial disease.

    PubMed

    Khalil, Michael A; Kim, Hyun K; Kim, In-Kyong; Flexman, Molly; Dayal, Rajeev; Shrikhande, Gautam; Hielscher, Andreas H

    2012-09-01

    Peripheral arterial disease (PAD) is the narrowing of arteries due to plaque accumulation in the vascular walls. This leads to insufficient blood supply to the extremities and can ultimately cause cell death. Currently available methods are ineffective in diagnosing PAD in patients with calcified arteries, such as those with diabetes. In this paper we investigate the potential of dynamic diffuse optical tomography (DDOT) as an alternative way to assess PAD in the lower extremities. DDOT is a non-invasive, non-ionizing imaging modality that uses near-infrared light to create spatio-temporal maps of oxy- and deoxy-hemoglobin in tissue. We present three case studies in which we used DDOT to visualize vascular perfusion of a healthy volunteer, a PAD patient and a diabetic PAD patient with calcified arteries. These preliminary results show significant differences in DDOT time-traces and images between all three cases, underscoring the potential of DDOT as a new diagnostic tool.

  19. Beryllium dimer: a bond based on non-dynamical correlation.

    PubMed

    El Khatib, Muammar; Bendazzoli, Gian Luigi; Evangelisti, Stefano; Helal, Wissam; Leininger, Thierry; Tenti, Lorenzo; Angeli, Celestino

    2014-08-21

    The bond nature in beryllium dimer has been theoretically investigated using high-level ab initio methods. A series of ANO basis sets of increasing quality, going from sp to spdf ghi contractions, has been employed, combined with HF, CAS-SCF, CISD, and MRCI calculations with several different active spaces. The quality of these calculations has been checked by comparing the results with valence Full-CI calculations, performed with the same basis sets. It is shown that two quasi-degenerated partly occupied orbitals play a crucial role to give a qualitatively correct description of the bond. Their nature is similar to that of the edge orbitals that give rise to the quasi-degenerated singlet-triplet states in longer beryllium chains.

  20. Bimodal dynamics of mechanically constrained hydrogen bonds revealed by vibrational photon echoes

    NASA Astrophysics Data System (ADS)

    Bodis, Pavol; Yeremenko, Sergiy; Berná, José; Buma, Wybren J.; Leigh, David A.; Woutersen, Sander

    2011-04-01

    We have investigated the dynamics of the hydrogen bonds that connect the components of a [2]rotaxane in solution. In this rotaxane, the amide groups in the benzylic-amide macrocycle and the succinamide thread are connected by four equivalent N-HṡṡṡO=C hydrogen bonds. The fluctuations of these hydrogen bonds are mirrored by the frequency fluctuations of the NH-stretch modes, which are probed by means of three-pulse photon-echo peak shift spectroscopy. The hydrogen-bond fluctuations occur on three different time scales, with time constants of 0.1, 0.6, and ⩾200 ps. Comparing these three time scales to the ones found in liquid formamide, which contains the same hydrogen-bonded amide motif but without mechanical constraints, we find that the faster two components, which are associated with small-amplitude fluctuations in the strength of the N-HṡṡṡO=C hydrogen bonds, are very similar in the liquid and the rotaxane. However, the third component, which is associated with the breaking and subsequent reformation of hydrogen bonds, is found to be much slower in the rotaxane than in the liquid. It can be concluded that the mechanical bonding in a rotaxane does not influence the amplitude and time scale of the small-amplitude fluctuations of the hydrogen bonds, but strongly slows down the complete dissociation of these hydrogen bonds. This is probably because in a rotaxane breaking of the macrocycle-axle contacts is severely hindered by the mechanical constraints. The hydrogen-bond dynamics in rotaxane-based molecular machines can therefore be regarded as liquidlike on a time scale 1 ps and less, but structurally frozen on longer (up to at least 200 ps) time scales.

  1. Critical Dynamics Behavior of the Wolff Algorithm in the Site-Bond-Correlated Ising Model

    NASA Astrophysics Data System (ADS)

    Campos, P. R. A.; Onody, R. N.

    Here we apply the Wolff single-cluster algorithm to the site-bond-correlated Ising model and study its critical dynamical behavior. We have verified that the autocorrelation time diminishes in the presence of dilution and correlation, showing that the Wolff algorithm performs even better in such situations. The critical dynamical exponents are also estimated.

  2. Topological Properties of Chemical Bonds from Static and Dynamic Electron Densities.

    PubMed

    Jagannatha Prathapa, Siriyara; Held, Jeanette; van Smaalen, Sander

    2013-09-01

    Dynamic and static electron densities (EDs) based on the independent spherical atom model (IAM) and multipole (MP) models of crambin were successfully computed, holding no series-termination effects. The densities are compared to EDs of small biological molecules at diverse temperatures. It is outlined that proteins exhibit an intrinsic flexibility, present as frozen disorder at 100 K, in contrast to small molecules. The flexibility of the proteins is reflected by atomic displacement parameters (B-factors), which are considerably larger than for small molecules at 298 K. Thus, an optimal deconvolution of deformation density and thermal motion is not guaranteed, which prevents a free refinement of MP parameters but allows an application of transferable, fixed MP parameters. The analysis of the topological properties, such as the density at bond critical points (BCPs) and the Laplacian, reveals systematic differences between static and dynamic EDs. Zero-point-vibrations, yet present in dynamic EDs at low temperature, affect but marginally the EDs of small molecules. The zero-point-vibrations cause a smearing of the ED, which becomes more pronounced with increasing temperature. Topological properties, primarily the Laplacian, of covalent bonds appear to be more sensitive to effects by temperature and the polarity of the bonds. However, dynamic EDs at ca. 20 K based on MP models provide a good characterization of chemical bonding. Both the density at BCPs and the Laplacian of hydrogen bonds constitute similar values from static and dynamic EDs for all studied temperatures. Deformation densities demonstrate the necessity of the employment of MP parameters in order to comprise the nature of covalent bonds. The character of hydrogen bonds can be roughly pictured by IAM, whereas MP parameters are recommended for a classification of hydrogen bonds beyond a solely interpretation of topological properties.

  3. Topological Properties of Chemical Bonds from Static and Dynamic Electron Densities

    PubMed Central

    Jagannatha Prathapa, Siriyara; Held, Jeanette; van Smaalen, Sander

    2013-01-01

    Dynamic and static electron densities (EDs) based on the independent spherical atom model (IAM) and multipole (MP) models of crambin were successfully computed, holding no series-termination effects. The densities are compared to EDs of small biological molecules at diverse temperatures. It is outlined that proteins exhibit an intrinsic flexibility, present as frozen disorder at 100 K, in contrast to small molecules. The flexibility of the proteins is reflected by atomic displacement parameters (B-factors), which are considerably larger than for small molecules at 298 K. Thus, an optimal deconvolution of deformation density and thermal motion is not guaranteed, which prevents a free refinement of MP parameters but allows an application of transferable, fixed MP parameters. The analysis of the topological properties, such as the density at bond critical points (BCPs) and the Laplacian, reveals systematic differences between static and dynamic EDs. Zero-point-vibrations, yet present in dynamic EDs at low temperature, affect but marginally the EDs of small molecules. The zero-point-vibrations cause a smearing of the ED, which becomes more pronounced with increasing temperature. Topological properties, primarily the Laplacian, of covalent bonds appear to be more sensitive to effects by temperature and the polarity of the bonds. However, dynamic EDs at ca. 20 K based on MP models provide a good characterization of chemical bonding. Both the density at BCPs and the Laplacian of hydrogen bonds constitute similar values from static and dynamic EDs for all studied temperatures. Deformation densities demonstrate the necessity of the employment of MP parameters in order to comprise the nature of covalent bonds. The character of hydrogen bonds can be roughly pictured by IAM, whereas MP parameters are recommended for a classification of hydrogen bonds beyond a solely interpretation of topological properties. PMID:25995522

  4. Hydrogen bond dynamics governs the effective photoprotection mechanism of plant phenolic sunscreens.

    PubMed

    Liu, Fang; Du, Likai; Lan, Zhenggang; Gao, Jun

    2017-02-15

    Sinapic acid derivatives are important sunscreen species in natural plants, which could provide protection from solar UV radiation. Using a combination of ultrafast excited state dynamics, together with classical molecular dynamics studies, we demonstrate that there is direct coupling of hydrogen bond motion with excited state photoprotection dynamics as part of the basic mechanism in solution. Beyond the intra-molecular degree of freedom, the inter-molecular motions on all timescales are potentially important for the photochemical or photophysical events, ranging from the ultrafast hydrogen bond motion to solvent rearrangements. This provides not only an enhanced understanding of the anomalous experimental spectroscopic results, but also the key idea in the development of sunscreen agents with improved photo-chemical properties. We suggest that the hydrogen bond dynamics coupled excited state photoprotection mechanism may also be possible in a broad range of bio-related molecules in the condensed phase.

  5. Dynamic studies of proton diffusion in mesoscopic heterogeneous matrix

    PubMed Central

    Gutman, M.; Nachliel, E.; Kiryati, S.

    1992-01-01

    The thin water layer, as found in chloroplast or mitochondria, is confined between low dielectric amphypathic surfaces a few nm apart. The physical properties of this mesoscopic space, and how its dimensions affect the rate of chemical reactions proceeding in it, is the subject for this study. The method selected for this purpose is time resolved fluorometry which can monitor the reversible dissociation of a proton from excited molecule of pyranine (8 hydroxy pyrene 1,3,6 tri sulfonate) trapped in thin water layers of a multilamellar vesicle made of neutral or slightly charged phospholipids. The results were analyzed by a computer program of N. Agmon (Pines, E., D. Huppert, and N. Agmon. 1988. J. Am. Chem. Soc. 88:5620-5630) that simulates the diffusion of a proton, subjected to electrostatic attraction, in a thin water layer enclosed between low affinity, proton binding surfaces. The analysis determines the diffusion coefficient of the proton, the effective dielectric constant of the water and the water accessibility of the phosphomoieties of the lipids. These parameters were measured for various lipids [egg-phosphatidylcholine (egg PC), dipalmitoyl phosphatidylcholine (DPPC), cholesterol + DPPC (1:1) and egg PC plus phosphatidyl serine (9:1)] and under varying osmotic pressure which reduces the width of the water layer down to ∼10 ∼ across. We found that: (a) The effective dielectric constant of the aqueous layer, depending on the lipid composition, is ∼40. (b) The diffusion coefficient of the proton in the thin layer (30-10 ∼ across) is that measured in bulk water D = 9.3 10-5 cm2/s, indicating that the water retains its normal liquid state even on contact with the membrane. (c) The reactivity of the phosphomoiety, quantitated by rate of its reaction with proton, diminishes under lateral pressure which reduces the surface area per lipid. We find no evidence for abnormal dynamics of proton transfer at the lipid water interface which, by any mechanism

  6. HBonanza: a computer algorithm for molecular-dynamics-trajectory hydrogen-bond analysis.

    PubMed

    Durrant, Jacob D; McCammon, J Andrew

    2011-11-01

    In the current work, we present a hydrogen-bond analysis of 2673 ligand-receptor complexes that suggests the total number of hydrogen bonds formed between a ligand and its receptor is a poor predictor of ligand potency; furthermore, even that poor prediction does not suggest a statistically significant correlation between hydrogen-bond formation and potency. While we are not the first to suggest that hydrogen bonds on average do not generally contribute to ligand binding affinities, this additional evidence is nevertheless interesting. The primary role of hydrogen bonds may instead be to ensure specificity, to correctly position the ligand within the active site, and to hold the protein active site in a ligand-friendly conformation. We also present a new computer program called HBonanza (hydrogen-bond analyzer) that aids the analysis and visualization of hydrogen-bond networks. HBonanza, which can be used to analyze single structures or the many structures of a molecular dynamics trajectory, is open source and python implemented, making it easily editable, customizable, and platform independent. Unlike many other freely available hydrogen-bond analysis tools, HBonanza provides not only a text-based table describing the hydrogen-bond network, but also a Tcl script to facilitate visualization in VMD, a popular molecular visualization program. Visualization in other programs is also possible. A copy of HBonanza can be obtained free of charge from http://www.nbcr.net/hbonanza. Copyright © 2011 Elsevier Inc. All rights reserved.

  7. HBonanza: A Computer Algorithm for Molecular-Dynamics-Trajectory Hydrogen-Bond Analysis

    PubMed Central

    Durrant, Jacob D.; McCammon, J. Andrew

    2011-01-01

    In the current work, we present a hydrogen-bond analysis of 2,673 ligand-receptor complexes that suggests the total number of hydrogen bonds formed between a ligand and its protein receptor is a poor predictor of ligand potency; furthermore, even that poor prediction does not suggest a statistically significant correlation between hydrogen-bond formation and potency. While we are not the first to suggest that hydrogen bonds on average do not generally contribute to ligand binding affinities, this additional evidence is nevertheless interesting. The primary role of hydrogen bonds may instead be to ensure specificity, to correctly position the ligand within the active site, and to hold the protein active site in a ligand-friendly conformation. We also present a new computer program called HBonanza (hydrogen-bond analyzer) that aids the analysis and visualization of hydrogen-bond networks. HBonanza, which can be used to analyze single structures or the many structures of a molecular dynamics trajectory, is open source and python implemented, making it easily editable, customizable, and platform independent. Unlike many other freely available hydrogen-bond analysis tools, HBonanza provides not only a text-based table describing the hydrogen-bond network, but also a Tcl script to facilitate visualization in VMD, a popular molecular visualization program. Visualization in other programs is also possible. A copy of HBonanza can be obtained free of charge from http://www.nbcr.net/hbonanza. PMID:21880522

  8. Thermodynamics of hydration of fullerols [C60(OH)n] and hydrogen bond dynamics in their hydration shells

    NASA Astrophysics Data System (ADS)

    Keshri, Sonanki; Tembe, B. L.

    2017-02-01

    Molecular dynamics simulations of fullerene and fullerols [C60(OH)n, where n = 2-30] in aqueous solutions have been performed for the purpose of obtaining a detailed understanding of the structural and dynamic properties of these nanoparticles in water. The structures, dynamics and hydration free energies of the solute molecules in water have been analysed. Radial distribution functions, spatial density distribution functions and hydrogen bond analyses are employed to characterize the solvation shells of water around the central solute molecules. We have found that water molecules form two solvation shells around the central solute molecule. Hydrogen bonding in the bulk solvent is unaffected by increasing n. The large decrease in solvation enthalpies of these solute molecules for n > 14 enhances solubilisation. The diffusion constants of solute molecules decrease with increasing n. The solvation free energy of C60 in water is positive (52.8 kJ/mol), whereas its value for C60(OH)30 is highly negative (-427.1 kJ/mol). The effects of surface hydroxylation become more dominant once the fullerols become soluble.

  9. Comparison of structural behavior of superplastically formed/diffusion-bonded sandwich structures and honeycomb core sandwich structures

    NASA Technical Reports Server (NTRS)

    Ko, W. L.

    1980-01-01

    A superplasticity formed/diffusion-bonded (SPF/DB) orthogonally corrugated core sandwich structure is discussed and its structural behavior is compared to that of a conventional honeycomb core sandwich structure. The stiffness and buckling characteristics of the two types of sandwich structures are compared under conditions of equal structural density. It is shown that under certain conditions, the SPF/DB orthogonally corrugated core sandwich structure is slightly more efficient than the optimum honeycomb core (square-cell core) sandwich structure. However, under different conditions, this effect can be reversed.

  10. 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.

  11. Transient Liquid Phase Diffusion Bonding of Magnesium Alloy (Mg-AZ31) to Titanium Alloy (Ti-6Al-4V)

    NASA Astrophysics Data System (ADS)

    Atieh, Anas Mahmoud

    The magnesium alloy Mg-AZ31 and titanium alloy Ti-6Al-4V have physical characteristics and mechanical properties that makes it attractive for a wide range of engineering applications in the aerospace and automotive industries. However, the differences in melting temperature and coefficient of thermal expansion hinder the use of traditional fusion welding techniques. Transient liquid phase (TLP) bonding of magnesium alloy Mg-AZ31 and titanium alloy Ti-6Al- 4V was performed and different interlayer types and configurations were used to facilitate joint formation. The joining of these alloys using Ni foils was successful at a bonding temperature of 515°C, bonding pressure 0.2 MPa, for bonding time of 5 minutes. At the Ni/Mg-AZ31 bond interface, the formation of a eutectic liquid between Mg and Ni was observed. The formation of Mg2Ni and Mg3AlNi2 were identified along the bond interface resulting in an isothermally solidified joint. At the Ni/Ti-6Al-4V interface, the solid-state diffusion process results in joint formation. The use of double Ni-Cu sandwich joint resulted in further enhancement in joint formation and this produced joints with greater shear strength values. The configuration of Mg-AZ31/Cu- Ni/Ti-6Al-4V or Mg-AZ31/Ni-Cu/Ti-6Al-4V influence the mechanism of bonding and the type of intermetallics formed within the joint. The application of thin Ni electrodeposited coatings resulted in further enhancements of joint quality due to better surface-to-surface contact and a reduction in the formation of intermetallics at the joint. The effect of Cu nano-particles in the coatings was found to decrease the eutectic zone width and this resulted in an increase the shear strength of the joints. The highest shear strength of 69 MPa was possible with bonds made using coatings containing Cu nano-particle dispersion.

  12. Molecular dynamics simulations reveal that water diffusion between graphene oxide layers is slow

    DOE PAGES

    Devanathan, Ram; Chase-Woods, Dylan; Shin, Yongsoon; ...

    2016-07-08

    Membranes made of stacked layers of graphene oxide (GO) hold the tantalizing promise of revolutionizing desalination and water filtration if selective transport of molecules can be controlled. We present the findings of a molecular dynamics simulation study of water intercalated between GO layers that have a C/O ratio of 4. We simulated a range of hydration levels from 1 wt.% to 23.3 wt.% water. The interlayer spacing increased upon hydration from 0.8 nm to 1.1 nm. We also synthesized GO membranes that showed an increase in spacing from about 0.7 nm to 0.8 nm and an increase in mass ofmore » about 14% on hydration. Water diffusion through GO layers is an order of magnitude slower than that in bulk water, because of strong hydrogen bonded interactions. Most of the water molecules are bound to OH groups even at the highest hydration level. We observed large water clusters that could span graphitic regions, oxidized regions and holes that have been experimentally observed in GO. As a result, slow interlayer diffusion can be consistent with experimentally observed water transport in GO if holes lead to a shorter path length than previously assumed and sorption serves as a key rate-limiting step.« less

  13. Molecular dynamics simulations reveal that water diffusion between graphene oxide layers is slow

    SciTech Connect

    Devanathan, Ram; Chase-Woods, Dylan; Shin, Yongsoon; Gotthold, David W.

    2016-07-08

    Membranes made of stacked layers of graphene oxide (GO) hold the tantalizing promise of revolutionizing desalination and water filtration if selective transport of molecules can be controlled. We present the findings of a molecular dynamics simulation study of water intercalated between GO layers that have a C/O ratio of 4. We simulated a range of hydration levels from 1 wt.% to 23.3 wt.% water. The interlayer spacing increased upon hydration from 0.8 nm to 1.1 nm. We also synthesized GO membranes that showed an increase in spacing from about 0.7 nm to 0.8 nm and an increase in mass of about 14% on hydration. Water diffusion through GO layers is an order of magnitude slower than that in bulk water, because of strong hydrogen bonded interactions. Most of the water molecules are bound to OH groups even at the highest hydration level. We observed large water clusters that could span graphitic regions, oxidized regions and holes that have been experimentally observed in GO. As a result, slow interlayer diffusion can be consistent with experimentally observed water transport in GO if holes lead to a shorter path length than previously assumed and sorption serves as a key rate-limiting step.

  14. Molecular Dynamics Simulations Reveal that Water Diffusion between Graphene Oxide Layers is Slow

    NASA Astrophysics Data System (ADS)

    Devanathan, Ram; Chase-Woods, Dylan; Shin, Yongsoon; Gotthold, David W.

    2016-07-01

    Membranes made of stacked layers of graphene oxide (GO) hold the tantalizing promise of revolutionizing desalination and water filtration if selective transport of molecules can be controlled. We present the findings of an integrated study that combines experiment and molecular dynamics simulation of water intercalated between GO layers. We simulated a range of hydration levels from 1 wt.% to 23.3 wt.% water. The interlayer spacing increased upon hydration from 0.8 nm to 1.1 nm. We also synthesized GO membranes that showed an increase in layer spacing from about 0.7 nm to 0.8 nm and an increase in mass of about 15% on hydration. Water diffusion through GO layers is an order of magnitude slower than that in bulk water, because of strong hydrogen bonded interactions. Most of the water molecules are bound to OH groups even at the highest hydration level. We observed large water clusters that could span graphitic regions, oxidized regions and holes that have been experimentally observed in GO. Slow interlayer diffusion can be consistent with experimentally observed water transport in GO if holes lead to a shorter path length than previously assumed and sorption serves as a key rate-limiting step.

  15. Molecular Dynamics Simulations Reveal that Water Diffusion between Graphene Oxide Layers is Slow

    PubMed Central

    Devanathan, Ram; Chase-Woods, Dylan; Shin, Yongsoon; Gotthold, David W.

    2016-01-01

    Membranes made of stacked layers of graphene oxide (GO) hold the tantalizing promise of revolutionizing desalination and water filtration if selective transport of molecules can be controlled. We present the findings of an integrated study that combines experiment and molecular dynamics simulation of water intercalated between GO layers. We simulated a range of hydration levels from 1 wt.% to 23.3 wt.% water. The interlayer spacing increased upon hydration from 0.8 nm to 1.1 nm. We also synthesized GO membranes that showed an increase in layer spacing from about 0.7 nm to 0.8 nm and an increase in mass of about 15% on hydration. Water diffusion through GO layers is an order of magnitude slower than that in bulk water, because of strong hydrogen bonded interactions. Most of the water molecules are bound to OH groups even at the highest hydration level. We observed large water clusters that could span graphitic regions, oxidized regions and holes that have been experimentally observed in GO. Slow interlayer diffusion can be consistent with experimentally observed water transport in GO if holes lead to a shorter path length than previously assumed and sorption serves as a key rate-limiting step. PMID:27388562

  16. Dynamic control of vapor diffusion protein crystal growth

    SciTech Connect

    Bray, Terry L.; Powell, Deborah L.; DeLucas, Lawrence J.

    1997-01-10

    Two laboratory based systems have been constructed to demonstrate methods which will allow for dynamic control of protein crystal growth. The technologies developed in these systems will be incorporated into future flight hardware for use in microgravity studies. The first system uses a precisely controlled vapor diffusion approach to monitor and control protein crystal growth. The system utilizes a humidity sensor and various interfaces under computer control to effect virtually any evaporation rate from up to 40 different growth solutions simultaneously. A second system utilizes the key features of the first system with the addition of a static laser light scattering sensor which can be used to detect aggregation events and trigger a change in the evaporation rate for a growth solution. This system also demonstrates that a Control/Follower configuration can be used to actively monitor one chamber and accurately control replicate chambers relative to the Control chamber. Results from experiments with both systems demonstrate that evaporation rate and dynamic control produce systematic effects on the size and number of crystals obtained. Both of these systems demonstrate significant advances in the ability of researchers to gain control of the protein crystal growth process and will provide tremendous opportunities for both terrestrial and microgravity research.

  17. Diffusion dynamics of synaptic molecules during inhibitory postsynaptic plasticity

    PubMed Central

    Petrini, Enrica Maria; Barberis, Andrea

    2014-01-01

    The plasticity of inhibitory transmission is expected to play a key role in the modulation of neuronal excitability and network function. Over the last two decades, the investigation of the determinants of inhibitory synaptic plasticity has allowed distinguishing presynaptic and postsynaptic mechanisms. While there has been a remarkable progress in the characterization of presynaptically-expressed plasticity of inhibition, the postsynaptic mechanisms of inhibitory long-term synaptic plasticity only begin to be unraveled. At postsynaptic level, the expression of inhibitory synaptic plasticity involves the rearrangement of the postsynaptic molecular components of the GABAergic synapse, including GABAA receptors, scaffold proteins and structural molecules. This implies a dynamic modulation of receptor intracellular trafficking and receptor surface lateral diffusion, along with regulation of the availability and distribution of scaffold proteins. This Review will focus on the mechanisms of the multifaceted molecular reorganization of the inhibitory synapse during postsynaptic plasticity, with special emphasis on the key role of protein dynamics to ensure prompt and reliable activity-dependent adjustments of synaptic strength. PMID:25294987

  18. Hydrogen bond network rearrangement dynamics in water clusters: Effects of intermolecular vibrational excitation on tunneling rates

    NASA Astrophysics Data System (ADS)

    Cole, William T. S.; Saykally, Richard J.

    2017-08-01

    Theoretical studies of hydrogen bond network rearrangement (HBNR) dynamics in liquid water have indicated that librational motions initiate the hydrogen bond breaking/formation processes. We present the results of using a simple time evolution method to extract and compare the tunneling lifetimes for motions that break and reform the hydrogen bond for the water dimer, trimer, and pentamer from the experimentally measured tunneling splittings in the ground and excited intermolecular vibrational states. We find that the specific nature of the intermolecular vibrational excitation does not significantly influence the tunneling lifetime of the dimer, but that only excitations to a librational vibration affect the water trimer and pentamer lifetimes. The specific enhancement of bifurcation tunneling in larger clusters relative to the dimer also indicates that hydrogen bond cooperativity is a vital element of these dynamics.

  19. Hydrogen bond network rearrangement dynamics in water clusters: Effects of intermolecular vibrational excitation on tunneling rates.

    PubMed

    Cole, William T S; Saykally, Richard J

    2017-08-14

    Theoretical studies of hydrogen bond network rearrangement (HBNR) dynamics in liquid water have indicated that librational motions initiate the hydrogen bond breaking/formation processes. We present the results of using a simple time evolution method to extract and compare the tunneling lifetimes for motions that break and reform the hydrogen bond for the water dimer, trimer, and pentamer from the experimentally measured tunneling splittings in the ground and excited intermolecular vibrational states. We find that the specific nature of the intermolecular vibrational excitation does not significantly influence the tunneling lifetime of the dimer, but that only excitations to a librational vibration affect the water trimer and pentamer lifetimes. The specific enhancement of bifurcation tunneling in larger clusters relative to the dimer also indicates that hydrogen bond cooperativity is a vital element of these dynamics.

  20. The effect of hydrogen bonding on the diffusion of water in n-alkanes and n-alcohols measured with a novel single microdroplet method

    NASA Astrophysics Data System (ADS)

    Su, Jonathan T.; Duncan, P. Brent; Momaya, Amit; Jutila, Arimatti; Needham, David

    2010-01-01

    While the Stokes-Einstein (SE) equation predicts that the diffusion coefficient of a solute will be inversely proportional to the viscosity of the solvent, this relation is commonly known to fail for solutes, which are the same size or smaller than the solvent. Multiple researchers have reported that for small solutes, the diffusion coefficient is inversely proportional to the viscosity to a fractional power, and that solutes actually diffuse faster than SE predicts. For other solvent systems, attractive solute-solvent interactions, such as hydrogen bonding, are known to retard the diffusion of a solute. Some researchers have interpreted the slower diffusion due to hydrogen bonding as resulting from the effective diffusion of a larger complex of a solute and solvent molecules. We have developed and used a novel micropipette technique, which can form and hold a single microdroplet of water while it dissolves in a diffusion controlled environment into the solvent. This method has been used to examine the diffusion of water in both n-alkanes and n-alcohols. It was found that the polar solute water, diffusing in a solvent with which it cannot hydrogen bond, closely resembles small nonpolar solutes such as xenon and krypton diffusing in n-alkanes, with diffusion coefficients ranging from 12.5×10-5 cm2/s for water in n-pentane to 1.15×10-5 cm2/s for water in hexadecane. Diffusion coefficients were found to be inversely proportional to viscosity to a fractional power, and diffusion coefficients were faster than SE predicts. For water diffusing in a solvent (n-alcohols) with which it can hydrogen bond, diffusion coefficient values ranged from 1.75×10-5 cm2/s in n-methanol to 0.364×10-5 cm2/s in n-octanol, and diffusion was slower than an alkane of corresponding viscosity. We find no evidence for solute-solvent complex diffusion. Rather, it is possible that the small solute water may be retarded by relatively longer residence times (compared to non-H-bonding solvents

  1. The effect of hydrogen bonding on the diffusion of water in n-alkanes and n-alcohols measured with a novel single microdroplet method.

    PubMed

    Su, Jonathan T; Duncan, P Brent; Momaya, Amit; Jutila, Arimatti; Needham, David

    2010-01-28

    While the Stokes-Einstein (SE) equation predicts that the diffusion coefficient of a solute will be inversely proportional to the viscosity of the solvent, this relation is commonly known to fail for solutes, which are the same size or smaller than the solvent. Multiple researchers have reported that for small solutes, the diffusion coefficient is inversely proportional to the viscosity to a fractional power, and that solutes actually diffuse faster than SE predicts. For other solvent systems, attractive solute-solvent interactions, such as hydrogen bonding, are known to retard the diffusion of a solute. Some researchers have interpreted the slower diffusion due to hydrogen bonding as resulting from the effective diffusion of a larger complex of a solute and solvent molecules. We have developed and used a novel micropipette technique, which can form and hold a single microdroplet of water while it dissolves in a diffusion controlled environment into the solvent. This method has been used to examine the diffusion of water in both n-alkanes and n-alcohols. It was found that the polar solute water, diffusing in a solvent with which it cannot hydrogen bond, closely resembles small nonpolar solutes such as xenon and krypton diffusing in n-alkanes, with diffusion coefficients ranging from 12.5x10(-5) cm(2)/s for water in n-pentane to 1.15x10(-5) cm(2)/s for water in hexadecane. Diffusion coefficients were found to be inversely proportional to viscosity to a fractional power, and diffusion coefficients were faster than SE predicts. For water diffusing in a solvent (n-alcohols) with which it can hydrogen bond, diffusion coefficient values ranged from 1.75x10(-5) cm(2)/s in n-methanol to 0.364x10(-5) cm(2)/s in n-octanol, and diffusion was slower than an alkane of corresponding viscosity. We find no evidence for solute-solvent complex diffusion. Rather, it is possible that the small solute water may be retarded by relatively longer residence times (compared to non-H-bonding

  2. The effect of hydrogen bonding on the diffusion of water in n-alkanes and n-alcohols measured with a novel single microdroplet method

    PubMed Central

    Su, Jonathan T.; Duncan, P. Brent; Momaya, Amit; Jutila, Arimatti; Needham, David

    2010-01-01

    While the Stokes–Einstein (SE) equation predicts that the diffusion coefficient of a solute will be inversely proportional to the viscosity of the solvent, this relation is commonly known to fail for solutes, which are the same size or smaller than the solvent. Multiple researchers have reported that for small solutes, the diffusion coefficient is inversely proportional to the viscosity to a fractional power, and that solutes actually diffuse faster than SE predicts. For other solvent systems, attractive solute-solvent interactions, such as hydrogen bonding, are known to retard the diffusion of a solute. Some researchers have interpreted the slower diffusion due to hydrogen bonding as resulting from the effective diffusion of a larger complex of a solute and solvent molecules. We have developed and used a novel micropipette technique, which can form and hold a single microdroplet of water while it dissolves in a diffusion controlled environment into the solvent. This method has been used to examine the diffusion of water in both n-alkanes and n-alcohols. It was found that the polar solute water, diffusing in a solvent with which it cannot hydrogen bond, closely resembles small nonpolar solutes such as xenon and krypton diffusing in n-alkanes, with diffusion coefficients ranging from 12.5×10−5 cm2∕s for water in n-pentane to 1.15×10−5 cm2∕s for water in hexadecane. Diffusion coefficients were found to be inversely proportional to viscosity to a fractional power, and diffusion coefficients were faster than SE predicts. For water diffusing in a solvent (n-alcohols) with which it can hydrogen bond, diffusion coefficient values ranged from 1.75×10−5 cm2∕s in n-methanol to 0.364×10−5 cm2∕s in n-octanol, and diffusion was slower than an alkane of corresponding viscosity. We find no evidence for solute-solvent complex diffusion. Rather, it is possible that the small solute water may be retarded by relatively longer residence times (compared to non-H-bonding

  3. Intermolecular dynamical charge fluctuations in water: a signature of the H-bond network.

    PubMed

    Sharma, Manu; Resta, Raffaele; Car, Roberto

    2005-10-28

    We report a simulation of deuterated water using a Car-Parrinello approach based on maximally localized Wannier functions. This provides local information on the dynamics of the hydrogen-bond network and on the origin of the low-frequency infrared activity. The oscillator strength of the translational modes, peaked around approximately 200 cm-1, is anisotropic and originates from intermolecular--not intramolecular--charge fluctuations. These fluctuations are a signature of a tetrahedral hydrogen-bonding environment.

  4. Catastrophic fault diagnosis in dynamic systems using bond graph methods

    SciTech Connect

    Yarom, Tamar.

    1990-01-01

    Detection and diagnosis of faults has become a critical issue in high performance engineering systems as well as in mass-produced equipment. It is particularly helpful when the diagnosis can be made at the initial design level with respect to a prospective fault list. A number of powerful methods have been developed for aiding in the general fault analysis of designs. Catastrophic faults represent the limit case of complete local failure of connections or components. They result in the interruption of energy transfer between corresponding points in the system. In this work the conventional approach to fault detection and diagnosis is extended by means of bond-graph methods to a wide variety of engineering systems. Attention is focused on catastrophic fault diagnosis. A catastrophic fault dictionary is generated from the system model based on topological properties of the bond graph. The dictionary is processed by existing methods to extract a catastrophic fault report to aid the engineer in performing a design analysis.

  5. NMR spectra and translational diffusion of protons in crystals with hydrogen bonds

    NASA Astrophysics Data System (ADS)

    Timokhin, V. M.; Garmash, V. M.; Tarasov, V. P.

    2015-07-01

    Investigation of proton transport in hydrogen-bond crystals at low temperatures is currently one of important problems in the semiconductor physics. With the use of the NMR spectra of wide-band-gap hydrogen-bond crystals grown in H2O and D2O solutions, we have succeeded in finding a direct proof of the presence of protons in the mobile phase, determined their activation energy in good agreement with the spectra of thermally stimulated depolarization currents and with the infrared spectra, and, as a result, clarified the mechanism of proton transport and tunneling.

  6. Multicomponent diffusion in molten salt LiF-BeF{sub 2}: Dynamical correlations and Maxwell–Stefan diffusivities

    SciTech Connect

    Chakraborty, Brahmananda Ramaniah, Lavanya M.

    2015-06-24

    Applying Green–Kubo formalism and equilibrium molecular dynamics (MD) simulations, we have studied the dynamic correlation, Onsager coeeficients and Maxwell–Stefan (MS) Diffusivities of molten salt LiF-BeF{sub 2}, which is used as coolant in high temperature reactor. All the diffusive flux correlations show back-scattering or cage dynamics which becomes pronouced at higher temperature. Although the MS diffusivities are expected to depend very lightly on the composition due to decoupling of thermodynamic factor, the diffusivity Đ{sub Li-F} and Đ{sub Be-F} decreases sharply for higher concentration of LiF and BeF{sub 2} respectively. Interestingly, all three MS diffusivities have highest magnitude for eutectic mixture at 1000K (except Đ{sub Be-F} at lower LiF mole fraction) which is desirable from coolant point of view. Although the diffusivity for positive-positive ion pair is negative it is not in violation of the second law of thermodynamics as it satisfies the non-negative entropic constraints.

  7. Moderately nonlinear diffuse-charge dynamics under an ac voltage

    NASA Astrophysics Data System (ADS)

    Stout, Robert F.; Khair, Aditya S.

    2015-09-01

    The response of a symmetric binary electrolyte between two parallel, blocking electrodes to a moderate amplitude ac voltage is quantified. The diffuse charge dynamics are modeled via the Poisson-Nernst-Planck equations for a dilute solution of point-like ions. The solution to these equations is expressed as a Fourier series with a voltage perturbation expansion for arbitrary Debye layer thickness and ac frequency. Here, the perturbation expansion in voltage proceeds in powers of Vo/(kBT /e ) , where Vo is the amplitude of the driving voltage and kBT /e is the thermal voltage with kB as Boltzmann's constant, T as the temperature, and e as the fundamental charge. We show that the response of the electrolyte remains essentially linear in voltage amplitude at frequencies greater than the RC frequency of Debye layer charging, D /λDL , where D is the ion diffusivity, λD is the Debye layer thickness, and L is half the cell width. In contrast, nonlinear response is predicted at frequencies below the RC frequency. We find that the ion densities exhibit symmetric deviations from the (uniform) equilibrium density at even orders of the voltage amplitude. This leads to the voltage dependence of the current in the external circuit arising from the odd orders of voltage. For instance, the first nonlinear contribution to the current is O (Vo3) which contains the expected third harmonic but also a component oscillating at the applied frequency. We use this to compute a generalized impedance for moderate voltages, the first nonlinear contribution to which is quadratic in Vo. This contribution predicts a decrease in the imaginary part of the impedance at low frequency, which is due to the increase in Debye layer capacitance with increasing Vo. In contrast, the real part of the impedance increases at low frequency, due to adsorption of neutral salt from the bulk to the Debye layer.

  8. Moderately nonlinear diffuse-charge dynamics under an ac voltage.

    PubMed

    Stout, Robert F; Khair, Aditya S

    2015-09-01

    The response of a symmetric binary electrolyte between two parallel, blocking electrodes to a moderate amplitude ac voltage is quantified. The diffuse charge dynamics are modeled via the Poisson-Nernst-Planck equations for a dilute solution of point-like ions. The solution to these equations is expressed as a Fourier series with a voltage perturbation expansion for arbitrary Debye layer thickness and ac frequency. Here, the perturbation expansion in voltage proceeds in powers of V_{o}/(k_{B}T/e), where V_{o} is the amplitude of the driving voltage and k_{B}T/e is the thermal voltage with k_{B} as Boltzmann's constant, T as the temperature, and e as the fundamental charge. We show that the response of the electrolyte remains essentially linear in voltage amplitude at frequencies greater than the RC frequency of Debye layer charging, D/λ_{D}L, where D is the ion diffusivity, λ_{D} is the Debye layer thickness, and L is half the cell width. In contrast, nonlinear response is predicted at frequencies below the RC frequency. We find that the ion densities exhibit symmetric deviations from the (uniform) equilibrium density at even orders of the voltage amplitude. This leads to the voltage dependence of the current in the external circuit arising from the odd orders of voltage. For instance, the first nonlinear contribution to the current is O(V_{o}^{3}) which contains the expected third harmonic but also a component oscillating at the applied frequency. We use this to compute a generalized impedance for moderate voltages, the first nonlinear contribution to which is quadratic in V_{o}. This contribution predicts a decrease in the imaginary part of the impedance at low frequency, which is due to the increase in Debye layer capacitance with increasing V_{o}. In contrast, the real part of the impedance increases at low frequency, due to adsorption of neutral salt from the bulk to the Debye layer.

  9. Light-induced hydrogen evolution from hydrogenated amorphous silicon: Hydrogen diffusion by formation of bond centered hydrogen

    NASA Astrophysics Data System (ADS)

    Tanimoto, H.; Arai, H.; Mizubayashi, H.; Yamanaka, M.; Sakata, I.

    2014-02-01

    The light-induced hydrogen evolution (LIHE) from amorphous (a-) Si:H by the order of at. % is observed during white light soaking (WLS) of 100-400 mW/cm2 at 350-500 K or ultra violet light soaking (UVLS) of 30-120 mW/cm2 at 305-320 K in a vacuum. The thermal desorption spectroscopy indicates that LIHE originated from bonded hydrogen takes place through the diffusion of light-induced mobile hydrogen (LIMH) with the activation energy of 0.5 eV. LIMH is assigned to bond centered hydrogen and the hydrogen diffusion process becomes prominent when LIMH can leave from a-Si:H such under light soaking in a vacuum above room temperature. For H2 in microvoids, the hydrogen evolution rate is governed by the surface barrier and its activation energy of 1.0 eV in dark decreases to 0.4 eV under WLS or UVLS.

  10. Separation of strong (bond-breaking) from weak (dynamical) correlation

    NASA Astrophysics Data System (ADS)

    Kutzelnigg, Werner

    2012-06-01

    A CC (coupled-cluster) ansatz based on a GVB (generalized valence bond) or an APSG (antisymmetrized product of strongly orthogonal geminals) reference function arises naturally if one tries to treat strong correlations exactly (to infinite order), and weak correlations by TCC (traditional coupled cluster) theory. This ansatz is proposed as an alternative to MC-CC (multi-configuration coupled cluster) theory. One uses especially that APSG and GVB are of CC type, but allow to combine separability with the variation principle. The energy and the stationarity conditions are formulated in terms of spinfree density cumulants. The replacement operators corresponding to the APSG ansatz generate a Lie algebra which is a subalgebra of that of all replacement operators.

  11. Local bonds anomalies and dynamics in bismuth ferrite

    NASA Astrophysics Data System (ADS)

    Lin, J. W.; Gardner, J. S.; Wang, C.-W.; Deng, G.; Wu, C. M.; Peterson, V. K.; Lin, J. G.

    2017-05-01

    The temperature evolution of the chemical and magnetic sublattice of bismuth ferrite has been investigated by neutron scattering below room temperature. Although the bulk lattice structure performed as expected, anomalies were measured in the local Bi-Fe and Fe-O bond lengths around 205 K, distorting the Fe polyhedra. The intensity and width of magnetic Bragg reflections were observed not to monotonically decrease as the system cooled, with distinct anomalies at 205 K. Inelastic neutron scattering above and below the 205 K transition revealed no significant difference in the low energy acoustic phonon. These insights will underpin and stimulate more detailed work aimed at understanding further the bismuth ferrite ordering taking place around 205 K.

  12. Different dynamics and pathway of disulfide bonds reduction of two human defensins, a molecular dynamics simulation study.

    PubMed

    Zhang, Liqun

    2017-04-01

    Human defensins are a class of antimicrobial peptides that are crucial components of the innate immune system. Both human α defensin type 5 (HD5) and human β defensin type 3 (hBD-3) have 6 cysteine residues which form 3 pairs of disulfide bonds in oxidizing condition. Disulfide bond linking is important to the protein structure stabilization, and the disulfide bond linking and breaking order have been shown to influence protein function. In this project, microsecond long molecular dynamics simulations were performed to study the structure and dynamics of HD5 and hBD-3 wildtype and analogs which have all 3 disulfide bonds released in reducing condition. The structure of hBD-3 was found to be more dynamic and flexible than HD5, based on RMSD, RMSF, and radius of gyration calculations. The disulfide bridge breaking order of HD5 and hBD-3 in reducing condition was predicted by two kinds of methods, which gave consistent results. It was found that the disulfide bonds breaking pathways for HD5 and hBD-3 are very different. The breaking of disulfide bonds can influence the dimer interface by making the dimer structure less stable for both kinds of defensin. In order to understand the difference in dynamics and disulfide bond breaking pathway, hydrophilic and hydrophobic accessible surface areas (ASA), buried surface area between cysteine pairs, entropy of cysteine pairs, and internal energy were calculated. Comparing to the wildtype, hBD-3 analog is more hydrophobic, while HD5 is more hydrophilic. For hBD-3, the disulfide breaking is mainly entropy driven, while other factors such as the solvation effects may take the major role in controlling HD5 disulfide breaking pathway. Proteins 2017; 85:665-681. © 2016 Wiley Periodicals, Inc.

  13. Diffusion Bonding of TA15 and Ti2AlNb Alloys: Interfacial Microstructure and Mechanical Properties

    NASA Astrophysics Data System (ADS)

    Li, Ping; Ji, Xiaohu; Xue, Kemin

    2017-03-01

    TA15 and Ti2AlNb alloys were joined by diffusion welding. The influence of holding time on morphology and mechanical properties of the joint was studied under two conditions of different bonding pressure and temperature. The interface structure was analyzed by BSE and EDS. The mechanical properties of joints were tested. The results show that the typical interfacial microstructure consists of lath α-phase (TA15 alloy)/flake α phase + α-interfacial phase + α2 phase/B2-rich phase/Ti2AlNb alloy. When bonding at 920 °C and 15 MPa with increasing holding time, the interface microstructure evolves into flake α phase and distributes as a basket-weave and the interfacial coarse spherical α phase distributes as a line. α2 phase and O phase disappear gradually while the content of the B2 phase increases. The tensile strength of the joints is 870, 892 and 903 MPa, for 120, 150 and 210 min holding time, respectively, while the elongation rises as well. When bonding at 940 °C and 10 MPa with increasing holding time, the interfacial area includes more Widmanstatten structure and B2 phase. The tensile strength of joints decreases from 921 to 908 MPa, while the elongation increases from 12 to 15.5%, for holding 120 and 210 min, respectively. The tendency of plastic fracture also increases with holding time for both temperature-pressure combinations.

  14. Structure and hydrogen bond dynamics of water-dimethyl sulfoxide mixtures by computer simulations

    NASA Astrophysics Data System (ADS)

    Luzar, Alenka; Chandler, David

    1993-05-01

    We have used two different force field models to study concentrated dimethyl sulfoxide (DMSO)-water solutions by molecular dynamics. The results of these simulations are shown to compare well with recent neutron diffraction experiments using H/D isotope substitution [A. K. Soper and A. Luzar, J. Chem. Phys. 97, 1320 (1992)]. Even for the highly concentrated 1 DMSO : 2 H2O solution, the water hydrogen-hydrogen radial distribution function, gHH(r), exhibits the characteristic tetrahedral ordering of water-water hydrogen bonds. Structural information is further obtained from various partial atom-atom distribution functions, not accessible experimentally. The behavior of water radial distribution functions, gOO(r) and gOH(r) indicate that the nearest neighbor correlations among remaining water molecules in the mixture increase with increasing DMSO concentration. No preferential association of methyl groups on DMSO is detected. The pattern of hydrogen bonding and the distribution of hydrogen bond lifetimes in the simulated mixtures is further investigated. Molecular dynamics results show that DMSO typically forms two hydrogen bonds with water molecules. Hydrogen bonds between DMSO and water molecules are longer lived than water-water hydrogen bonds. The hydrogen bond lifetimes determined by reactive flux correlation function approach are about 5 and 3 ps for water-DMSO and water-water pairs, respectively, in 1 DMSO : 2 H2O mixture. In contrast, for pure water, the hydrogen bond lifetime is about 1 ps. We discuss these times in light of experimentally determined rotational relaxation times. The relative values of the hydrogen bond lifetimes are consistent with a statistical (i.e., transition state theory) interpretation.

  15. EFFECT OF TEMPERATURE AND GLYCEROL ON THE HYDROGEN-BOND DYNAMICS OF WATER

    SciTech Connect

    Ghattyvenkatakrishna, Pavan K; Uberbacher, Edward C

    2013-01-01

    The effect of glycerol, water and glycerol-water binary mixtures on the structure and dynamics of biomolecules has been well studied. However, the effect of varying glycerol concentration and temperature on the dynamics of water has not received due attention. We have studied the effect of concentration and temperature on the hydrogen bonded network formed by water molecules. A strong correlation between the relaxation time of the network and average number of hydrogen bonds per water molecules was found. The radial distribution function of water oxygens and hydrogens clarifies the effect of concentration on the structure and clustering of water.

  16. Contributions of Microtubule Dynamic Instability and Rotational Diffusion to Kinetochore Capture.

    PubMed

    Blackwell, Robert; Sweezy-Schindler, Oliver; Edelmaier, Christopher; Gergely, Zachary R; Flynn, Patrick J; Montes, Salvador; Crapo, Ammon; Doostan, Alireza; McIntosh, J Richard; Glaser, Matthew A; Betterton, Meredith D

    2017-02-07

    Microtubule dynamic instability allows search and capture of kinetochores during spindle formation, an important process for accurate chromosome segregation during cell division. Recent work has found that microtubule rotational diffusion about minus-end attachment points contributes to kinetochore capture in fission yeast, but the relative contributions of dynamic instability and rotational diffusion are not well understood. We have developed a biophysical model of kinetochore capture in small fission-yeast nuclei using hybrid Brownian dynamics/kinetic Monte Carlo simulation techniques. With this model, we have studied the importance of dynamic instability and microtubule rotational diffusion for kinetochore capture, both to the lateral surface of a microtubule and at or near its end. Over a range of biologically relevant parameters, microtubule rotational diffusion decreased capture time, but made a relatively small contribution compared to dynamic instability. At most, rotational diffusion reduced capture time by 25%. Our results suggest that while microtubule rotational diffusion can speed up kinetochore capture, it is unlikely to be the dominant physical mechanism for typical conditions in fission yeast. In addition, we found that when microtubules undergo dynamic instability, lateral captures predominate even in the absence of rotational diffusion. Counterintuitively, adding rotational diffusion to a dynamic microtubule increases the probability of end-on capture.

  17. Contributions of Microtubule Dynamic Instability and Rotational Diffusion to Kinetochore Capture

    NASA Astrophysics Data System (ADS)

    Blackwell, Robert; Sweezy-Schindler, Oliver; Edelmaier, Christopher; Gergely, Zachary R.; Flynn, Patrick J.; Montes, Salvador; Crapo, Ammon; Doostan, Alireza; McIntosh, J. Richard; Glaser, Matthew A.; Betterton, Meredith D.

    2017-02-01

    Microtubule dynamic instability allows search and capture of kinetochores during spindle formation, an important process for accurate chromosome segregation during cell division. Recent work has found that microtubule rotational diffusion about minus-end attachment points contributes to kinetochore capture in fission yeast, but the relative contributions of dynamic instability and rotational diffusion are not well understood. We have developed a biophysical model of kinetochore capture in small fission-yeast nuclei using hybrid Brownian dynamics/kinetic Monte Carlo simulation techniques. With this model, we have studied the importance of dynamic instability and microtubule rotational diffusion for kinetochore capture, both to the lateral surface of a microtubule and at or near its end. Over a range of biologically relevant parameters, microtubule rotational diffusion decreased capture time, but made a relatively small contribution compared to dynamic instability. At most, rotational diffusion reduced capture time by 25%. Our results suggest that while microtubule rotational diffusion can speed up kinetochore capture, it is unlikely to be the dominant physical mechanism. In addition, we found that when microtubules undergo dynamic instability, lateral captures predominate even in the absence of rotational diffusion. Counterintuitively, adding rotational diffusion to a dynamic microtubule increases the probability of end-on capture.

  18. Stochastic fire-diffuse-fire model with realistic cluster dynamics

    NASA Astrophysics Data System (ADS)

    Calabrese, Ana; Fraiman, Daniel; Zysman, Daniel; Ponce Dawson, Silvina

    2010-09-01

    Living organisms use waves that propagate through excitable media to transport information. Ca2+ waves are a paradigmatic example of this type of processes. A large hierarchy of Ca2+ signals that range from localized release events to global waves has been observed in Xenopus laevis oocytes. In these cells, Ca2+ release occurs trough inositol 1,4,5-trisphosphate receptors (IP3Rs) which are organized in clusters of channels located on the membrane of the endoplasmic reticulum. In this article we construct a stochastic model for a cluster of IP3R ’s that replicates the experimental observations reported in [D. Fraiman , Biophys. J. 90, 3897 (2006)10.1529/biophysj.105.075911]. We then couple this phenomenological cluster model with a reaction-diffusion equation, so as to have a discrete stochastic model for calcium dynamics. The model we propose describes the transition regimes between isolated release and steadily propagating waves as the IP3 concentration is increased.

  19. The dynamics of multimodal integration: The averaging diffusion model.

    PubMed

    Turner, Brandon M; Gao, Juan; Koenig, Scott; Palfy, Dylan; L McClelland, James

    2017-03-08

    We combine extant theories of evidence accumulation and multi-modal integration to develop an integrated framework for modeling multimodal integration as a process that unfolds in real time. Many studies have formulated sensory processing as a dynamic process where noisy samples of evidence are accumulated until a decision is made. However, these studies are often limited to a single sensory modality. Studies of multimodal stimulus integration have focused on how best to combine different sources of information to elicit a judgment. These studies are often limited to a single time point, typically after the integration process has occurred. We address these limitations by combining the two approaches. Experimentally, we present data that allow us to study the time course of evidence accumulation within each of the visual and auditory domains as well as in a bimodal condition. Theoretically, we develop a new Averaging Diffusion Model in which the decision variable is the mean rather than the sum of evidence samples and use it as a base for comparing three alternative models of multimodal integration, allowing us to assess the optimality of this integration. The outcome reveals rich individual differences in multimodal integration: while some subjects' data are consistent with adaptive optimal integration, reweighting sources of evidence as their relative reliability changes during evidence integration, others exhibit patterns inconsistent with optimality.

  20. Ice crystal growth in a dynamic thermal diffusion chamber

    NASA Technical Reports Server (NTRS)

    Keller, V. W.

    1980-01-01

    Ice crystals were grown in a supersaturated environment produced by a dynamic thermal diffusion chamber, which employed two horizontal plates separated by a distance of 2.5 cm. Air was circulated between and along the 1.2 m length of the plates past ice crystals which nucleated and grew from a fiber suspended vertically between the two plates. A zoom stereo microscope with a magnification which ranged from 3X to 80X and both 35 mm still photographs and 16 mm time lapse cine films taken through the microscope were used to study the variation of the shape and linear growth rate of ice crystals as a function of the ambient temperature, the ambient supersaturation, and the forced ventilation velocity. The ambient growth conditions were varied over the range of temperature 0 to -40 C, over the range of supersaturation 4% to 50% with respect to ice, and over the range of forced ventilation velocities 0 cm/s to 20 cm/s.

  1. Simulating Hydrogen-Bond Structure and Dynamics in Glassy Solids Composed of Imidazole Oligomers.

    PubMed

    Harvey, Jacob A; Auerbach, Scott M

    2014-07-01

    We simulated structural and dynamical properties of imidazoles tethered to aliphatic backbones to determine how chain length influences the competition between extended hydrogen-bond networks and imidazole reorientation dynamics. We performed molecular dynamics simulations on hypothetical solids using the GAFF Amber force field over the temperature range 300-800 K, for chain lengths varying from monomers to pentamers. We investigated the effect of heterogeneity by simulating monodisperse and polydisperse solids with the same average chain length. We computed hydrogen-bond cluster sizes and percolation ratios; orientational order parameters associated with imidazole rings, tethering linkers, and backbones; and orientational correlation functions for imidazole rings. We found the surprising result that chain-length heterogeneity negligibly affects system density at standard pressure, the fraction of percolating hydrogen-bonded clusters, and the order parameters for backbone, linker, and imidazole ring. Decreasing oligomer chain length from pentamers to shorter chains decreases the tendency to form percolating hydrogen-bond networks while dramatically decreasing imidazole ring reorientation times from a broad range of 100-700 ps for pentamers down to 20 ps for monomers, hence quantifying the competition between hydrogen-bond cluster size and reorientation rate. The computed orientational order parameters suggest the following hierarchy of structural excitations: imidazole ring reorientation in the range 400-500 K, linker motion around 500-600 K, and backbone relaxation at 600-700 K in this model. The question remains for this class of systems which of these motions is crucial for facile proton transport.

  2. Scaling of the dynamics of flexible Lennard-Jones chains: Effects of harmonic bonds.

    PubMed

    Veldhorst, Arno A; Dyre, Jeppe C; Schrøder, Thomas B

    2015-11-21

    The previous paper [A. A. Veldhorst et al., J. Chem. Phys. 141, 054904 (2014)] demonstrated that the isomorph theory explains the scaling properties of a liquid of flexible chains consisting of ten Lennard-Jones particles connected by rigid bonds. We here investigate the same model with harmonic bonds. The introduction of harmonic bonds almost completely destroys the correlations in the equilibrium fluctuations of the potential energy and the virial. According to the isomorph theory, if these correlations are strong a system has isomorphs, curves in the phase diagram along which structure, dynamics, and the excess entropy are invariant. The Lennard-Jones chain liquid with harmonic bonds does have curves in the phase diagram along which the structure and dynamics are invariant. The excess entropy is not invariant on these curves, which we refer to as "pseudoisomorphs." In particular, this means that Rosenfeld's excess-entropy scaling (the dynamics being a function of excess entropy only) does not apply for the Lennard-Jones chain with harmonic bonds.

  3. 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

  4. Molecular Dynamics Study of Hsp90 and ADP: Hydrogen Bond Analysis for ADP Dissociation

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Kazutomo; Saito, Hiroaki; Nagao, Hidemi

    The contacts between the N-terminal domain of heat shock protein 90 (N-Hsp90) and ADP involve both direct and water-mediated hydrogen bonds in X-ray crystallographic structure. We perform all-atom molecular dynamics (MD) simulations of N-Hsp90 and ADP to investigate the changes of the hydrogen bond lengths during ADP dissociation. We show the difference between the hydrogen bonds in the crystal structure and MD simulations. Moreover, the N6 group of ADP does not contact with the Cγ group of Asp93, and the hydrogen bonds between Asn51 side chain and ADP are stable in the early step of ADP dissociation.

  5. Reprogrammable Assembly of Molecular Motor on Solid Surfaces via Dynamic Bonds.

    PubMed

    Yu, Li; Sun, Jian; Wang, Qian; Guan, Yan; Zhou, Le; Zhang, Jingxuan; Zhang, Lanying; Yang, Huai

    2017-06-01

    Controllable assembly of molecular motors on solid surfaces is a fundamental issue for providing them to perform physical tasks. However, it can hardly be achieved by most previous methods due to their inherent limitations. Here, a general strategy is designed for the reprogrammable assembly of molecular motors on solid surfaces based on dynamic bonds. In this method, molecular motors with disulfide bonds can be remotely, reversibly, and precisely attached to solid surfaces with disulfide bonds, regardless of their chemical composition and microstructure. More importantly, it not only allows encoding geometric information referring to a pattern of molecular motors, but also enables erasing and re-encoding of geometric information via hemolytic photocleavage and recombination of disulfide bonds. Thus, solid surfaces can be regarded as "computer hardware", where molecular motors can be reformatted and reprogramed as geometric information. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Hydrogen bonding in liquid methanol, methylamine, and methanethiol studied by molecular-dynamics simulations

    NASA Astrophysics Data System (ADS)

    Kosztolányi, T.; Bakó, I.; Pálinkás, G.

    2003-03-01

    Molecular-dynamics computer simulations have been carried out on liquid methanol, methylamine, and methanethiol. The local structure of the liquids was studied based on radial distribution functions and the density projections of the neighboring molecules obtained on the basis of simulated molecular configurations. The extent of hydrogen bonding was investigated by direct analysis of the connectivity of molecules forming hydrogen-bonded clusters in these liquids. By this analysis, the methanol molecules were found to form linear chainlike structures. The local structure of hydrogen-bonded molecules of methylamine proved to be rather space filling due to the great extent of chain branching. Methanethiol molecules also proved to form hydrogen bonds forming small compact clusters. No evidence was found, however, for the clustering of hydrophobic methyl groups in any of the liquids. The quality of simulations was checked by derivation of neutron total and composite radial distribution functions and by comparison of those with available experimental data.

  7. Dynamic covalent bond based on reversible photo [4 + 4] cycloaddition of anthracene for construction of double-dynamic polymers.

    PubMed

    Xu, Jiang-Fei; Chen, Yu-Zhe; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

    2013-12-20

    Dynamic covalent bonds supplied by reversible anthracene dimerization were combined with pillar[5]arene/imidazole host-guest interactions to construct double-dynamic polymers. Heating such polymers (in solution or as a gel) led to depolymerization by dissociation of either the host-guest complexes alone or the complexes and the anthracene dimers, depending on the extent of heating. The polymers reformed readily upon cooling or irradiation.

  8. The impact of interface bonding efficiency on high-burnup spent nuclear fuel dynamic performance

    SciTech Connect

    Jiang, Hao; Wang, Jy-An John; Wang, Hong

    2016-09-26

    Finite element analysis (FEA) was used to investigate the impact of interfacial bonding efficiency at pellet-pellet and pellet-clad interfaces of high-burnup (HBU) spent nuclear fuel (SNF) on system dynamic performance. Bending moments M were applied to FEA model to evaluate the system responses. From bending curvature, κ, flexural rigidity EI can be estimated as EI = M/κ. The FEA simulation results were benchmarked with experimental results from cyclic integrated reversal bending fatigue test (CIRFT) of HBR fuel rods. The consequence of interface debonding between fuel pellets and cladding is a redistribution of the loads carried by the fuel pellets to the clad, which results in a reduction in composite rod system flexural rigidity. Furthermore, the interface bonding efficiency at the pellet-pellet and pellet-clad interfaces can significantly dictate the SNF system dynamic performance. With the consideration of interface bonding efficiency, the HBU SNF fuel property was estimated with CIRFT test data.

  9. The impact of interface bonding efficiency on high-burnup spent nuclear fuel dynamic performance

    SciTech Connect

    Jiang, Hao; Wang, Jy-An John; Wang, Hong

    2016-09-26

    Finite element analysis (FEA) was used to investigate the impact of interfacial bonding efficiency at pellet-pellet and pellet-clad interfaces of high-burnup (HBU) spent nuclear fuel (SNF) on system dynamic performance. Bending moments M were applied to FEA model to evaluate the system responses. From bending curvature, κ, flexural rigidity EI can be estimated as EI = M/κ. The FEA simulation results were benchmarked with experimental results from cyclic integrated reversal bending fatigue test (CIRFT) of HBR fuel rods. The consequence of interface debonding between fuel pellets and cladding is a redistribution of the loads carried by the fuel pellets to the clad, which results in a reduction in composite rod system flexural rigidity. Furthermore, the interface bonding efficiency at the pellet-pellet and pellet-clad interfaces can significantly dictate the SNF system dynamic performance. With the consideration of interface bonding efficiency, the HBU SNF fuel property was estimated with CIRFT test data.

  10. Static and dynamic descriptions of bond breaking/formation: A complementary view?

    NASA Astrophysics Data System (ADS)

    Joubert, Laurent; Adamo, Carlo

    2005-12-01

    Ab initio molecular-dynamic simulations using density-functional theory and the recent atom-centered density-matrix propagation (ADMP) method were used to study the bond breaking and formation for a case-study substitution nucleophilic bimolecular reaction, namely, the Walden inversion. Using the atoms-in-molecule approach, we have performed a detailed analysis to investigate intra- and intermolecular charge transfer along the ADMP trajectory. These results were compared to those obtained considering a static approach, such as the intrinsic reaction path. In particular, the topological properties computed along the dynamic trajectory well evidence a stronger electron exchange tending to spontaneously maximize the rising covalent interaction. Furthermore, their analysis suggests that the bond formation mechanism involves a reactive intermediate with a bonding interaction stronger than in the final product.

  11. Photoresponsive liquid crystalline epoxy networks with shape memory behavior and dynamic ester bonds

    DOE PAGES

    Rios, Orlando; Chen, Jihua; Li, Yuzhan; ...

    2016-06-01

    Functional polymers are intelligent materials that can respond to a variety of external stimuli. However, these materials have not yet found widespread real world applications because of the difficulties in fabrication and the limited number of functional building blocks that can be incorporated into a material. Here, we demonstrate a simple route to incorporate three functional building blocks (azobenzene chromophores, liquid crystals, and dynamic covalent bonds) into an epoxy-based liquid crystalline network (LCN), in which an azobenzene-based epoxy monomer is polymerized with an aliphatic dicarboxylic acid to create exchangeable ester bonds that can be thermally activated. Lastly, all three functionalmore » building blocks exhibited good compatibility, and the resulting materials exhibits various photomechanical, shape memory, and self-healing properties because of the azobenzene molecules, liquid crystals, and dynamic ester bonds, respectively.« less

  12. Colloidal crystals: Structure, dynamics, and the importance of dimer bonds

    NASA Astrophysics Data System (ADS)

    Gerbode, Sharon Jane

    Colloidal crystals, periodic arrays of micron-sized solid particles in solution, offer a unique glimpse of the particle-scale structures and dynamics within a true thermodynamic ensemble. Experimental colloidal studies of melting and crystallization [55, 56, 13, 76, 2] as well as non-equilibrium states such as colloidal glasses [67, 68, 29, 49] have uncovered numerous mechanisms that are experimentally inaccessible in atomic systems due to both small timescales and small lengthscales. The great successes of colloidal physics have emerged as a result of technological advances enabling synthesis of large batches of monodisperse spherical particles. Yet, the crystal structures formed by such particles are limited to variations on layers of close-packed spheres. Consequently, one of the current frontiers in colloidal physics is the study of novel crystal structures formed by non-spherical particles. My thesis work has focused on crystals formed by colloidal dimer particles consisting of two connected spherical lobes. Surprisingly, while the structure of two dimensional crystals formed by the dimers are quite similar to those observed for spheres, the motion of defects within the dimer crystals is significantly different. Geometric obstacles formed by interlocking dimers restrict the motion of defects and ultimately introduce a completely unexpected, previously unreported glassy defect dynamics within a colloidal crystal.

  13. M3B2 and M5B3 Formation in Diffusion-Affected Zone During Transient Liquid Phase Bonding Single-Crystal Superalloys

    NASA Astrophysics Data System (ADS)

    Sheng, Naicheng; Hu, Xiaobing; Liu, Jide; Jin, Tao; Sun, Xiaofeng; Hu, Zhuangqi

    2015-04-01

    Precipitates in the diffusion-affected zone (DAZ) during transient liquid phase bonding (TLP) single-crystal superalloys were observed and investigated. Small size and dendritic-shaped precipitates were identified to be M3B2 borides and intergrowth of M3B2/M5B3 borides. The orientation relationships among M3B2, M5B3, and matrix were determined using transmission electron microscope (TEM). Composition characteristics of these borides were also analyzed by TEM energy-dispersive spectrometer. Because this precipitating phenomenon deviates from the traditional parabolic transient liquid phase bonding model which assumed a precipitates free DAZ during TLP bonding, some correlations between the deviation of the isothermal solidification kinetics and these newly observed precipitating behaviors were discussed and rationalized when bonding the interlayer containing the high diffusivity melting point depressant elements and substrates of low solubility.

  14. Self-assembly of a "double dynamic covalent" amphiphile featuring a glucose-responsive imine bond.

    PubMed

    Wu, Xin; Chen, Xuan-Xuan; Zhang, Miao; Li, Zhao; Gale, Philip A; Jiang, Yun-Bao

    2016-05-19

    Glucose binding via boronate ester linkages selectively triggers imine bond formation between 4-formylphenylboronic acid and octylamine, leading to the formation of vesicular aggregates in aqueous solutions. This "double dynamic covalent assembly" allows the facile selective sensing of glucose against the otherwise serious interferant fructose, without the need to resort to synthetic effort.

  15. Diffusion in a Cu-Zr metallic glass studied by microsecond-scale molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Wang, C. Z.; Mendelev, M. I.; Zhang, F.; Kramer, M. J.; Ho, K. M.

    2015-05-01

    Icosahedral short-range order (ISRO) has been widely accepted to be dominant in Cu-Zr metallic glasses (MGs). However, the diffusion mechanism and correlation of ISRO and medium-range order (MRO) to diffusion in MGs remain largely unexplored. Here, we perform a long time annealing up to 1.8 μs in molecular dynamics simulations to study the diffusion mechanism and the relationship between atomic structures and the diffusion path in a C u64.5Z r35.5 MG. It is found that most of the diffusing events performed by the diffusing atoms are outside ISRO and the Bergman-type MRO. The long-range diffusion in MGs is highly heterogeneous, via collective diffusing events through the liquidlike channels in the glass. Our results clearly demonstrate a strong correlation between the atomic structures and transport in MGs.

  16. Constructing covalent organic frameworks in water via dynamic covalent bonding

    PubMed Central

    Thote, Jayshri; Barike Aiyappa, Harshitha; Rahul Kumar, Raya; Kandambeth, Sharath; Biswal, Bishnu P.; Balaji Shinde, Digambar; Chaki Roy, Neha; Banerjee, Rahul

    2016-01-01

    The formation of keto-enamine based crystalline, porous polymers in water is investigated for the first time. Facile access to the Schiff base reaction in water has been exploited to synthesize stable porous structures using the principles of Dynamic Covalent Chemistry (DCC). Most credibly, the water-based Covalent Organic Frameworks (COFs) possess chemical as well as physical properties such as crystallinity, surface area and porosity, which is comparable to their solvothermal counterparts. The formation of COFs in water is further investigated by understanding the nature of the monomers formed using hydroxy and non-hydroxy analogues of the aldehyde. This synthetic route paves a new way to synthesize COFs using a viable, greener route by utilization of the DCC principles in conjunction with the keto–enol tautomerism to synthesize useful, stable and porous COFs in water. PMID:27840679

  17. 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).

  18. Peptide dynamics by molecular dynamics simulation and diffusion theory method with improved basis sets

    NASA Astrophysics Data System (ADS)

    Hsu, Po Jen; Lai, S. K.; Rapallo, Arnaldo

    2014-03-01

    Improved basis sets for the study of polymer dynamics by means of the diffusion theory, and tests on a melt of cis-1,4-polyisoprene decamers, and a toluene solution of a 71-mer syndiotactic trans-1,2-polypentadiene were presented recently [R. Gaspari and A. Rapallo, J. Chem. Phys. 128, 244109 (2008)]. The proposed hybrid basis approach (HBA) combined two techniques, the long time sorting procedure and the maximum correlation approximation. The HBA takes advantage of the strength of these two techniques, and its basis sets proved to be very effective and computationally convenient in describing both local and global dynamics in cases of flexible synthetic polymers where the repeating unit is a unique type of monomer. The question then arises if the same efficacy continues when the HBA is applied to polymers of different monomers, variable local stiffness along the chain and with longer persistence length, which have different local and global dynamical properties against the above-mentioned systems. Important examples of this kind of molecular chains are the proteins, so that a fragment of the protein transthyretin is chosen as the system of the present study. This peptide corresponds to a sequence that is structured in β-sheets of the protein and is located on the surface of the channel with thyroxin. The protein transthyretin forms amyloid fibrils in vivo, whereas the peptide fragment has been shown [C. P. Jaroniec, C. E. MacPhee, N. S. Astrof, C. M. Dobson, and R. G. Griffin, Proc. Natl. Acad. Sci. U.S.A. 99, 16748 (2002)] to form amyloid fibrils in vitro in extended β-sheet conformations. For these reasons the latter is given considerable attention in the literature and studied also as an isolated fragment in water solution where both experimental and theoretical efforts have indicated the propensity of the system to form β turns or α helices, but is otherwise predominantly unstructured. Differing from previous computational studies that employed implicit

  19. Peptide dynamics by molecular dynamics simulation and diffusion theory method with improved basis sets

    SciTech Connect

    Hsu, Po Jen; Lai, S. K.; Rapallo, Arnaldo

    2014-03-14

    Improved basis sets for the study of polymer dynamics by means of the diffusion theory, and tests on a melt of cis-1,4-polyisoprene decamers, and a toluene solution of a 71-mer syndiotactic trans-1,2-polypentadiene were presented recently [R. Gaspari and A. Rapallo, J. Chem. Phys. 128, 244109 (2008)]. The proposed hybrid basis approach (HBA) combined two techniques, the long time sorting procedure and the maximum correlation approximation. The HBA takes advantage of the strength of these two techniques, and its basis sets proved to be very effective and computationally convenient in describing both local and global dynamics in cases of flexible synthetic polymers where the repeating unit is a unique type of monomer. The question then arises if the same efficacy continues when the HBA is applied to polymers of different monomers, variable local stiffness along the chain and with longer persistence length, which have different local and global dynamical properties against the above-mentioned systems. Important examples of this kind of molecular chains are the proteins, so that a fragment of the protein transthyretin is chosen as the system of the present study. This peptide corresponds to a sequence that is structured in β-sheets of the protein and is located on the surface of the channel with thyroxin. The protein transthyretin forms amyloid fibrils in vivo, whereas the peptide fragment has been shown [C. P. Jaroniec, C. E. MacPhee, N. S. Astrof, C. M. Dobson, and R. G. Griffin, Proc. Natl. Acad. Sci. U.S.A. 99, 16748 (2002)] to form amyloid fibrils in vitro in extended β-sheet conformations. For these reasons the latter is given considerable attention in the literature and studied also as an isolated fragment in water solution where both experimental and theoretical efforts have indicated the propensity of the system to form β turns or α helices, but is otherwise predominantly unstructured. Differing from previous computational studies that employed implicit

  20. Modulation of the dayside diffuse auroral intensity by the solar wind dynamic pressure

    NASA Astrophysics Data System (ADS)

    Shi, Run; Hu, Ze-Jun; Ni, Binbin; Han, Desheng; Chen, Xiang-Cai; Zhou, Chen; Gu, Xudong

    2014-12-01

    Compared to the recently improved understanding of the nightside diffuse aurora, the mechanism(s) responsible for the dayside diffuse auroral precipitation remains limitedly understood. We investigate the dayside diffuse aurora observed by the all-sky imagers of Chinese Arctic Yellow River Station in the time interval of 02:00-10:00 UT (05:00-13:00 magnetic local time) on 2 January 2006. In this interval, the intensity of dayside diffuse aurora is highly correlated with the solar wind dynamic pressure with a maximum coefficient of 0.89. Moreover, there are similar spectra characteristics in the Pc5 range between the intensity of dayside diffuse aurora and solar wind dynamic pressure (proton density) during a portion of the time interval, in which the interplanetary magnetic field Bz is northward. The observation indicates that changes in solar wind dynamic pressure can efficiently modulate the magnitude of the dayside diffuse aurora, except when the interplanetary magnetic field is southward. The enhancement of the solar wind dynamic pressure can provide favorable circumstances for dayside chorus wave generation, so we consider that the dayside chorus could be a candidate for the production of the dayside diffuse aurora. Furthermore, since the compressional Pc4-Pc5 pulsations can also modulate the intensity of whistler mode chorus waves, the solar wind dynamic pressure modulates the dayside diffuse aurora through affecting dayside chorus wave activity and the associated scattering process.

  1. New results on non-CP dynamics unearthed from urtexts of quantum state diffusion

    NASA Astrophysics Data System (ADS)

    Diósi, Lajos

    2017-04-01

    Thirty years ago, the present author discussed the pure state unraveling (stochastic quantum trajectories) of Markovian open system dynamics. The fact that he considered all positive dynamics, not restricted to the Lindblad–Gorini–Kossakowski–Sudarshan complete-positive subclass, has remained unnoticed so far. We emphasize the importance of the transition-rate-operator W and the merit of the invariant (representation-independent) approach. From the urtexts we point out the condition W≥slant 0 of positive dynamics, the extension of quantum state diffusion for positive dynamics, and as a major new result, the description of all the diffusive unravelings of positive dynamics.

  2. 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.

  3. On the Intramolecular Hydrogen Bond in Solution: Car-Parrinello and Path Integral Molecular Dynamics Perspective.

    PubMed

    Dopieralski, Przemyslaw; Perrin, Charles L; Latajka, Zdzislaw

    2011-11-08

    The issue of the symmetry of short, low-barrier hydrogen bonds in solution is addressed here with advanced ab initio simulations of a hydrogen maleate anion in different environments, starting with the isolated anion, going through two crystal structures (sodium and potassium salts), then to an aqueous solution, and finally in the presence of counterions. By Car-Parrinello and path integral molecular dynamics simulations, it is demonstrated that the position of the proton in the intramolecular hydrogen bond of an aqueous hydrogen maleate anion is entirely related to the solvation pattern around the oxygen atoms of the intramolecular hydrogen bond. In particular, this anion has an asymmetric hydrogen bond, with the proton always located on the oxygen atom that is less solvated, owing to the instantaneous solvation environment. Simulations of water solutions of hydrogen maleate ion with two different counterions, K(+) and Na(+), surprisingly show that the intramolecular hydrogen-bond potential in the case of the Na(+) salt is always asymmetric, regardless of the hydrogen bonds to water, whereas for the K(+) salt, the potential for H motion depends on the location of the K(+). It is proposed that repulsion by the larger and more hydrated K(+) is weaker than that by Na(+) and competitive with solvation by water.

  4. Liquid-phase diffusion bonding: Temperature effects and solute redistribution in high temperature lead-free composite solders

    SciTech Connect

    Anderson, Iver; Choquette, Stephanie

    2015-05-17

    Liquid-phase diffusion bonding (LPDB) is being studied as the primary phenomena occurring in the development of a high temperature lead-free composite solder paste composed of gas-atomized Cu-10Ni, wt.% (Cu-11Ni, at.%) powder blended with Sn-0.7Cu-0.05Ni-0.01Ge (Sn-1.3Cu-0.1Ni-0.02Ge, at.%) Nihon-Superior SN100C solder powder. Powder compacts were used as a model system. LPDB promotes enhanced interdiffusion of the low-melting alloy matrix with the solid Cu-10Ni reinforcement powder above the matrix liquidus temperature. The initial study involved the effective intermetallic compound (IMC) compositions and microstructures that occur at varying reflow temperatures and times between 250-300°C and 30-60s, respectively. Certain reflow temperatures encourage adequate interdiffusion to form a continuous highly-conductive network throughout the composite solder joints. The diffusion of nickel, in particular, has a disperse pattern that foreshadows the possibility of a highly-conductive low-melting solder that can be successfully utilized at high temperatures.

  5. 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.

  6. A molecular dynamics study of bond exchange reactions in covalent adaptable networks.

    PubMed

    Yang, Hua; Yu, Kai; Mu, Xiaoming; Shi, Xinghua; Wei, Yujie; Guo, Yafang; Qi, H Jerry

    2015-08-21

    Covalent adaptable networks are polymers that can alter the arrangement of network connections by bond exchange reactions where an active unit attaches to an existing bond then kicks off its pre-existing peer to form a new bond. When the polymer is stretched, bond exchange reactions lead to stress relaxation and plastic deformation, or the so-called reforming. In addition, two pieces of polymers can be rejoined together without introducing additional monomers or chemicals on the interface, enabling welding and reprocessing. Although covalent adaptable networks have been researched extensively in the past, knowledge about the macromolecular level network alternations is limited. In this study, molecular dynamics simulations are used to investigate the macromolecular details of bond exchange reactions in a recently reported epoxy system. An algorithm for bond exchange reactions is first developed and applied to study a crosslinking network formed by epoxy resin DGEBA with the crosslinking agent tricarballylic acid. The trace of the active units is tracked to show the migration of these units within the network. Network properties, such as the distance between two neighboring crosslink sites, the chain angle, and the initial modulus, are examined after each iteration of the bond exchange reactions to provide detailed information about how material behaviors and macromolecular structure evolve. Stress relaxation simulations are also conducted. It is found that even though bond exchange reactions change the macroscopic shape of the network, microscopic network characteristic features, such as the distance between two neighboring crosslink sites and the chain angle, relax back to the unstretched isotropic state. Comparison with a recent scaling theory also shows good agreement.

  7. Electrostatic interactions and hydrogen bond dynamics in chloride pumping by halorhodopsin.

    PubMed

    Jardón-Valadez, Eduardo; Bondar, Ana-Nicoleta; Tobias, Douglas J

    2014-12-01

    Translocation of negatively charged ions across cell membranes by ion pumps raises the question as to how protein interactions control the location and dynamics of the ion. Here we address this question by performing extensive molecular dynamics simulations of wild type and mutant halorhodopsin, a seven-helical transmembrane protein that translocates chloride ions upon light absorption. We find that inter-helical hydrogen bonds mediated by a key arginine group largely govern the dynamics of the protein and water groups coordinating the chloride ion.

  8. A Modified Shake Algorithm for Maintaining Rigid Bonds in Molecular Dynamics Simulations of Large Molecules

    NASA Astrophysics Data System (ADS)

    Lambrakos, S. G.; Boris, J. P.; Oran, E. S.; Chandrasekhar, I.; Nagumo, M.

    1989-12-01

    We present a new modification of the SHAKE algorithm, MSHAKE, that maintains fixed distances in molecular dynamics simulations of polyatomic molecules. The MSHAKE algorithm, which is applied by modifying the leapfrog algorithm to include forces of constraint, computes an initial estimate of constraint forces, then iteratively corrects the constraint forces required to maintain the fixed distances. Thus MSHAKE should always converge more rapidly than SHAKE. Further, the explicit determination of the constraint forces at each timestep makes MSHAKE convenient for use in molecular dynamics simulations where bond stress is a significant dynamical quantity.

  9. Effect of Bonding Temperature on Phase Transformation of Diffusion-Bonded Joints of Duplex Stainless Steel and Ti-6Al-4V Using Nickel and Copper as Composite Intermediate Metals

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    In the present study, the effect of bonding temperature on phase transformation of diffusion-bonded joints of duplex stainless steel (DSS) and Ti-6Al-4V (Ti64) using simultaneously both nickel (Ni) and copper (Cu) interlayers was investigated in the temperature range of 1148 K to 1223 K (875 °C to 950 °C) insteps of 25 K (25 °C) for 60 minutes under 4 MPa uniaxial pressure in vacuum. Interfaces were characterized by scanning electron microscopy and interdiffusion of the chemical species across the diffusion interfaces were witnessed by electron probe microanalysis. At 1148 K (875 °C), layer-wise Cu4Ti, Cu2Ti, Cu4Ti3, CuTi, and CuTi2 phases were observed at the Cu-Ti64 interface; however, DSS-Ni and Ni-Cu interfaces were free from any intermetallic. At 1173 K and 1198 K (900 °C and 925 °C), Cu interlayer could not restrict the diffusion of atoms from Ti64 to Ni, and vice versa; and Ni-Ti-based intermetallics were formed at the Ni-Cu interface and throughout the Cu zone as well; however, at 1223 K (950 °C), both Ni and Cu interlayers could not inhibit the diffusion of atoms from Ti64 to DSS, and vice versa. The maximum shear strength of ~377 MPa was obtained for the diffusion couple processed at 1148 K (875 °C) and strength of the bonded joints gradually decreased with the increasing bonding temperature due to the widening of brittle intermetallics at the diffusion zone. Fracture path indicated that failure took place through the Cu4Ti intermetallic at the Cu-Ti64 interface when bonding was processed at 1148 K (875 °C). When bonding was processed at 1173 K and 1198 K (900 °C and 925 °C), fracture took place through the Ni3Ti intermetallic at the Ni-(Ni + Cu + Ti64 diffusion reaction) interface; however, at 1223 K (950 °C), fracture morphology indicated the brittle nature and the fracture took place apparently through the σ phase at the DSS-(DSS + Ni + Cu + Ti64 diffusion reaction) interface.

  10. Solvent-dependent spectral diffusion in a hydrogen bonded "vibrational aggregate".

    PubMed

    King, John T; Baiz, Carlos R; Kubarych, Kevin J

    2010-10-07

    Two-dimensional infrared spectroscopy (2DIR) is used to measure the viscosity-dependent spectral diffusion of a model vibrational probe, Mn(2)(CO)(10) (dimanganese decacarbonyl, DMDC), in a series of alcohols with time scales ranging from 2.67 ps in methanol to 5.33 ps in 1-hexanol. Alcohol-alkane solvent mixtures were found to produce indistinguishable linear IR spectra, while still demonstrating viscosity-dependent spectral diffusion. Using a vibrational exciton model to characterize the inhomogeneous energy landscape, several analogies emerge with multichromophoric electronic systems, such as J-aggregates and light-harvesting protein complexes. An excitonic, local vibrational mode Hamiltonian parametrized to reproduce the vibrational structure of DMDC serves as a starting point from which site energies (i.e., local carbonyl frequencies) are given Gaussian distributed disorder. The model gives excellent agreement with both the linear IR spectrum and the inhomogeneous widths extracted from 2DIR, indicating the system can be considered to be a "vibrational aggregate." This model naturally leads to exchange narrowing due to disorder-induced exciton localization, producing line widths consistent with our 1D and 2D measurements. Further, the diagonal disorder alone effectively reduces the molecular symmetry, leading to the appearance of Raman bands in the IR spectrum in accord with the measurements. Here, we show that the static inhomogeneity of the excitonic model with disorder successfully captures the essential details of the 1D spectrum while predicting the degree of IR activity of forbidden modes as well as the inhomogeneous widths and relative magnitudes of the transition moments.

  11. Inter-diffusion and its correlation with dynamical cross correlation in liquid Ce80Ni20

    NASA Astrophysics Data System (ADS)

    Hu, J. L.; Zhong, L. X.; Zhu, C. A.; Zhang, B.

    2017-03-01

    We reported the inter-diffusion coefficients in liquid Ce_{80}Ni_{20} measured by the sliding cell technique. Combined with the self-diffusion data of Ni measured by quasi-elastic neutron scattering in the literature, it was found that the relationship between inter-diffusion and self-diffusion in liquid Ce_{80}Ni_{20} was strongly deviated from the standard Darken equation with an abnormally small dynamical cross correlation factor S (the so called Manning factor) in a range of 0.6-0.8, less than unity in standard systems. Through the calculated distinct diffusion coefficient and its deviation from the standard one, it was discovered that the small S value was directly originated from enhanced distinct diffusion between Ce and Ni atoms and reduced distinct diffusion between Ni and Ni atoms. Because the inter-atomic interaction was not considered in the standard liquids, the present small S factor and intrinsic distinct diffusion coefficients were believed to be resulted from the chemical interaction between Ce and Ni in the liquid. The results provide new evidence of the dynamic cross correlation in liquid diffusion, and thus shed light on the understanding of the correlation between dynamics and structure in liquid alloys.

  12. Changing the dynamical behavior of nonlinear reaction diffusion systems by stochastic electric fields

    SciTech Connect

    Enderlein, J.; Kuhnert, L.

    1996-12-12

    The idea of changing the diffusivities of charged ions in a solution by the application of an external stochastic electric field is proposed. The effect of such a change of the diffusion coefficients on the dynamical behavior of the Belouzov-Zhabotinsky reaction is theoretically studied and discussed. 35 refs., 3 figs.

  13. Magnetization dynamics and spin diffusion in semiconductors and metals

    NASA Astrophysics Data System (ADS)

    Cywinski, Lukasz

    2007-12-01

    Spintronics is an emerging field of research focused on introducing the electron spin degree of freedom into electronics. Its aims include devising new means of magnetization manipulation in ferromagnets and creating systems in which the electrical expression of spin-related phenomena is possible. In this dissertation we present theoretical work important for both of these goals. In a process of ultrafast light-induced demagnetization the magnetization of a ferromagnet decreases on a sub-picosecond time-scale following an excitation by a strong laser pulse. We present a theory of this phenomenon which is applicable to ferromagnetic (III,Mn)V semiconductors. Using it we qualitatively explain the experimental results obtained recently in these materials. We also give a theory of ultrafast demagnetization in transition metals, in which we put previously proposed approaches on a sound conceptual basis, and analyze a new mechanism of demagnetization due to emission of spin waves by hot carriers. Recent progress in growth of metal-semiconductor interfaces has enabled efficient spin-polarized transport between metallic ferromagnets and semiconductors such as GaAs. We present a theory of diffusive spin transport in such metal-semiconductor structures. In contrast to popular one-dimensional approach, we take into account realistic two-dimensional lateral geometry of these systems. We also focus on room temperature regime. Our analysis of spin accumulation achievable in systems of sub-micron dimensions leads to a proposal of a new family of spintronic devices with multiple ferromagnetic terminals in contact with a semiconductor channel. We show that in a three-terminal "spin transistor" digital electric expression of spin accumulation is possible. We also calculate the time-dependent spin transport induced by rotation of one of the magnets in this system, and we show that electrical sensing of magnetization dynamics is realistic in metal-semiconductor structures. An

  14. Maxwell-Stefan diffusion and dynamical correlation in molten LiF-KF: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Jain, Richa Naja; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

    2016-05-01

    In this work our main objective is to compute Dynamical correlations, Onsager coefficients and Maxwell-Stefan (MS) diffusivities for molten salt LiF-KF mixture at various thermodynamic states through Green-Kubo formalism for the first time. The equilibrium molecular dynamics (MD) simulations were performed using BHM potential for LiF-KF mixture. The velocity autocorrelations functions involving Li ions reflect the endurance of cage dynamics or backscattering with temperature. The magnitude of Onsager coefficients for all pairs increases with increase in temperature. Interestingly most of the Onsager coefficients has almost maximum magnitude at the eutectic composition indicating the most dynamic character of the eutectic mixture. MS diffusivity hence diffusion for all ion pairs increases in the system with increasing temperature. Smooth variation of the diffusivity values denies any network formation in the mixture. Also, the striking feature is the noticeable concentration dependence of MS diffusivity between cation-cation pair, ĐLi-K which remains negative for most of the concentration range but changes sign to become positive for higher LiF concentration. The negative MS diffusivity is acceptable as it satisfies the non-negative entropy constraint governed by 2nd law of thermodynamics. This high diffusivity also vouches the candidature of molten salt as a coolant.

  15. Maxwell–Stefan diffusion and dynamical correlation in molten LiF-KF: A molecular dynamics study

    SciTech Connect

    Jain, Richa Naja Chakraborty, Brahmananda; Ramaniah, Lavanya M.

    2016-05-23

    In this work our main objective is to compute Dynamical correlations, Onsager coefficients and Maxwell-Stefan (MS) diffusivities for molten salt LiF-KF mixture at various thermodynamic states through Green–Kubo formalism for the first time. The equilibrium molecular dynamics (MD) simulations were performed using BHM potential for LiF–KF mixture. The velocity autocorrelations functions involving Li ions reflect the endurance of cage dynamics or backscattering with temperature. The magnitude of Onsager coefficients for all pairs increases with increase in temperature. Interestingly most of the Onsager coefficients has almost maximum magnitude at the eutectic composition indicating the most dynamic character of the eutectic mixture. MS diffusivity hence diffusion for all ion pairs increases in the system with increasing temperature. Smooth variation of the diffusivity values denies any network formation in the mixture. Also, the striking feature is the noticeable concentration dependence of MS diffusivity between cation-cation pair, Đ{sub Li-K} which remains negative for most of the concentration range but changes sign to become positive for higher LiF concentration. The negative MS diffusivity is acceptable as it satisfies the non-negative entropy constraint governed by 2{sup nd} law of thermodynamics. This high diffusivity also vouches the candidature of molten salt as a coolant.

  16. Dynamic interactions between a membrane binding protein and lipids induce fluctuating diffusivity

    PubMed Central

    Yamamoto, Eiji; Akimoto, Takuma; Kalli, Antreas C.; Yasuoka, Kenji; Sansom, Mark S. P.

    2017-01-01

    Pleckstrin homology (PH) domains are membrane-binding lipid recognition proteins that interact with phosphatidylinositol phosphate (PIP) molecules in eukaryotic cell membranes. Diffusion of PH domains plays a critical role in biological reactions on membrane surfaces. Although diffusivity can be estimated by long-time measurements, it lacks information on the short-time diffusive nature. We reveal two diffusive properties of a PH domain bound to the surface of a PIP-containing membrane using molecular dynamics simulations. One is fractional Brownian motion, attributed to the motion of the lipids with which the PH domain interacts. The other is temporally fluctuating diffusivity; that is, the short-time diffusivity of the bound protein changes substantially with time. Moreover, the diffusivity for short-time measurements is intrinsically different from that for long-time measurements. This fluctuating diffusivity results from dynamic changes in interactions between the PH domain and PIP molecules. Our results provide evidence that the complexity of protein-lipid interactions plays a crucial role in the diffusion of proteins on biological membrane surfaces. Changes in the diffusivity of PH domains and related membrane-bound proteins may in turn contribute to the formation/dissolution of protein complexes in membranes. PMID:28116358

  17. Dynamics of Plug Formation in a Circular Cylinder Under Low Bond Number Conditions: Experiment and Simulation

    NASA Astrophysics Data System (ADS)

    Hallaby, Ghazi; Kizito, John P.

    2016-08-01

    The goal of the current study is to investigate the dynamics of two phase interface under a low Bond number condition. Silicone oil is injected into a cylinder under a Bond number of about 0.47 via a side tube forming a T-junction with the former. The time evolution of the interface of silicon oil in a cylinder is captured using a high speed camera. The volume at which the plug is formed is then determined using an image processing tool to analyze the captured images. A numerical simulation is carried out where fluid is injected into a cylinder, under a less than unity Bond number condition, via a side tube. Numerical and experimental results are then compared.

  18. Molecular dynamics of neutral polymer bonding agent (NPBA) as revealed by solid-state NMR spectroscopy.

    PubMed

    Hu, Wei; Su, Yongchao; Zhou, Lei; Pang, Aimin; Cai, Rulin; Ma, Xingang; Li, Shenhui

    2014-01-22

    Neutral polymer bonding agent (NPBA) is one of the most promising polymeric materials, widely used in nitrate ester plasticized polyether (NEPE) propellant as bonding agent. The structure and dynamics of NPBA under different conditions of temperatures and sample processing are comprehensively investigated by solid state NMR (SSNMR). The results indicate that both the main chain and side chain of NPBA are quite rigid below its glass transition temperature (Tg). In contrast, above the Tg, the main chain remains relatively immobilized, while the side chains become highly flexible, which presumably weakens the interaction between bonding agent and the binder or oxidant fillers and in turn destabilizes the high modulus layer formed around the oxidant fillers. In addition, no obvious variation is found for the microstructure of NPBA upon aging treatment or soaking with acetone. These experimental results provide useful insights for understanding the structural properties of NPBA and its interaction with other constituents of solid composite propellants under different processing and working conditions.

  19. Communication: Relationship between solute localization and diffusion in a dynamically constrained polymer system

    NASA Astrophysics Data System (ADS)

    Saylor, David M.; Jawahery, Sudi; Silverstein, Joshua S.; Forrey, Christopher

    2016-07-01

    We investigate the link between dynamic localization, characterized by the Debye-Waller factor, , and solute self-diffusivity, D, in a polymer system using atomistic molecular dynamics simulations and vapor sorption experiments. We find a linear relationship between lnD and 1/ over more than four decades of D, encompassing most of the glass formation regime. The observed linearity is consistent with the Langevin dynamics in a periodically varying potential field and may offer a means to rapidly assess diffusion based on the characterization of dynamic localization.

  20. LETTER TO THE EDITOR: Fractal diffusion coefficient from dynamical zeta functions

    NASA Astrophysics Data System (ADS)

    Cristadoro, Giampaolo

    2006-03-01

    Dynamical zeta functions provide a powerful method to analyse low-dimensional dynamical systems when the underlying symbolic dynamics is under control. On the other hand, even simple one-dimensional maps can show an intricate structure of the grammar rules that may lead to a non-smooth dependence of global observables on parameters changes. A paradigmatic example is the fractal diffusion coefficient arising in a simple piecewise linear one-dimensional map of the real line. Using the Baladi-Ruelle generalization of the Milnor-Thurnston kneading determinant, we provide the exact dynamical zeta function for such a map and compute the diffusion coefficient from its smallest zero.

  1. Communication: Relationship between solute localization and diffusion in a dynamically constrained polymer system.

    PubMed

    Saylor, David M; Jawahery, Sudi; Silverstein, Joshua S; Forrey, Christopher

    2016-07-21

    We investigate the link between dynamic localization, characterized by the Debye-Waller factor, 〈u(2)〉, and solute self-diffusivity, D, in a polymer system using atomistic molecular dynamics simulations and vapor sorption experiments. We find a linear relationship between lnD and 1/〈u(2)〉 over more than four decades of D, encompassing most of the glass formation regime. The observed linearity is consistent with the Langevin dynamics in a periodically varying potential field and may offer a means to rapidly assess diffusion based on the characterization of dynamic localization.

  2. Malleable and Self-Healing Covalent Polymer Networks through Tunable Dynamic Boronic Ester Bonds.

    PubMed

    Cromwell, Olivia R; Chung, Jaeyoon; Guan, Zhibin

    2015-05-27

    Despite numerous strategies involving dynamic covalent bond exchange for dynamic and self-healing materials, it remains a challenge to be able to tune the malleability and self-healing properties of bulk materials through simple small molecule perturbations. Here we describe the use of tunable rates of boronic ester transesterification to tune the malleability and self-healing efficiencies of bulk materials. Specifically, we used two telechelic diboronic ester small molecules with variable transesterification kinetics to dynamically cross-link 1,2-diol-containing polymer backbones. The sample cross-linked with fast-exchanging diboronic ester showed enhanced malleability and accelerated healing compared to the slow-exchanging variant under the same conditions. Our report demonstrates the possibility of transferring small molecule kinetics to dynamic properties of bulk solid material and may serve as a guide for the rational design of tunable dynamic materials.

  3. Effect of loading rate on dynamic fracture of reaction bonded silicon nitride

    NASA Technical Reports Server (NTRS)

    Liaw, B. M.; Kobayashi, A. S.; Emery, A. F.

    1986-01-01

    Wedge-loaded, modified tapered double cantilever beam (WL-MTDCB) specimens under impact loading were used to determine the room temperature dynamic fracture response of reaction bonded silicon nitride (RBSN). The crack extension history, with the exception of the terminal phase, was similar to that obtained under static loading. Like its static counterpart, a distinct crack acceleration phase, which was not observed in dynamic fracture of steel and brittle polymers, was noted. Unlike its static counterpart, the crack continued to propagate at nearly its terminal velocity under a low dynamic stress intensity factor during the terminal phase of crack propagation. These and previously obtained results for glass and RBSN show that dynamic crack arrest under a positive dynamic stress intensity factor is unlikely in static and impact loaded structural ceramics.

  4. Investigation on W/Fe diffusion bonding using Ti foil and Ti powder interlayer by SPS

    NASA Astrophysics Data System (ADS)

    Chen, Hong-Yu; Luo, Lai-Ma; Zhang, Jun; Zan, Xiang; Zhu, Xiao-Yong; Luo, Guang-Nan; Wu, Yu-Cheng

    2015-12-01

    W/steel composites are being developed for potential application in He gas-cooled divertors and plasma-facing components in fusion reactors. In this study, the dissimilar metal joints between W and Fe were fabricated at 950 °C via spark plasma sintering method with Ti foil (Ti-F) and Ti powder (Ti-P) as the interlayer under Ar atmosphere for 5 min at 57 MPa. Microscopic structures of the W/Fe diffusion joints with Ti-F and Ti-P were investigated and compared via field-emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. Thermal cycling tests were employed to measure the thermal stability of different types of W/Ti/Fe samples. The hardness distribution across joining interfaces was also determined. After thermal cycling tests, a crack occurred along the W/Ti-P interface in the W/Ti-P/Fe samples, whereas the W/Ti-F/Fe samples were intact at the interfaces. Results revealed that Ti-F is more suitable as an interlayer than Ti-P, and the interfaces of the W/Ti-F/Fe samples have better thermal stability than those of the W/Ti-P/Fe ones.

  5. Molecular Simulations of Hydrogen Bond Cluster Size and Reorientation Dynamics in Liquid and Glassy Azole Systems.

    PubMed

    Sun, Qinfang; Harvey, Jacob A; Greco, Katharine V; Auerbach, Scott M

    2016-10-06

    We simulated the dynamics of azole groups (pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, and tetrazole) as neat liquids and tethered via linkers to aliphatic backbones to determine how tethering and varying functional groups affect hydrogen bond networks and reorientation dynamics, both factors which are thought to influence proton conduction. We used the DL_Poly_2 molecular dynamics code with the GAFF force field to simulate tethered systems over the temperature range 200-900 K and the corresponding neat liquids under liquid state temperatures at standard pressure. We computed hydrogen bond cluster sizes; orientational order parameters; orientational correlation functions associated with functional groups, linkers, and backbones; time scales; and activation energies associated with orientational randomization. All tethered systems exhibit a liquid to glassy-solid transition upon cooling from 600 to 500 K, as evidenced by orientational order parameters and correlation functions. Tethering the azoles was generally found to produce hydrogen bond cluster sizes similar to those in untethered liquids and hydrogen bond lifetimes longer than those in liquids. The simulated rates of functional group reorientation decreased dramatically upon tethering. The activation energies associated with orientational randomization agree well with NMR data for tethered imidazole systems at lower temperatures and for tethered 1,2,3-triazole systems at both low- and high-temperature ranges. Overall, our simulations corroborate the notion that tethering functional groups dramatically slows the process of reorientation. We found a linear correlation between gas-phase hydrogen bond energies and tethered functional group reorientation barriers for all azoles except for imidazole, which acts as an outlier because of both atomic charges and molecular structure.

  6. Car-Parrinello simulation of hydrogen bond dynamics in sodium hydrogen bissulfate.

    PubMed

    Pirc, Gordana; Stare, Jernej; Mavri, Janez

    2010-06-14

    We studied proton dynamics of a short hydrogen bond of the crystalline sodium hydrogen bissulfate, a hydrogen-bonded ferroelectric system. Our approach was based on the established Car-Parrinello molecular dynamics (CPMD) methodology, followed by an a posteriori quantization of the OH stretching motion. The latter approach is based on snapshot structures taken from CPMD trajectory, calculation of proton potentials, and solving of the vibrational Schrodinger equation for each of the snapshot potentials. The so obtained contour of the OH stretching band has the center of gravity at about 1540 cm(-1) and a half width of about 700 cm(-1), which is in qualitative agreement with the experimental infrared spectrum. The corresponding values for the deuterated form are 1092 and 600 cm(-1), respectively. The hydrogen probability densities obtained by solving the vibrational Schrodinger equation allow for the evaluation of potential of mean force along the proton transfer coordinate. We demonstrate that for the present system the free energy profile is of the single-well type and features a broad and shallow minimum near the center of the hydrogen bond, allowing for frequent and barrierless proton (or deuteron) jumps. All the calculated time-averaged geometric parameters were in reasonable agreement with the experimental neutron diffraction data. As the present methodology for quantization of proton motion is applicable to a variety of hydrogen-bonded systems, it is promising for potential use in computational enzymology.

  7. "Zwitterionic Proton Sponge" Hydrogen Bonding Investigations on the Basis of Car-Parrinello Molecular Dynamics.

    PubMed

    Jezierska, Aneta; Panek, Jarosław J

    2015-06-22

    1,8-Bis(dimethylamino)-4,5-dihydroxynaphthalene has been investigated on the basis of static DFT computations and Car-Parrinello molecular dynamics. The simulations were performed in the gas phase and in the solid state. The studied "zwitterionic proton sponge" possesses two, short intramolecular hydrogen bonds (O-H···O and N-H···N) classified as Low Barrier Hydrogen Bonds (LBHBs); therefore, the system studied is strongly anharmonic. In addition, the compound exists as a "zwitterion" in solution and in the solid state, thus the intramolecular hydrogen bonds belong to the class of charge-assisted interactions. The applied quantum-chemical methods enabled investigations of metric and spectroscopic parameters of the molecule. The time-evolution investigations of the H-bonding showed a strong delocalization of the bridge protons and their high mobility, reflected in the low barriers on the free energy surfaces. Frequent proton transfer phenomena were noticed. The power spectra of atomic velocity were computed to analyze the vibrational features associated with O-H and N-H stretching. A broad absorption was indicated for both hydrogen bridges. For the first time, Car-Parrinello molecular dynamics results are reported for the compound, and they indicate a broad, shallow but not barrierless, potential well for each of the bridge protons.

  8. Hydrogen Bond Dynamic Propensity Studies for Protein Binding and Drug Design

    PubMed Central

    2016-01-01

    We study the dynamic propensity of the backbone hydrogen bonds of the protein MDM2 (the natural regulator of the tumor suppressor p53) in order to determine its binding properties. This approach is fostered by the observation that certain backbone hydrogen bonds at the p53-binding site exhibit a dynamical propensity in simulations that differs markedly form their state-value (that is, formed/not formed) in the PDB structure of the apo protein. To this end, we conduct a series of hydrogen bond propensity calculations in different contexts: 1) computational alanine-scanning studies of the MDM2-p53 interface; 2) the formation of the complex of MDM2 with the disruptive small molecule Nutlin-3a (dissecting the contribution of the different molecular fragments) and 3) the binding of a series of small molecules (drugs) with different affinities for MDM2. Thus, the relevance of the hydrogen bond propensity analysis for protein binding studies and as a useful tool to complement existing methods for drug design and optimization will be made evident. PMID:27792778

  9. Car-Parrinello simulation of hydrogen bond dynamics in sodium hydrogen bissulfate

    NASA Astrophysics Data System (ADS)

    Pirc, Gordana; Stare, Jernej; Mavri, Janez

    2010-06-01

    We studied proton dynamics of a short hydrogen bond of the crystalline sodium hydrogen bissulfate, a hydrogen-bonded ferroelectric system. Our approach was based on the established Car-Parrinello molecular dynamics (CPMD) methodology, followed by an a posteriori quantization of the OH stretching motion. The latter approach is based on snapshot structures taken from CPMD trajectory, calculation of proton potentials, and solving of the vibrational Schrödinger equation for each of the snapshot potentials. The so obtained contour of the OH stretching band has the center of gravity at about 1540 cm-1 and a half width of about 700 cm-1, which is in qualitative agreement with the experimental infrared spectrum. The corresponding values for the deuterated form are 1092 and 600 cm-1, respectively. The hydrogen probability densities obtained by solving the vibrational Schrödinger equation allow for the evaluation of potential of mean force along the proton transfer coordinate. We demonstrate that for the present system the free energy profile is of the single-well type and features a broad and shallow minimum near the center of the hydrogen bond, allowing for frequent and barrierless proton (or deuteron) jumps. All the calculated time-averaged geometric parameters were in reasonable agreement with the experimental neutron diffraction data. As the present methodology for quantization of proton motion is applicable to a variety of hydrogen-bonded systems, it is promising for potential use in computational enzymology.

  10. Atomic packing and diffusion in Fe85Si2B9P4 amorphous alloy analyzed by ab initio molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Wang, Yaocen; Takeuchi, Akira; Makino, Akihiro; Liang, Yunye; Kawazoe, Yoshiyuki

    2015-05-01

    In the work reported in this paper, ab initio molecular dynamics simulation was performed on Fe85Si2B9P4 amorphous alloy. Preferred atomic environment of the elements was analyzed with Voronoi polyhedrons. It showed that B and P atoms prefer less neighbors compared with Fe and Si, making them structurally incompatible with Fe rich structure and repulsive to the formation of α-Fe. However, due to the low bonding energy of B and P caused by low coordination number, the diffusion rates of them were considerably large, resulting in the requirement of fast annealing for achieving optimum nano-crystallization for its soft magnetic property. The simulation work also indicates that diffusion rate in amorphous alloy is largely determined by bonding energy rather than atomic size.

  11. Fick diffusion coefficients of liquid mixtures directly obtained from equilibrium molecular dynamics.

    PubMed

    Liu, Xin; Schnell, Sondre K; Simon, Jean-Marc; Bedeaux, Dick; Kjelstrup, Signe; Bardow, André; Vlugt, Thijs J H

    2011-11-10

    A methodology for computing Fick diffusivities directly from equilibrium molecular dynamics (MD) simulations is presented and validated for acetone-methanol and acetone-tetrachloromethane liquid mixtures. Fick diffusivities are obtained from Maxwell-Stefan (MS) diffusivities and the so-called thermodynamic factor. MS diffusivities describe the friction between different components, while the thermodynamic factor is the concentration derivative of the activity describing the deviation from ideal mixing behavior. It is important to note that all mutual diffusion experiments measure Fick diffusion coefficients, while molecular simulation provides MS diffusivities. The required thermodynamic factor to convert MS into Fick diffusivities and vice versa, however, is usually difficult to extract from both simulations and experiments leaving a gap between theory and application. Here, we employ our novel method to compute the thermodynamic factor from small-scale density fluctuations in equilibrium MD simulations [Chem. Phys. Lett.2011, 504, 199-201]. Previously, this method was developed and validated for molecules with single interaction sites only. In this work, we applied this method to acetone-methanol and acetone-tetrachloromethane liquid mixtures and show that the method also works well in these more complex systems. This provides the missing step to extract Fick diffusion coefficients directly from equilibrium MD simulations. The computed Fick diffusivities of acetone-methanol and acetone-tetrachloromethane mixtures are in excellent agreement with experimental values. The suggested framework thus provides an efficient route to model diffusion in liquids on the basis of a consistent molecular picture.

  12. Static and Dynamic Effects of Lateral Carrier Diffusion in Semiconductor Lasers

    NASA Technical Reports Server (NTRS)

    Li, Jian-Zhong; Cheung, Samson H.; Ning, C. Z.; Biegel, Bryan A. (Technical Monitor)

    2002-01-01

    Electron and hole diffusions in the plane of semiconductor quantum wells play an important part in the static and dynamic operations of semiconductor lasers. It is well known that the value of diffusion coefficients affects the threshold pumping current of a semiconductor laser. At the same time, the strength of carrier diffusion process is expected to affect the modulation bandwidth of an AC-modulated laser. It is important not only to investigate the combined DC and AC effects due to carrier diffusion, but also to separate the AC effects from that of the combined effects in order to provide design insights for high speed modulation. In this presentation, we apply a hydrodynamic model developed by the present authors recently from the semiconductor Bloch equations. The model allows microscopic calculation of the lateral carrier diffusion coefficient, which is a nonlinear function of the carrier density and plasma temperature. We first studied combined AC and DC effects of lateral carrier diffusion by studying the bandwidth dependence on diffusion coefficient at a given DC current under small signal modulation. The results show an increase of modulation bandwidth with decrease in the diffusion coefficient. We simultaneously studied the effects of nonlinearity in the diffusion coefficient. To clearly identify how much of the bandwidth increase is a result of decrease in the threshold pumping current for smaller diffusion coefficient, thus an effective increase of DC pumping, we study the bandwidth dependence on diffusion coefficient at a given relative pumping. A detailed comparison of the two cases will be presented.

  13. The hydrogen diffusion in liquid aluminum alloys from ab initio molecular dynamics

    NASA Astrophysics Data System (ADS)

    Jakse, N.; Pasturel, A.

    2014-09-01

    We study the hydrogen diffusion in liquid aluminum alloys through extensive ab initio molecular dynamics simulations. At the microscopic scale, we show that the hydrogen motion is characterized by a broad distribution of spatial jumps that does not correspond to a Brownian motion. To determine the self-diffusion coefficient of hydrogen in liquid aluminum alloys, we use a generalized continuous time random walk model recently developed to describe the hydrogen diffusion in pure aluminum. In particular, we show that the model successfully accounts the effects of alloying elements on the hydrogen diffusion in agreement with experimental features.

  14. Perturbations and dynamics of reaction-diffusion systems with mass conservation.

    PubMed

    Kuwamura, Masataka; Morita, Yoshihisa

    2015-07-01

    In some reaction-diffusion systems where the total mass of their components is conserved, solutions with initial values near a homogeneous equilibrium converge to a simple localized pattern (spike) after exhibiting Turing-like patterns near the equilibrium for appropriate diffusion coefficients. In this study, we investigate the perturbed reaction-diffusion systems of such conserved systems. We show that a reaction-diffusion model with a globally stable homogeneous equilibrium can exhibit large amplitude Turing-like patterns in the transient dynamics. Moreover, we propose a three-component model, which exhibits an alternating repetition of spatially (almost) homogeneous oscillations and large amplitude Turing-like patterns.

  15. The hydrogen diffusion in liquid aluminum alloys from ab initio molecular dynamics.

    PubMed

    Jakse, N; Pasturel, A

    2014-09-07

    We study the hydrogen diffusion in liquid aluminum alloys through extensive ab initio molecular dynamics simulations. At the microscopic scale, we show that the hydrogen motion is characterized by a broad distribution of spatial jumps that does not correspond to a Brownian motion. To determine the self-diffusion coefficient of hydrogen in liquid aluminum alloys, we use a generalized continuous time random walk model recently developed to describe the hydrogen diffusion in pure aluminum. In particular, we show that the model successfully accounts the effects of alloying elements on the hydrogen diffusion in agreement with experimental features.

  16. Dynamics of information diffusion and its applications on complex networks

    NASA Astrophysics Data System (ADS)

    Zhang, Zi-Ke; Liu, Chuang; Zhan, Xiu-Xiu; Lu, Xin; Zhang, Chu-Xu; Zhang, Yi-Cheng

    2016-09-01

    The ongoing rapid expansion of the Word Wide Web (WWW) greatly increases the information of effective transmission from heterogeneous individuals to various systems. Extensive research for information diffusion is introduced by a broad range of communities including social and computer scientists, physicists, and interdisciplinary researchers. Despite substantial theoretical and empirical studies, unification and comparison of different theories and approaches are lacking, which impedes further advances. In this article, we review recent developments in information diffusion and discuss the major challenges. We compare and evaluate available models and algorithms to respectively investigate their physical roles and optimization designs. Potential impacts and future directions are discussed. We emphasize that information diffusion has great scientific depth and combines diverse research fields which makes it interesting for physicists as well as interdisciplinary researchers.

  17. Diffusion in energy materials: Governing dynamics from atomistic modelling

    NASA Astrophysics Data System (ADS)

    Parfitt, D.; Kordatos, A.; Filippatos, P. P.; Chroneos, A.

    2017-09-01

    Understanding diffusion in energy materials is critical to optimising the performance of solid oxide fuel cells (SOFCs) and batteries both of which are of great technological interest as they offer high efficiency for cleaner energy conversion and storage. In the present review, we highlight the insights offered by atomistic modelling of the ionic diffusion mechanisms in SOFCs and batteries and how the growing predictive capability of high-throughput modelling, together with our new ability to control compositions and microstructures, will produce advanced materials that are designed rather than chosen for a given application. The first part of the review focuses on the oxygen diffusion mechanisms in cathode and electrolyte materials for SOFCs and in particular, doped ceria and perovskite-related phases with anisotropic structures. The second part focuses on disordered oxides and two-dimensional materials as these are very promising systems for battery applications.

  18. Impact of hydrogen bonding on dynamics of hydroxyl-terminated polydimethylsiloxane

    SciTech Connect

    Xing, Kunyue; Chatterjee, Sabornie; Saito, Tomonori; Gainaru, Catalin P.; Sokolov, Alexei P.

    2016-04-06

    Dielectric spectroscopy, rheology, and differential scanning calorimetry were employed to study the effect of chain-end hydrogen bonding on the dynamics of hydroxylterminated polydimethylsiloxane. We demonstrate that hydrogen bonding has a strong influence on both segmental and slower dynamics in the systems with low molecular weights. In particular, the decrease in the chain length leads to an increase of the glass transition temperature, viscosity, and fragility index, at variance with the usual behavior of nonassociating polymers. The supramolecular association of hydroxylterminated chains leads to the emergence in dielectric and mechanical relaxation spectra of the so-called Debye process traditionally observed in monohydroxy alcohols. Our analysis suggests that the hydroxyl-terminated PDMS oligomers may associate in brush-like or chain-like structures, depending on the size of their covalent chains. Finally, the effective length of the linear-associated chains was estimated from the rheological measurements.

  19. Impact of hydrogen bonding on dynamics of hydroxyl-terminated polydimethylsiloxane

    DOE PAGES

    Xing, Kunyue; Chatterjee, Sabornie; Saito, Tomonori; ...

    2016-04-06

    Dielectric spectroscopy, rheology, and differential scanning calorimetry were employed to study the effect of chain-end hydrogen bonding on the dynamics of hydroxylterminated polydimethylsiloxane. We demonstrate that hydrogen bonding has a strong influence on both segmental and slower dynamics in the systems with low molecular weights. In particular, the decrease in the chain length leads to an increase of the glass transition temperature, viscosity, and fragility index, at variance with the usual behavior of nonassociating polymers. The supramolecular association of hydroxylterminated chains leads to the emergence in dielectric and mechanical relaxation spectra of the so-called Debye process traditionally observed in monohydroxymore » alcohols. Our analysis suggests that the hydroxyl-terminated PDMS oligomers may associate in brush-like or chain-like structures, depending on the size of their covalent chains. Finally, the effective length of the linear-associated chains was estimated from the rheological measurements.« less

  20. Local density augmentation and dynamic properties of hydrogen-and non-hydrogen-bonded supercritical fluids: a molecular dynamics study.

    PubMed

    Skarmoutsos, Ioannis; Samios, Jannis

    2007-01-28

    The local density inhomogeneities in neat supercritical fluids were investigated via canonical molecular dynamics simulations. The selected systems under investigation were the polar and hydrogen-bonded fluid methanol as well as the quadrupolar non-hydrogen-bonded carbon dioxide one. Effective local densities, local density augmentation, and enhancement factors were calculated at state points along an isotherm close to the critical temperature of each system (T(r)=1.03). The results obtained reveal strong influence of the polarity and hydrogen bonding upon the intensity of the local density augmentation. It is found that this effect is sufficiently larger in the case of the polar and associated methanol in comparison to those predicted for carbon dioxide. For both fluids the local density augmentation values are maximized in the bulk density region near 0.7rho(c), a result that is in agreement with experiment. In addition, the local density dynamics of each fluid were investigated in terms of the appropriate time correlation functions. The behavior of these functions reveals that the bulk density dependence of the local density reorganization times is very sensitive to the specific intermolecular interactions and to the size of the local region. Also, the estimated local density reorganization time as a function of bulk density of each fluid was further analyzed and successfully related to two different time-scale relaxation mechanisms. Finally, the results obtained indicate a possible relationship between the single-molecule reorientational dynamics and the local density reorganization ones.

  1. Ab initio molecular-dynamics study of diffusion and defects in solid Li3N

    NASA Astrophysics Data System (ADS)

    Sarnthein, J.; Schwarz, K.; Blöchl, P. E.

    1996-04-01

    We investigate defects and diffusion in solid Li3N, a superionic conductor, using the projector-augmented-wave implementation of Car-Parrinello molecular dynamics. Static calculations are used to discuss the structure and formation of Li vacancies, where we also consider hydrogen interstitials. The barrier for lithium jumps to vacant adjacent sites in the Li2N plane (⊥c) was found to be extremely small, namely, 0.004 eV, whereas jumps perpendicular to the Li2N plane (∥c) have a barrier of 0.58 eV. Therefore diffusion in the plane (⊥c) is limited by the formation of vacancies, whereas the barrier dominates perpendicular (∥c) to the plane. A molecular-dynamics run at 800 K confirms the anisotropy of diffusion and leads to diffusion coefficients consistent with experiment. From the trajectories we deduce a microscopic diffusion mechanism and find that mainly isolated jumps take place.

  2. Diffusion of GPI-anchored proteins is influenced by the activity of dynamic cortical actin.

    PubMed

    Saha, Suvrajit; Lee, Il-Hyung; Polley, Anirban; Groves, Jay T; Rao, Madan; Mayor, Satyajit

    2015-11-05

    Molecular diffusion at the surface of living cells is believed to be predominantly driven by thermal kicks. However, there is growing evidence that certain cell surface molecules are driven by the fluctuating dynamics of cortical cytoskeleton. Using fluorescence correlation spectroscopy, we measure the diffusion coefficient of a variety of cell surface molecules over a temperature range of 24-37 °C. Exogenously incorporated fluorescent lipids with short acyl chains exhibit the expected increase of diffusion coefficient over this temperature range. In contrast, we find that GPI-anchored proteins exhibit temperature-independent diffusion over this range and revert to temperature-dependent diffusion on cell membrane blebs, in cells depleted of cholesterol, and upon acute perturbation of actin dynamics and myosin activity. A model transmembrane protein with a cytosolic actin-binding domain also exhibits the temperature-independent behavior, directly implicating the role of cortical actin. We show that diffusion of GPI-anchored proteins also becomes temperature dependent when the filamentous dynamic actin nucleator formin is inhibited. However, changes in cortical actin mesh size or perturbation of branched actin nucleator Arp2/3 do not affect this behavior. Thus cell surface diffusion of GPI-anchored proteins and transmembrane proteins that associate with actin is driven by active fluctuations of dynamic cortical actin filaments in addition to thermal fluctuations, consistent with expectations from an "active actin-membrane composite" cell surface.

  3. Diffusion of GPI-anchored proteins is influenced by the activity of dynamic cortical actin

    PubMed Central

    Saha, Suvrajit; Lee, Il-Hyung; Polley, Anirban; Groves, Jay T.; Rao, Madan; Mayor, Satyajit

    2015-01-01

    Molecular diffusion at the surface of living cells is believed to be predominantly driven by thermal kicks. However, there is growing evidence that certain cell surface molecules are driven by the fluctuating dynamics of cortical cytoskeleton. Using fluorescence correlation spectroscopy, we measure the diffusion coefficient of a variety of cell surface molecules over a temperature range of 24–37°C. Exogenously incorporated fluorescent lipids with short acyl chains exhibit the expected increase of diffusion coefficient over this temperature range. In contrast, we find that GPI-anchored proteins exhibit temperature-independent diffusion over this range and revert to temperature-dependent diffusion on cell membrane blebs, in cells depleted of cholesterol, and upon acute perturbation of actin dynamics and myosin activity. A model transmembrane protein with a cytosolic actin-binding domain also exhibits the temperature-independent behavior, directly implicating the role of cortical actin. We show that diffusion of GPI-anchored proteins also becomes temperature dependent when the filamentous dynamic actin nucleator formin is inhibited. However, changes in cortical actin mesh size or perturbation of branched actin nucleator Arp2/3 do not affect this behavior. Thus cell surface diffusion of GPI-anchored proteins and transmembrane proteins that associate with actin is driven by active fluctuations of dynamic cortical actin filaments in addition to thermal fluctuations, consistent with expectations from an “active actin-membrane composite” cell surface. PMID:26378258

  4. Studying Smad2 intranuclear diffusion dynamics by mathematical modelling of FRAP experiments.

    PubMed

    González-Pérez, Vinicio; Schmierer, Bernhard; Hill, Caroline S; Sear, Richard P

    2011-03-01

    We combine Fluorescence Recovery After Photobleaching (FRAP) experiments with mathematical modelling to study the dynamics inside the nucleus of both the TGF-β-sensitive transcriptional regulator Smad2, and Green-Fluorescent Protein (GFP). We show how combining modelling with bleaching strips of different areas allows a rigorous test of whether or not a protein is moving via diffusion as a single species. As noted recently by others, it is important to consider diffusion during the bleaching process. Neglecting it can cause serious error. Also, it is possible to use the bleaching process itself to provide an extra consistency test to the models predicting the recovery. With our method we show that the dynamics of GFP are consistent with it diffusing as a single species in a uniform environment in which flow is negligible. In contrast, the dynamics of the intracellular signal transducer Smad2 are never consistent with it moving as a single species via simple diffusion in a homogeneous environment without flow. Adding TGF-β slows down the dynamics of Smad2 but even without TGF-β, the Smad2 dynamics are influenced by one or more of: association, flow, and inhomogeneity in space of the dynamics. We suggest that the dynamics inside cells of many proteins may be poorly described by simple diffusion of a single species, and that our methodology provides a general and powerful way to test this hypothesis.

  5. Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites

    SciTech Connect

    Holt, Adam P.; Bocharova, Vera; Cheng, Shiwang; Kisliuk, Alexander M.; White, B. Tyler; Saito, Tomonori; Uhrig, David; Mahalik, J. P.; Kumar, Rajeev; Imel, Adam E.; Etampawala, Thusitha; Martin, Halie; Sikes, Nicole; Sumpter, Bobby G.; Dadmun, Mark D.; Sokolov, Alexei P.

    2016-06-23

    It is generally believed that the strength of the polymer nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (RNP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as low as 6 kg/mol (RNP/Rg = 5.4) or as high as 140 kg/mol (RNP/Rg= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (RNP/Rg = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface is affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretching a parameter accessible from the MW or grafting density.

  6. Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites

    SciTech Connect

    Holt, Adam P.; Bocharova, Vera; Cheng, Shiwang; Kisliuk, Alexander M.; White, B. Tyler; Saito, Tomonori; Uhrig, David; Mahalik, J. P.; Kumar, Rajeev; Imel, Adam E.; Etampawala, Thusitha; Martin, Halie; Sikes, Nicole; Sumpter, Bobby G.; Dadmun, Mark D.; Sokolov, Alexei P.

    2016-06-23

    It is generally believed that the strength of the polymer nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (RNP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as low as 6 kg/mol (RNP/Rg = 5.4) or as high as 140 kg/mol (RNP/Rg= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (RNP/Rg = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface is affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretching a parameter accessible from the MW or grafting density.

  7. Controlling Interfacial Dynamics: Covalent Bonding versus Physical Adsorption in Polymer Nanocomposites

    DOE PAGES

    Holt, Adam P.; Bocharova, Vera; Cheng, Shiwang; ...

    2016-06-23

    It is generally believed that the strength of the polymer nanoparticle interaction controls the modification of near-interface segmental mobility in polymer nanocomposites (PNCs). However, little is known about the effect of covalent bonding on the segmental dynamics and glass transition of matrix-free polymer-grafted nanoparticles (PGNs), especially when compared to PNCs. In this article, we directly compare the static and dynamic properties of poly(2-vinylpyridine)/silica-based nanocomposites with polymer chains either physically adsorbed (PNCs) or covalently bonded (PGNs) to identical silica nanoparticles (RNP = 12.5 nm) for three different molecular weight (MW) systems. Interestingly, when the MW of the matrix is as lowmore » as 6 kg/mol (RNP/Rg = 5.4) or as high as 140 kg/mol (RNP/Rg= 1.13), both small-angle X-ray scattering and broadband dielectric spectroscopy show similar static and dynamic properties for PNCs and PGNs. However, for the intermediate MW of 18 kg/mol (RNP/Rg = 3.16), the difference between physical adsorption and covalent bonding can be clearly identified in the static and dynamic properties of the interfacial layer. We ascribe the differences in the interfacial properties of PNCs and PGNs to changes in chain stretching, as quantified by self-consistent field theory calculations. These results demonstrate that the dynamic suppression at the interface is affected by the chain stretching; that is, it depends on the anisotropy of the segmental conformations, more so than the strength of the interaction, which suggests that the interfacial dynamics can be effectively tuned by the degree of stretching a parameter accessible from the MW or grafting density.« less

  8. Normal and Anomalous Diffusion: An Analytical Study Based on Quantum Collision Dynamics and Boltzmann Transport Theory.

    PubMed

    Mahakrishnan, Sathiya; Chakraborty, Subrata; Vijay, Amrendra

    2016-09-15

    Diffusion, an emergent nonequilibrium transport phenomenon, is a nontrivial manifestation of the correlation between the microscopic dynamics of individual molecules and their statistical behavior observed in experiments. We present a thorough investigation of this viewpoint using the mathematical tools of quantum scattering, within the framework of Boltzmann transport theory. In particular, we ask: (a) How and when does a normal diffusive transport become anomalous? (b) What physical attribute of the system is conceptually useful to faithfully rationalize large variations in the coefficient of normal diffusion, observed particularly within the dynamical environment of biological cells? To characterize the diffusive transport, we introduce, analogous to continuous phase transitions, the curvature of the mean square displacement as an order parameter and use the notion of quantum scattering length, which measures the effective interactions between the diffusing molecules and the surrounding, to define a tuning variable, η. We show that the curvature signature conveniently differentiates the normal diffusion regime from the superdiffusion and subdiffusion regimes and the critical point, η = ηc, unambiguously determines the coefficient of normal diffusion. To solve the Boltzmann equation analytically, we use a quantum mechanical expression for the scattering amplitude in the Boltzmann collision term and obtain a general expression for the effective linear collision operator, useful for a variety of transport studies. We also demonstrate that the scattering length is a useful dynamical characteristic to rationalize experimental observations on diffusive transport in complex systems. We assess the numerical accuracy of the present work with representative experimental results on diffusion processes in biological systems. Furthermore, we advance the idea of temperature-dependent effective voltage (of the order of 1 μV or less in a biological environment, for example

  9. Analysis of molecular diffusion in resist polymer films simulated by molecular dynamics

    NASA Astrophysics Data System (ADS)

    Toriumi, Minoru; Ohfuji, Takeshi; Endo, Masayuki; Morimoto, Hiroaki

    1999-06-01

    The diffusion process of acids plays important roles in chemically amplified resists. Polymer matrices from the diffusion path, and the structure significantly influences the behavior of the acid diffusion. We have simulated the diffusions of molecules in polymer matrices by molecular dynamics in order to analyze the diffusion mechanism in chemically amplified resist syste. To represent bulk state conditions of the polymer film, we prepared the molecular structures under the 3D periodic boundary conditions utilizing the molecular simulation. This amorphous cell contained three chains of methacrylate polymers such as poly(methacrylate), poly(tert-butylmethacrylate), poly(isobornylmethacrylate) and one diffusion molecule such as oxygen and methanesulfonic acid. The structure was energy-minimized and equilibrated under stable conditions. The free volumes in the system were estimated as the volumes enclosed by the iso-potential surfaces around the polymer using the Gusev-Suter method. The average size of the free volumes in the poly(methylmethacrylate) system was obtained as 3.7 angstrom3 with large standard deviation of 11.1 angstrom3, which indicates the large width of the size- distribution of free volumes scattered at random in the system. Molecular diffusion in the energy-minimized cell was simulated for 50 picoseconds by the molecular dynamics. The time dependence of the mean-square displacements of diffusing molecules was obtained from the dynamics treatments and it determined the diffusion constant in the resist systems. It is shown that the molecules do not always rapidly diffuse with larger free volumes, but the diffusions also depend upon the interaction with the polymer, and that the computer simulation tools provide the potentia for the molecular level study of resists chemistry.

  10. Relation between frequency and H bond length in heavy water: Towards the understanding of the unusual properties of H bond dynamics in nanoporous media

    NASA Astrophysics Data System (ADS)

    Pommeret, Stanislas; Musat, Raluca; Renault, Jean Philippe; Leicknam, Jean-Claude; Bratos, Savo

    2009-06-01

    The published work on H bond dynamics mainly refers to diluted solutions HDO/D2O rather than to normal water. The reasons for this choice are both theoretical and experimental. Mechanical isolation of the OH vibrator eliminating the resonant energy transfer makes it a better probe of the local H bond network, while the dilution in heavy water reduces the infrared absorption, which permits the use of thicker experimental cells. The isotopic substitution does not alter crucially the nature of the problem. The length r of an OH . . . O group is statistically distributed over a large interval comprised between 2.7 and 3.2 A with a mean value r0 = 2.86 A. Liquid water may thus be viewed as a mixture of hydrogen bonds of different length. Two important characteristics of hydrogen bonding must be mentioned. (i) The OH stretching vibrations are strongly affected by this interaction. The shorter the length r of the hydrogen bond, the strongest the H bond link and the lower is its frequency ω: the covalent OH bond energy is lent to the OH. . .O bond and reinforces the latter. A number of useful relationships between ω and r were published to express this correlation. The one adopted in our previous work is the relationship due to Mikenda. (ii) Not only the OH vibrations, but also the HDO rotations are influenced noticeably by hydrogen bonding. This is due to steric forces that hinder the HDO rotations. As they are stronger in short than in long hydrogen bonds, rotations are slower in the first case than in the second. This effect was only recently discovered, but its existence is hardly to be contested. In the present contribution, we want to revisit the relationship between the frequency of the OH vibrator and the distance OH. . .O.

  11. Hydrogen bonding and vibrational energy relaxation of interfacial water: A full DFT molecular dynamics simulation

    NASA Astrophysics Data System (ADS)

    Jeon, Jonggu; Hsieh, Cho-Shuen; Nagata, Yuki; Bonn, Mischa; Cho, Minhaeng

    2017-07-01

    The air-water interface has been a subject of extensive theoretical and experimental studies due to its ubiquity in nature and its importance as a model system for aqueous hydrophobic interfaces. We report on the structure and vibrational energy transfer dynamics of this interfacial water system studied with equilibrium and non-equilibrium molecular dynamics simulations employing a density functional theory -based description of the system and the kinetic energy spectral density analysis. The interfacial water molecules are found to make fewer and weaker hydrogen (H)-bonds on average compared to those in the bulk. We also find that (i) the H-bonded OH groups conjugate to the free OH exhibit rather low vibrational frequencies (3000-3500 cm-1); (ii) the presence of a significant fraction (>10%) of free and randomly oriented water molecules at the interface ("labile water"), neither of whose OH groups are strong H-bond donors; (iii) the inertial rotation of free OH groups, especially from the labile water, contribute to the population decay of excited free OH groups with comparable rate and magnitude as intramolecular energy transfer between the OH groups. These results suggest that the labile water, which might not be easily detectable by the conventional vibrational sum frequency generation method, plays an important role in the surface water dynamics.

  12. Hydrogen bonding and vibrational energy relaxation of interfacial water: A full DFT molecular dynamics simulation.

    PubMed

    Jeon, Jonggu; Hsieh, Cho-Shuen; Nagata, Yuki; Bonn, Mischa; Cho, Minhaeng

    2017-07-28

    The air-water interface has been a subject of extensive theoretical and experimental studies due to its ubiquity in nature and its importance as a model system for aqueous hydrophobic interfaces. We report on the structure and vibrational energy transfer dynamics of this interfacial water system studied with equilibrium and non-equilibrium molecular dynamics simulations employing a density functional theory -based description of the system and the kinetic energy spectral density analysis. The interfacial water molecules are found to make fewer and weaker hydrogen (H)-bonds on average compared to those in the bulk. We also find that (i) the H-bonded OH groups conjugate to the free OH exhibit rather low vibrational frequencies (3000-3500 cm(-1)); (ii) the presence of a significant fraction (>10%) of free and randomly oriented water molecules at the interface ("labile water"), neither of whose OH groups are strong H-bond donors; (iii) the inertial rotation of free OH groups, especially from the labile water, contribute to the population decay of excited free OH groups with comparable rate and magnitude as intramolecular energy transfer between the OH groups. These results suggest that the labile water, which might not be easily detectable by the conventional vibrational sum frequency generation method, plays an important role in the surface water dynamics.

  13. Diffusion dynamics of small molecules from mesoporous silicon films by real-time optical interferometry

    SciTech Connect

    Mares, Jeremy W.; Weiss, Sharon M.

    2011-09-20

    Time-dependent laser reflectometry measurements are presented as a means to rigorously characterize analyte diffusion dynamics of small molecules from mesoporous silicon (PSi) films for drug delivery and membrane physics applications. Calculations based on inclusion of a spatially and temporally dependent solute concentration profile in a one-dimensional Fickian diffusion flow model are performed to determine the diffusion coefficients for the selected prototypical polar species, sucrose (340 Da), exiting from PSi films. The diffusion properties of the molecules depend on both PSi pore size and film thickness. For films with average pore diameters between 10-30 nm and film thicknesses between 300-900 nm, the sucrose diffusion coefficient can be tuned between approximately 100 and 550 {mu}m{sup 2}/s. Extensions of the real-time measurement and modeling approach for determining the diffusivity of small molecules that strongly interact with and corrode the internal surfaces of PSi films are also discussed.

  14. A molecular dynamics study of radiation induced diffusion in uranium dioxide

    NASA Astrophysics Data System (ADS)

    Martin, G.; Maillard, S.; Brutzel, L. Van; Garcia, P.; Dorado, B.; Valot, C.

    2009-03-01

    The nuclear oxide fuels are submitted 'in-pile' to strong structural and chemical modifications due to the fissions and temperature. The diffusion of species is notably the result of a thermal activation and of radiation induced diffusion. This study proposes to estimate to what extent the radiation induced diffusion contributes to the diffusion of lattice atoms in UO2. Irradiations are simulated using molecular dynamics simulation by displacement cascades induced by uranium primary knock-on atoms between 1 and 80 keV. As atoms are easier to displace when their vibration amplitude increases, the temperature range which have been investigated is 300-1400 K. Cascade overlaps were also simulated. The material is shown to melt at the end of cascades, yielding a reduced threshold energy displacement. The nuclear contribution to the radiation induced diffusion is compared to thermally activated diffusion under in-reactor and long-term storage conditions.

  15. Magnetic diffusion and ion nonlinear dynamics in magnetic reconnection

    NASA Astrophysics Data System (ADS)

    Zenitani, S.; Shinohara, I.; Nagai, T.; Wada, T.

    2013-12-01

    Magnetic reconnection is a fundamental process in many plasma systems, ranging from laboratory and solar-terrestrial environments to extreme astrophysical settings. The reconnection process is controlled by magnetic dissipation physics in a small-scale region near the reconnection point (X-line), and therefore the structure of the reconnection site is of strong interest. According to the standard picture of collisionless reconnection, the X-line is surrounded by a compact electron diffusion region and by an outer ion diffusion region. While the electron region has been extensively studied, much less is known about the ion region. In this work, we examine key aspects of the ion region in magnetic reconnection. First, we evaluate the ''diffusion'' of magnetic field lines, going back to the topology theorems. Unlike in the MHD, the idealness, the frozen-in, magnetic diffusion, and the energy dissiation can be all different in a kinetic plasma. We will apply these concepts to the reconnection site in two-dimensional particle-in-cell (PIC) simulations. Importantly, in the outer part of the ion region, even though the ion ideal condition is violated, the magnetic fields are frozen to plasma fluids. This raises a serious question to the widespread definition of the ion diffusion region, based on the ion nonidealness. We further examine the ion velocity distribution function in the same region. The distribution function contains multiple populations such as global Speiser ions, local Speiser ions, and trapped ions. The particle motion of the local Speiser ions in an appropriately rotated frame explains the plasma nonidealness. The trapped ions are the first demonstration of the regular orbits in Chen & Palmadesso (1986), in self-consistent PIC simulations. They would be observational signatures in the ion current layer near reconnection sites.

  16. Fluid dynamics of double diffusive systems. Final report

    SciTech Connect

    Koseff, J.R.

    1995-07-01

    Over the past seven years the authors have conducted an experimental, numerical, and theoretical study of the stability of doubly diffusive systems, and of mixing processes in stratified turbulence. For the study of the stability of doubly diffusive systems continuous gradients of two diffusing components (heat and salinity in this case) were used as the initial condition, and forcing was introduced by lateral heating and surface shear. The goals of this work included (1) quantification of the effects of finite amplitude disturbances on stable, double diffusive systems, particularly with respect to lateral heating, (2) development of an improved understanding of the physical phenomena present in sheardriven flows in doubly diffusive stratified environments, (3) increasing their knowledge-base on turbulent flow in stratified environments and how to represent it, and (4) formulation of a numerical code for such flows. In particular, the overall goals of this aspect of the research were as follows: (1) develop more general stability and scaling criteria for the destabilization of doubly-stratified systems, (2) study the variation of flow structure and scales with Rayleigh ratio and lateral heating ratio, (3) delineate the mechanisms governing convective layer formation and merging, (4) study the mixing processes within the convective layers and across interfaces, and estimate the heat and mass fluxes in such a system, (5) quantify the effects of turbulence and coherent structures (due to a wind-driven surface shear) on a doubly stratified system, and (6) study the interaction between surface shear and side-wall heating destabilization mechanisms. Goals 1 through 4 have been successfully completed and the results are described in this report.

  17. Nonadiabatic dynamics of floppy hydrogen bonded complexes: the case of the ionized ammonia dimer.

    PubMed

    Chalabala, Jan; Slavíček, Petr

    2016-07-27

    In the case of the ammonia dimer, we address the following questions: how ultrafast ionization dynamics is controlled by hydrogen bonding and whether we can control the products via selective ionization of a specific electron. We use quantum chemical calculations and ab initio non-adiabatic molecular dynamics simulations to model the femtosecond dynamics of the ammonia dimer upon ionization. The role of nuclear quantum effects and thermal fluctuations in predicting the structure of the dimer is emphasized; it is shown that the minimum energy and vibrationally averaged structures are rather different. The ground state structure subsequently controls the ionization dynamics. We describe reaction pathways, electronic population transfers and reaction yields with respect to ionization from different molecular orbitals. The simulations showed that the ionized ammonia dimer is highly unstable and its decay rate is primarily driven by the position of the electron hole. In the case of ground state ionization (i.e. the HOMO electron is ionized), the decay is likely to be preceded by a proton transfer (PT) channel yielding NH4(+) and NH2˙ fragments. The PT is less intense and slower compared with the ionized water dimer. After ionizing deeper lying electrons, mainly NH3(+)˙ and NH3 fragments are formed. Overall, our results show that the ionization dynamics of the ammonia and water dimers differ due to the nature of the hydrogen bond in these systems.

  18. 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.

  19. Ethylene glycol revisited: Molecular dynamics simulations and visualization of the liquid and its hydrogen-bond network☆

    PubMed Central

    Kaiser, Alexander; Ismailova, Oksana; Koskela, Antti; Huber, Stefan E.; Ritter, Marcel; Cosenza, Biagio; Benger, Werner; Nazmutdinov, Renat; Probst, Michael

    2014-01-01

    Molecular dynamics simulations of liquid ethylene glycol described by the OPLS-AA force field were performed to gain insight into its hydrogen-bond structure. We use the population correlation function as a statistical measure for the hydrogen-bond lifetime. In an attempt to understand the complicated hydrogen-bonding, we developed new molecular visualization tools within the Vish Visualization shell and used it to visualize the life of each individual hydrogen-bond. With this tool hydrogen-bond formation and breaking as well as clustering and chain formation in hydrogen-bonded liquids can be observed directly. Liquid ethylene glycol at room temperature does not show significant clustering or chain building. The hydrogen-bonds break often due to the rotational and vibrational motions of the molecules leading to an H-bond half-life time of approximately 1.5 ps. However, most of the H-bonds are reformed again so that after 50 ps only 40% of these H-bonds are irreversibly broken due to diffusional motion. This hydrogen-bond half-life time due to diffusional motion is 80.3 ps. The work was preceded by a careful check of various OPLS-based force fields used in the literature. It was found that they lead to quite different angular and H-bond distributions. PMID:24748697

  20. The Effect of Cellular Receptor Diffusion on Receptor-Mediated Viral Binding Using Brownian Adhesive Dynamics (BRAD) Simulations

    PubMed Central

    English, Thomas J.; Hammer, Daniel A.

    2005-01-01

    Brownian adhesive dynamics (BRAD) is a new method for simulating the attachment of viruses to cell surfaces. In BRAD, the motion of the virus is subject to stochastic bond formation and breakage, and thermal motion owing to collisions from the solvent. In the model, the virus is approximated as a rigid sphere and the cell surface is approximated as a rigid plane coated with receptors. In this article, we extend BRAD to allow for the mobility of receptors in the plane of the membrane, both before and after they are ligated by viral attachment proteins. Allowing the proteins to move within the membrane produced several differences in behavior from when the receptors are immobilized. First, the mean steady-state bond number is unaffected by changes in cellular receptor density because proteins are now free to diffuse into the contact area, and the extent of binding is dictated by the availability of viral attachment proteins. Second, the time required to reach steady-state binding increases as both the cellular receptor number decreases and the receptor mobility decreases. This is because receptor diffusion is a slower process than the binding kinetics of the proteins. Decreasing the rate of protein binding was found to decrease the fraction of viruses bound to steady state, but not the extent of binding for those viruses that were bound. Increasing the binding rate increased the fraction of viruses bound, until no further viruses could bind. Alterations in receptor binding kinetics had no discernable effect on the mean steady-state bond number between virus and cell, because interactions were of sufficiently high affinity that all available receptor-viral attachment proteins were destined to bind at steady state. PMID:15556985

  1. A molecular dynamics study of guest-host hydrogen bonding in alcohol clathrate hydrates.

    PubMed

    Hiratsuka, Masaki; Ohmura, Ryo; Sum, Amadeu K; Alavi, Saman; Yasuoka, Kenji

    2015-05-21

    Clathrate hydrates are typically stabilized by suitably sized hydrophobic guest molecules. However, it has been experimentally reported that isomers of amyl-alcohol C5H11OH can be enclosed into the 5(12)6(4) cages in structure II (sII) clathrate hydrates, even though the effective radii of the molecules are larger than the van der Waals radii of the cages. To reveal the mechanism of the anomalous enclathration of hydrophilic molecules, we performed ab initio and classical molecular dynamics simulations (MD) and analyzed the structure and dynamics of a guest-host hydrogen bond for sII 3-methyl-1-butanol and structure H (sH) 2-methyl-2-butanol clathrate hydrates. The simulations clearly showed the formation of guest-host hydrogen bonds and the incorporation of the O-H group of 3-methyl-1-butanol guest molecules into the framework of the sII 5(12)6(4) cages, with the remaining hydrophobic part of the amyl-alcohol molecule well accommodated into the cages. The calculated vibrational spectra of alcohol O-H bonds showed large frequency shifts due to the strong guest-host hydrogen bonding. The 2-methyl-2-butanol guests form strong hydrogen bonds with the cage water molecules in the sH clathrate, but are not incorporated into the water framework. By comparing the structures of the alcohols in the hydrate phases, the effect of the location of O-H groups in the butyl chain of the guest molecules on the crystalline structure of the clathrate hydrates is indicated.

  2. Determination of rotary diffusivity of poly(n-propyl isocyanate) by molecular dynamics

    NASA Astrophysics Data System (ADS)

    Laso, M.; Jimeno, N.; Muneta, L. M.; Müller, M.

    2006-12-01

    The rotational dynamics of a nondilute solution of the rodlike polymer poly(n-propyl isocyanate) (PPIC) has been studied on an atomistic model by means of a large-scale classical molecular dynamics investigation. The rotary diffusivity of PPIC in toluene solution has been determined from the Einsteinian diffusion regime of the end-to-end vector on the surface of the unit sphere and has been found to be Dr=10.5×105(±2.7)s-1, which falls in the range of the experimental data available. A comparison of molecular dynamics predictions with theoretical and perturbation expansion predictions has also been performed.

  3. Determination of rotary diffusivity of poly(n-propyl isocyanate) by molecular dynamics.

    PubMed

    Laso, M; Jimeno, N; Muneta, L M; Müller, M

    2006-12-28

    The rotational dynamics of a nondilute solution of the rodlike polymer poly(n-propyl isocyanate) (PPIC) has been studied on an atomistic model by means of a large-scale classical molecular dynamics investigation. The rotary diffusivity of PPIC in toluene solution has been determined from the Einsteinian diffusion regime of the end-to-end vector on the surface of the unit sphere and has been found to be Dr=10.5x10(5)(+/-2.7) s-1, which falls in the range of the experimental data available. A comparison of molecular dynamics predictions with theoretical and perturbation expansion predictions has also been performed.

  4. A scintillator fabricated by solid-state diffusion bonding for high spatial resolution x-ray imaging

    NASA Astrophysics Data System (ADS)

    Kameshima, Takashi; Sato, Takahiro; Kudo, Togo; Ono, Shun; Ozaki, Kyosuke; Katayama, Tetsuo; Hatsui, Takaki; Yabashi, Makina

    2016-07-01

    Lens-coupled two-dimensional indirect X-ray detectors with thin-film scintillators are important for high spatial resolution X-ray imaging. To achieve high quality high-resolution images, we propose a novel fabrication method for thin-film scintillators based on solid-state diffusion bonding. Scintillators were successfully produced with thicknesses of 5, 10, and 20 μm, with a surface flatness better than λ/10. X-ray imaging performance with a point spread function of 8 μm FWHM was demonstrated with a prototype X-ray detector equipped with a 20-μm-thick scintillator, at an effective spatial sampling of 4 μm/pixel and a field of view of 2.56 x 1.92 mm2. At the request of all authors of the paper and with the agreement of the proceedings editors an updated version of this article was published on 1 September 2016. An older version of the paper was inadvertently supplied to AIP Publishing and the final version is now available.

  5. Complex dynamics in initially separated reaction-diffusion systems

    NASA Astrophysics Data System (ADS)

    Havlin, S.; Araujo, M.; Lereah, Y.; Larralde, H.; Shehter, A.; Stanley, H. E.; Trunfio, P.; Vilensky, B.

    1995-02-01

    We review recent developments in the study of the diffusion reaction systems of the type A + B → C in which the reactants are initially separated. We consider the case where the A and B particles are initially placed uniformly in Euclidean space at x > 0 and x < 0, respectively. We find that whereas for d ⩾ 2 the mean field exponent characterizes the width of the reaction zone, fluctuations are relevant in the one-dimensional system. We present analytical and numerical results for the reaction rate on fractals and percolation systems at criticality.We also study the case where the particles are Lévy flights in d = 1. Finally, we consider experimentally, analytically, and numerically the reaction A + Bstatic → C, where species A diffuses from a localized source.

  6. Neutron Crystallography, Molecular Dynamics, and Quantum Mechanics Studies of the Nature of Hydrogen Bonding in Cellulose I beta

    USDA-ARS?s Scientific Manuscript database

    In the crystal structure of cellulose Ibeta, disordered hydrogen (H) bonding can be represented by the average of two mutually exclusive H bonding schemes that have been designated A and B. An unanswered question is whether A and B interconvert dynamically, or whether they are static but present in ...

  7. Dynamic response of a pulsed Burke-Schumann diffusion flame

    NASA Technical Reports Server (NTRS)

    Sheu, Jyh-Cherng; Stocker, Dennis P.; Chen, Lea-Der

    1995-01-01

    Turbulent flames are often envisioned as an ensemble of random vortices interacting with the combustion process. A better understanding of the vortex-flame interactions therefore would be useful in improving the modeling of turbulent diffusion flames. Substantial simplification may be made by investigating controlled interactions in a laminar flame, as opposed to random interactions in a turbulent flame. The general goals of the research project are to improve our understanding of (1) the influence of buoyancy on co-flow diffusion flames and (2) the effects of buoyancy on vortex-flame interactions in co-flow diffusion flames. As a first step toward objective (2), we conducted a joint experimental and numerical investigation of the vortex-flame interaction. Vortices were produced by mechanically pulsing the fuel flow at a low frequency, e.g., 10 Hz. Experiments were conducted using a nonflickering Burke-Schumann flame in both microgravity (mu-g) and normal gravity (1g) as a means of varying the buoyant force without modification of the pressure (i.e., density). The effects of buoyant convection may then be determined by a comparison of the mu-g and 1g results. The mu-g results may also reveal the important mechanisms which are masked or overwhelmed by buoyant convection in 1g. A numerical investigation was conducted using a validated, time-accurate numerical code to study the underlying physics during the flame interaction and to assist the interpretation of the experimental results.

  8. Massively parallel dual control volume grand canonical molecular dynamics with LADERA II. Gradient driven diffusion through polymers

    NASA Astrophysics Data System (ADS)

    Ford Grant, David M.; Heffelfinger, S.

    This paper, the second part of a series, extends the capabilities of the LADERA FORTRAN code for massively parallel dual control volume grand canonical molecular dynamics (DCVGCMD). DCV-GCMD is a hybrid of two more common molecular simulation techniques (grand canonical Monte Carlo and molecular dynamics) which allows the direct molecularlevel modelling of diffusion under a chemical potential gradient. The present version of the code, LADERA-B has the capability of modelling systems with explicit intramolecular interactions such as bonds, angles, and dihedral rotations. The utility of the new code for studying gradient-driven diffusion of small molecules through polymers is demonstrated by applying it to two model systems. LADERA-B includes another new feature, which is the use of neighbour lists in force calculations. This feature increases the speed of the code but presents several challenges in the parallel hybrid algorithm. There is discussion on how these problems were addressed and how our implementation results in a significant increase in speed over the original LADERA. Scaling results are presented for LADERA-B on two massively parallel message-passing machines.

  9. H-shaped supra-amphiphiles based on a dynamic covalent bond.

    PubMed

    Wang, Guangtong; Wang, Chao; Wang, Zhiqiang; Zhang, Xi

    2012-10-16

    The imine bond, a kind of dynamic covalent bond, is used to bind two bolaform amphiphiles together with spacers, yielding H-shaped supra-amphiphiles. Micellar aggregates formed by the self-assembly of the H-shaped supra-amphiphiles are observed. When pH is tuned down from basic to slightly acidic, the benzoic imine bond can be hydrolyzed, leading to the dissociation of H-shaped supra-amphiphiles. Moreover, H-shaped supra-amphiphiles have a lower critical micelle concentration than their building blocks, which is very helpful in enhancing the stability of the benzoic imine bond being hydrolyzed by acid. The surface tension isotherms of the H-shaped supra-amphiphiles with different spacers indicate their twisty conformation at a gas-water interface. The study of H-shaped supra-amphiphiles can enrich the family of amphiphiles, and moreover, the pH-responsiveness may make them apply to controlled or targetable drug delivery in a biological environment.

  10. Nitroxide/substrate weak hydrogen bonding: attitude and dynamics of collisions in solution.

    PubMed

    Russ, Jennifer L; Gu, Juan; Tsai, Kun-Hsiang; Glass, Tom; Duchamp, James C; Dorn, Harry C

    2007-06-06

    The study of intermolecular collisions and bonding interactions in solutions is of critical importance in understanding and predicting solute/solvent properties. Previous work has established that stable paramagnetic nitroxide molecules are excellent probes of intermolecular interactions for hydrogen bonding in polar solvents. In this study, 1H, 2H, 13C, 15N NMR and liquid/liquid intermolecular transfer dynamic nuclear polarization (L2IT DNP) results are obtained for the paramagnetic probe molecule, TEMPO, interacting with the common aprotic and protic polar solvents, CH3CN and CH3CONH2, yielding a profile of both dipolar and scalar interactions. A significant scalar contact hyperfine is observed for the N-O...H-C interaction (13CH3 hyperfine, a/h=0.66 MHz) in the CH3CN/TEMPO system, whereas the N-O...H-C and N-O...H-N interactions for the TEMPO/CH3CONH2 system yield 13CH3 and 15N hyperfine couplings of a/h=0.16 and -0.50 MHz, respectively. The distance and attitude of the scalar interaction for the nitroxide hydrogen bonding at the methyl group in CH3CN and the amino group in CH3CONH2 are computed using density functional theory (DFT), yielding good agreement with the experimental results. These results show that the hyperfine coupling provides a sensitive probe of weak hydrogen-bonding interactions in solution.

  11. Molecular dissociation in the presence of catalysts: interpreting bond breaking as a quantum dynamical phase transition

    NASA Astrophysics Data System (ADS)

    Ruderman, A.; Dente, A. D.; Santos, E.; Pastawski, H. M.

    2015-08-01

    In this work we show that molecular chemical bond formation and dissociation in the presence of the d-band of a metal catalyst can be described as a quantum dynamical phase transition (QDPT). This agrees with DFT calculations that predict sudden jumps in some observables as the molecule breaks. According to our model this phenomenon emerges because the catalyst provides for a non-Hermitian Hamiltonian. We show that when the molecule approaches the surface, as occurs in the Heyrovsky reaction of H2, the bonding H2 orbital has a smooth crossover into a bonding molecular orbital built with the closest H orbital and the surface metal d-states. The same occurs for the antibonding state. Meanwhile, two resonances appear within the continuous spectrum of the d-band, which are associated with bonding and antibonding orbitals between the furthest H atom and the d-states at the second metallic layer. These move toward the band center, where they collapse into a pure metallic resonance and an almost isolated H orbital. This phenomenon constitutes a striking example of the non-trivial physics enabled when one deals with non-Hermitian Hamiltonian beyond the usual wide band approximation.

  12. Hydrogen-bond-dynamics-based switching of conductivity and magnetism: a phase transition caused by deuterium and electron transfer in a hydrogen-bonded purely organic conductor crystal.

    PubMed

    Ueda, Akira; Yamada, Shota; Isono, Takayuki; Kamo, Hiromichi; Nakao, Akiko; Kumai, Reiji; Nakao, Hironori; Murakami, Youichi; Yamamoto, Kaoru; Nishio, Yutaka; Mori, Hatsumi

    2014-08-27

    A hydrogen bond (H-bond) is one of the most fundamental and important noncovalent interactions in chemistry, biology, physics, and all other molecular sciences. Especially, the dynamics of a proton or a hydrogen atom in the H-bond has attracted increasing attention, because it plays a crucial role in (bio)chemical reactions and some physical properties, such as dielectricity and proton conductivity. Here we report unprecedented H-bond-dynamics-based switching of electrical conductivity and magnetism in a H-bonded purely organic conductor crystal, κ-D3(Cat-EDT-TTF)2 (abbreviated as κ-D). This novel crystal κ-D, a deuterated analogue of κ-H3(Cat-EDT-TTF)2 (abbreviated as κ-H), is composed only of a H-bonded molecular unit, in which two crystallographically equivalent catechol-fused ethylenedithiotetrathiafulvalene (Cat-EDT-TTF) skeletons with a +0.5 charge are linked by a symmetric anionic [O···D···O](-1)-type strong H-bond. Although the deuterated and parent hydrogen systems, κ-D and κ-H, are isostructural paramagnetic semiconductors with a dimer-Mott-type electronic structure at room temperature (space group: C2/c), only κ-D undergoes a phase transition at 185 K, to change to a nonmagnetic insulator with a charge-ordered electronic structure (space group: P1). The X-ray crystal structure analysis demonstrates that this dramatic switching of the electronic structure and physical properties originates from deuterium transfer or displacement within the H-bond accompanied by electron transfer between the Cat-EDT-TTF π-systems, proving that the H-bonded deuterium dynamics and the conducting TTF π-electron are cooperatively coupled. Furthermore, the reason why this unique phase transition occurs only in κ-D is qualitatively discussed in terms of the H/D isotope effect on the H-bond geometry and potential energy curve.

  13. The impact of interface bonding efficiency on high-burnup spent nuclear fuel dynamic performance

    DOE PAGES

    Jiang, Hao; Wang, Jy-An John; Wang, Hong

    2016-09-26

    Finite element analysis (FEA) was used to investigate the impact of interfacial bonding efficiency at pellet-pellet and pellet-clad interfaces of high-burnup (HBU) spent nuclear fuel (SNF) on system dynamic performance. Bending moments M were applied to FEA model to evaluate the system responses. From bending curvature, κ, flexural rigidity EI can be estimated as EI = M/κ. The FEA simulation results were benchmarked with experimental results from cyclic integrated reversal bending fatigue test (CIRFT) of HBR fuel rods. The consequence of interface debonding between fuel pellets and cladding is a redistribution of the loads carried by the fuel pellets tomore » the clad, which results in a reduction in composite rod system flexural rigidity. Furthermore, the interface bonding efficiency at the pellet-pellet and pellet-clad interfaces can significantly dictate the SNF system dynamic performance. With the consideration of interface bonding efficiency, the HBU SNF fuel property was estimated with CIRFT test data.« less

  14. Dynamic contrast-enhanced diffuse optical tomography (DCE-DOT): experimental validation with a dynamic phantom

    PubMed Central

    Unlu, Mehmet Burcin; Lin, Yuting; Gulsen, Gultekin

    2010-01-01

    Dynamic contrast-enhanced diffuse optical tomography (DCE-DOT) can provide spatially resolved enhancement kinetics of an optical contrast agent. We undertook a systematic phantom study to evaluate the effects of the geometrical parameters such as the depth and size of the inclusion as well as the optical parameters of the background on the recovered enhancement kinetics of the most commonly used optical contrast agent, indocyanine green (ICG). For this purpose a computer-controlled dynamic phantom was constructed. An ICG–intralipid–water mixture was circulated through the inclusions while the DCE-DOT measurements were acquired with a temporal resolution of 16 s. The same dynamic study was repeated using inclusions of different sizes located at different depths. In addition to this, the effect of non-scattering regions was investigated by placing a second inclusion filled with water in the background. The phantom studies confirmed that although the peak enhancement varied substantially for each case, the recovered injection and dilution rates obtained from the percentage enhancement maps agreed within 15% independent of not only the depth and the size of the inclusion but also the presence of a non-scattering region in the background. Although no internal structural information was used in these phantom studies, it may be necessary to use it for small objects buried deep in tissue. However, the different contrast mechanisms of optical and other imaging modalities as well as imperfect co-registration between both modalities may lead to potential errors in the structural a priori. Therefore, the effect of erroneous selection of structural priors was investigated as the final step. Again, the injection and dilution rates obtained from the percentage enhancement maps were also immune to the systematic errors introduced by erroneous selection of the structural priors, e.g. choosing the diameter of the inclusion 20% smaller increased the peak enhancement 60% but

  15. 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.

  16. Conformational dynamics of a crystalline protein from microsecond-scale molecular dynamics simulations and diffuse X-ray scattering

    DOE PAGES

    Wall, Michael E.; Van Benschoten, Andrew H.; Sauter, Nicholas K.; ...

    2014-12-01

    X-ray diffraction from protein crystals includes both sharply peaked Bragg reflections and diffuse intensity between the peaks. The information in Bragg scattering is limited to what is available in the mean electron density. The diffuse scattering arises from correlations in the electron density variations and therefore contains information about collective motions in proteins. Previous studies using molecular-dynamics (MD) simulations to model diffuse scattering have been hindered by insufficient sampling of the conformational ensemble. To overcome this issue, we have performed a 1.1-μs MD simulation of crystalline staphylococcal nuclease, providing 100-fold more sampling than previous studies. This simulation enables reproducible calculationsmore » of the diffuse intensity and predicts functionally important motions, including transitions among at least eight metastable states with different active-site geometries. The total diffuse intensity calculated using the MD model is highly correlated with the experimental data. In particular, there is excellent agreement for the isotropic component of the diffuse intensity, and substantial but weaker agreement for the anisotropic component. The decomposition of the MD model into protein and solvent components indicates that protein–solvent interactions contribute substantially to the overall diffuse intensity. In conclusion, diffuse scattering can be used to validate predictions from MD simulations and can provide information to improve MD models of protein motions.« less

  17. Li ion diffusion mechanisms in LiFePO4: an ab initio molecular dynamics study.

    PubMed

    Yang, Jianjun; Tse, John S

    2011-11-17

    The mechanisms for thermal (self) diffusion of Li ions in fully lithiated LiFePO(4) have been investigated with spin polarized ab initio molecular dynamics calculations. The effect of electron correlation is taken into account with the GGA+U formalism. It was found that Li ion diffusion is not a continuous process but through a series of jumps from one site to another. A dominant process is the hopping between neighboring Li sites around the PO(4) groups, which results in a zigzag pathway along the crystallographic b-axis. This observation is in agreement with a recent neutron diffraction experiment. A second process involves the collaborative movements of the Fe ions leading to the formation of antisite defects and promotes Li diffusion across the Li ion channels. The finding of the second mechanism demonstrates the benefit of ab initio molecular dynamics simulation in sampling diffusion pathways that may not be anticipated.

  18. First-principles molecular dynamics study of deuterium diffusion in liquid tin

    NASA Astrophysics Data System (ADS)

    Liu, Xiaohui; Zheng, Daye; Ren, Xinguo; He, Lixin; Chen, Mohan

    2017-08-01

    Understanding the retention of hydrogen isotopes in liquid metals, such as lithium and tin, is of great importance in designing a liquid plasma-facing component in fusion reactors. However, experimental diffusivity data of hydrogen isotopes in liquid metals are still limited or controversial. We employ first-principles molecular dynamics simulations to predict diffusion coefficients of deuterium in liquid tin at temperatures ranging from 573 to 1673 K. Our simulations indicate faster diffusion of deuterium in liquid tin than the self-diffusivity of tin. In addition, we find that the structural and dynamic properties of tin are insensitive to the inserted deuterium at temperatures and concentrations considered. We also observe that tin and deuterium do not form stable solid compounds. These predicted results from simulations enable us to have a better understanding of the retention of hydrogen isotopes in liquid tin.

  19. Information and disease diffusion in dynamic social environments

    NASA Astrophysics Data System (ADS)

    Vespignani, Alessandro

    2013-03-01

    In recent years the increasing availability of computer power and informatics tools has enabled the gathering of reliable data quantifying the complexity of socio-technical systems. Data-driven computational models have emerged as appropriate tools to tackle the study of contagion and diffusion processes as diverse as epidemic outbreaks, information spreading and Internet packet routing. These models aim at providing a rationale for understanding the emerging tipping points and nonlinear properties that often underpin the most interesting characteristics of socio-technical systems. Here I review some of the recent progress in modeling contagion and epidemic processes that integrates the complex features and heterogeneities of real-world systems.

  20. Mass-dependent bond vibrational dynamics influence catalysis by HIV-1 protease.

    PubMed

    Kipp, D Randal; Silva, Rafael G; Schramm, Vern L

    2011-12-07

    Protein motions that occur on the microsecond to millisecond time scale have been linked to enzymatic rates observed for catalytic turnovers, but not to transition-state barrier crossing. It has been hypothesized that enzyme motions on the femtosecond time scale of bond vibrations play a role in transition state formation. Here, we perturb femtosecond motion by substituting all nonexchangeable carbon, nitrogen, and hydrogen atoms with (13)C, (15)N, and (2)H and observe the catalytic effects in HIV-1 protease. According to the Born-Oppenheimer approximation, isotopic substitution alters vibrational frequency with unchanged electrostatic properties. With the use of a fluorescent peptide to report on multiple steps in the reaction, we observe significantly reduced rates in the heavy enzyme relative to the light enzyme. A possible interpretation of our results is that there exists a dynamic link between mass-dependent bond vibrations of the enzyme and events in the reaction coordinate. © 2011 American Chemical Society

  1. Molecular dynamics models and thermodynamic characteristics of hydrogen bonds in 1,2-ethanediol

    NASA Astrophysics Data System (ADS)

    Usacheva, T. M.; Zhuravlev, V. I.; Lifanova, N. V.; Matveev, V. K.

    2017-06-01

    A correlation between the lifetimes of hydrogen bonds and the thermodynamic characteristics of their formation and breaking, and the experimental relaxation times of dielectric spectra and the energy characteristics of relaxation processes, is observed via molecular dynamics (MD) simulation of the rearranging of the network structure of 1,2-ethanediol. The MD torsional frequency of the transition of gauche conformer tGg' at 224.1 cm-1 and the experimental frequency of the band maximum of torsional vibrations at 230 cm-1 in the infrared spectrum correlate with the oscillation frequency of molecules at 240 cm-1 inside clusters in the Dissado-Hill (DH) model. The MD and DH models indicate a predominantly parallel alignment of the electric dipole moments of conformers tGg' in the three-dimensional network of hydrogen bonds of the liquid 1,2-ethanediol phase.

  2. Bolaform superamphiphile based on a dynamic covalent bond and its self-assembly in water.

    PubMed

    Wang, Guangtong; Wang, Chao; Wang, Zhiqiang; Zhang, Xi

    2011-10-18

    We have employed a dynamic covalent bond to fabricate a bolaform superamphiphile, which can be used as building blocks for controlled assembly and disassembly. In alkaline environment, one building block bearing a benzoic aldehyde group can react with the other building block bearing an amino group to form a bolaform superamphiphile. It is found that the bolaform superamphiphiles can self-assemble in water to form micellar aggregates. When the pH is tuned down to slightly acidic values, the benzoic imine bond can be hydrolyzed, leading to the dissociation of the superamphiphile. The micellar aggregates will also disassemble, and the loaded guest molecules are released subsequently. This line of research has enriched the family of bolaform amphiphiles, and the resulting assemblies may find application in the field of controlled and targetable drug-delivery in a biological environment. © 2011 American Chemical Society

  3. Emergence of hydrogen bonds from molecular dynamics simulation of substituted N-phenylthiourea-catechol oxidase complex.

    PubMed

    Park, Kyung-Lae

    2017-01-01

    A series of N-phenylthiourea derivatives was built starting from the X-ray structure in the molecular mechanics framework and the interaction profile in the complex with the catechol oxidase was traced using molecular dynamics simulation. The results showed that the geometry and interactions between ligand and receptor were highly related to the position of the substituted side chains of phenyl moiety. At the end of molecular dynamics run, a concentrated multicenter hydrogen bond was created between the substituted ligand and receptor. The conformation of the ligand itself were also restricted in the receptor pocket. Furthermore, the simulation time of 50 ns were found to be long enough to explore the relevant conformational space and the stationary behavior of the molecular dynamic could be observed.

  4. Computation of the hindrance factor for the diffusion for nanoconfined ions: molecular dynamics simulations versus continuum-based models

    NASA Astrophysics Data System (ADS)

    Zhu, Haochen; Ghoufi, Aziz; Szymczyk, Anthony; Balannec, Béatrice; Morineau, Denis

    2012-06-01

    We report the self-diffusion coefficients and hindrance factor for the diffusion of ions into cylindrical hydrophilic silica nanopores (hydrated silica) determined from molecular dynamics (MD) simulations. We make a comparison with the hindered diffusion coefficients used in continuum-based models of nanofiltration (NF). Hindrance factors for diffusion estimated from the macroscopic hydrodynamic theory were found to be in fair quantitative agreement with MD simulations for a protonated pore, but they strongly overestimate diffusion inside a deprotonated pore.

  5. 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.

  6. Turing pattern dynamics and adaptive discretization for a super-diffusive Lotka-Volterra model.

    PubMed

    Bendahmane, Mostafa; Ruiz-Baier, Ricardo; Tian, Canrong

    2016-05-01

    In this paper we analyze the effects of introducing the fractional-in-space operator into a Lotka-Volterra competitive model describing population super-diffusion. First, we study how cross super-diffusion influences the formation of spatial patterns: a linear stability analysis is carried out, showing that cross super-diffusion triggers Turing instabilities, whereas classical (self) super-diffusion does not. In addition we perform a weakly nonlinear analysis yielding a system of amplitude equations, whose study shows the stability of Turing steady states. A second goal of this contribution is to propose a fully adaptive multiresolution finite volume method that employs shifted Grünwald gradient approximations, and which is tailored for a larger class of systems involving fractional diffusion operators. The scheme is aimed at efficient dynamic mesh adaptation and substantial savings in computational burden. A numerical simulation of the model was performed near the instability boundaries, confirming the behavior predicted by our analysis.

  7. Dissipative particle dynamics of diffusion-NMR requires high Schmidt-numbers

    NASA Astrophysics Data System (ADS)

    Azhar, Mueed; Greiner, Andreas; Korvink, Jan G.; Kauzlarić, David

    2016-06-01

    We present an efficient mesoscale model to simulate the diffusion measurement with nuclear magnetic resonance (NMR). On the level of mesoscopic thermal motion of fluid particles, we couple the Bloch equations with dissipative particle dynamics (DPD). Thereby we establish a physically consistent scaling relation between the diffusion constant measured for DPD-particles and the diffusion constant of a real fluid. The latter is based on a splitting into a centre-of-mass contribution represented by DPD, and an internal contribution which is not resolved in the DPD-level of description. As a consequence, simulating the centre-of-mass contribution with DPD requires high Schmidt numbers. After a verification for fundamental pulse sequences, we apply the NMR-DPD method to NMR diffusion measurements of anisotropic fluids, and of fluids restricted by walls of microfluidic channels. For the latter, the free diffusion and the localisation regime are considered.

  8. Molecular dynamics simulations of gas diffusion in metal-organic frameworks: argon in CuBTC.

    PubMed

    Skoulidas, Anastasios I

    2004-02-11

    The class of coordination polymers known as metal-organic frameworks (MOFs) has three-dimensional porous structures that are considered as a promising alternative to zeolites and other nanoporous materials for catalysis, gas adsorption, and gas separation applications. In this paper, we present the first study of gas diffusion inside an MOF and compare the observed diffusion to known behaviors in zeolites. Using grand canonical Monte Carlo and equilibrium molecular dynamics, we calculate the adsorption isotherm and self-, corrected, and transport diffusivities for argon in the CuBTC metal-organic framework. Our results indicate that diffusion of Ar in CuBTC is very similar to Ar diffusion in silica zeolites in magnitude, concentration, and temperature dependence. This conclusion appears to apply to a broad range of MOF structures.

  9. Self-diffusion and structural properties of confined fluids in dynamic coexistence.

    PubMed

    de Sousa, N; Sáenz, J J; Scheffold, Frank; García-Martín, A; Froufe-Pérez, L S

    2016-04-06

    Self-diffusion and radial distribution functions are studied in a strongly confined Lennard-Jones fluid. Surprisingly, in the solid-liquid phase transition region, where the system exhibits dynamic coexistence, the self-diffusion constants are shown to present up to three-fold variations from solid to liquid phases at fixed temperature, while the radial distribution function corresponding to both the liquid and the solid phases are essentially indistinguishable.

  10. Diffusion dynamics of socially learned foraging techniques in squirrel monkeys.

    PubMed

    Claidière, Nicolas; Messer, Emily J E; Hoppitt, William; Whiten, Andrew

    2013-07-08

    Social network analyses and experimental studies of social learning have each become important domains of animal behavior research in recent years yet have remained largely separate. Here we bring them together, providing the first demonstration of how social networks may shape the diffusion of socially learned foraging techniques. One technique for opening an artificial fruit was seeded in the dominant male of a group of squirrel monkeys and an alternative technique in the dominant male of a second group. We show that the two techniques spread preferentially in the groups in which they were initially seeded and that this process was influenced by monkeys' association patterns. Eigenvector centrality predicted both the speed with which an individual would first succeed in opening the artificial fruit and the probability that they would acquire the cultural variant seeded in their group. These findings demonstrate a positive role of social networks in determining how a new foraging technique diffuses through a population. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Aggregation-fragmentation-diffusion model for trail dynamics

    DOE PAGES

    Kawagoe, Kyle; Huber, Greg; Pradas, Marc; ...

    2017-07-21

    We investigate statistical properties of trails formed by a random process incorporating aggregation, fragmentation, and diffusion. In this stochastic process, which takes place in one spatial dimension, two neighboring trails may combine to form a larger one, and also one trail may split into two. In addition, trails move diffusively. The model is defined by two parameters which quantify the fragmentation rate and the fragment size. In the long-time limit, the system reaches a steady state, and our focus is the limiting distribution of trail weights. We find that the density of trail weight has power-law tail P(w)~w–γ for smallmore » weight w. We obtain the exponent γ analytically and find that it varies continuously with the two model parameters. In conclusion, the exponent γ can be positive or negative, so that in one range of parameters small-weight trails are abundant and in the complementary range they are rare.« less

  12. Dynamics of diffuse pollution from US southern watersheds

    USGS Publications Warehouse

    Schreiber, J.D.; Rebich, R.A.; Cooper, C.M.

    2001-01-01

    To understand the effects of diffuse pollution information on the source of pollutants, quantities in transport, mode of transport, transient nature of the pollution event, and most importantly, a consideration of remediation efforts need to be known. For example, water quality research in the Yazoo Basin uplands in Mississippi has shown sediment loads from a conventional-till upland soybean watershed to be about 19,000kg/ha/yr, and responsible for 77-96% of P and N in transport. In contrast, sediment loads from a comparable no-till soybean watershed were only 500kg/ha/yr, transporting about 31% of P and N in transport. Sediment loads from a nearby forested area were low, about 200kg/ha/yr, but responsible for about 47-76% of P and N in transport. Transient pollution events are responsible for the transport of large quantities of sediment, nutrients, and pesticides; in some storm events nearly the annual load. Best management practices (BMPs) must be designed to remediate diffuse pollution and the transient nature of pollution events which can have a profound effect on the ecological health of steams and reservoirs. Copyright ?? 2001 .

  13. Anisotropic parallel self-diffusion coefficients near the calcite surface: A molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Franco, Luís F. M.; Castier, Marcelo; Economou, Ioannis G.

    2016-08-01

    Applying classical molecular dynamics simulations, we calculate the parallel self-diffusion coefficients of different fluids (methane, nitrogen, and carbon dioxide) confined between two { 10 1 ¯ 4 } calcite crystal planes. We have observed that the molecules close to the calcite surface diffuse differently in distinct directions. This anisotropic behavior of the self-diffusion coefficient is investigated for different temperatures and pore sizes. The ion arrangement in the calcite crystal and the strong interactions between the fluid particles and the calcite surface may explain the anisotropy in this transport property.

  14. Anisotropic parallel self-diffusion coefficients near the calcite surface: A molecular dynamics study.

    PubMed

    Franco, Luís F M; Castier, Marcelo; Economou, Ioannis G

    2016-08-28

    Applying classical molecular dynamics simulations, we calculate the parallel self-diffusion coefficients of different fluids (methane, nitrogen, and carbon dioxide) confined between two {101̄4} calcite crystal planes. We have observed that the molecules close to the calcite surface diffuse differently in distinct directions. This anisotropic behavior of the self-diffusion coefficient is investigated for different temperatures and pore sizes. The ion arrangement in the calcite crystal and the strong interactions between the fluid particles and the calcite surface may explain the anisotropy in this transport property.

  15. Ab initio path integral molecular dynamics simulation study on the dihydrogen bond of NH4+⋯BeH2

    NASA Astrophysics Data System (ADS)

    Hayashi, Aiko; Shiga, Motoyuki; Tachikawa, Masanori

    2005-07-01

    An ab initio path integral molecular dynamics simulation has been performed to study the quantum and thermal effects of a dihydrogen bonded cation, NH4+⋯BeH2. In this system, an attractive interaction exists between two neighboring hydrogen atoms as N δ- H δ+ ⋯H δ- Be δ+ involving large-amplitude of vibration. Some properties playing a key role for this dihydrogen bonded system, such as the bond length, bond angle, and distribution of atomic charges, are investigated in detail by comparing the results of path integral and classical molecular dynamics with those of the equilibrium structure. It was found that the atomic charges of H δ+ and H δ- are decreased and the dihydrogen H δ+ ⋯H δ- bond length is expanded as the thermal and zero-point quantum effects.

  16. Diffusion of molecules in the bulk of a low density amorphous ice from molecular dynamics simulations.

    PubMed

    Ghesquière, P; Mineva, T; Talbi, D; Theulé, P; Noble, J A; Chiavassa, T

    2015-05-07

    The diffusion of molecules in interstellar ice is a fundamental phenomenon to take into account while studying the formation of complex molecules in this ice. This work presents a theoretical study on the diffusion of H2O, NH3, CO2, CO, and H2CO in the bulk of a low density amorphous (LDA) ice, while taking into account the physical conditions prevailing in space, i.e. temperatures below 150 K and extremely low pressure. This study was undertaken by means of molecular dynamics simulations. For CO2 for which no experimental data were available we conducted our own experiments. From our calculations we show that, at low temperatures, the diffusion of molecules in the bulk of a LDA ice is driven by the self-diffusion of water molecules in the ice. With this study we demonstrate that molecular dynamics allows the calculation of diffusion coefficients for small molecules in LDA ice that are convincingly comparable to experimentally measured diffusion coefficients. We also provide diffusion coefficients for a series of molecules of astrochemical interest.

  17. Self Diffusion in Nano Filled Polymer Melts: a Molecular Dynamics Simulation Study

    NASA Astrophysics Data System (ADS)

    Desai, Tapan; Keblinski, Pawel

    2003-03-01

    SELF DIFFUSION IN NANO FILLED POLYMER MELTS: A MOLECULAR DYNAMICS SIMULATION STUDY* T. G. Desai,P. Keblinski, Material Science and Engineering Department, Rensselaer Polytechnic Institute, Troy, NY. Using molecular dynamics simulations, we studied the dynamics of the polymeric systems containing immobile and analytically smooth spherical nanoparticles. Each chain consisted of N monomers connected by an anharmonic springs described by the finite extendible nonlinear elastic, FENE potential. The system comprises of 3nanoparticles and the rest by freely rotating but not overlapping chains. The longest chain studied has a Radius of gyration equal to particle size radius and comparable to inter-particle distance. There is no effect on the structural characteristics such as Radius of gyration or end to end distance due to the nanoparticles. Diffusion of polymeric chains is not affected by the presence of either attractive or repulsive nanoparticles. In all cases Rouse dynamics is observed for short chains with a crossover to reptation dynamics for longer chains.

  18. Synchronization and local convergence analysis of networks with dynamic diffusive coupling

    NASA Astrophysics Data System (ADS)

    Burbano Lombana, Daniel Alberto; di Bernardo, Mario

    2016-11-01

    In this paper, we address the problem of achieving synchronization in networks of nonlinear units coupled by dynamic diffusive terms. We present two types of couplings consisting of a static linear term, corresponding to the diffusive coupling, and a dynamic term which can be either the integral or the derivative of the sum of the mismatches between the states of neighbouring agents. The resulting dynamic coupling strategy is a distributed proportional-integral (PI) or a proportional-derivative (PD) law that is shown to be effective in improving the network synchronization performance, for example, when the dynamics at nodes are nonidentical. We assess the stability of the network by extending the classical Master Stability Function approach to the case where the links are dynamic ones of PI/PD type. We validate our approach via a set of representative examples including networks of chaotic Lorenz and networks of nonlinear mechanical systems.

  19. Molecular diffusion and dc conductivity perfectly correlated with molecular rotational dynamics in a plastic crystalline electrolyte.

    PubMed

    Zachariah, M; Romanini, M; Tripathi, P; Tamarit, J Ll; Macovez, R

    2015-06-28

    We probe the ionic conduction and the molecular dynamics in a pure and lithium-salt doped dinitrile molecular plastic crystal. While the diffusion of the Li(+) ions is decoupled from the molecular reorientational dynamics, in the undoped plastic crystal the temperature dependence of the mobility of dinitrile ions and thus of the conductivity is virtually identical to that of on-site molecular rotations. The undoped material is found to obey the Walden and Stokes-Einstein rules typical of ideal liquid electrolytes, implying that an effective viscosity against diffusion can be defined even for a plastic crystalline phase. These surprising results, never reported before in a translationally ordered solid, indicate that in this dinitrile plastic crystalline material the timescale of translational diffusion is perfectly correlated with that of the purely reorientational on-site dynamics.

  20. Liquid Aluminum: Atomic diffusion and viscosity from ab initio molecular dynamics

    PubMed Central

    Jakse, Noel; Pasturel, Alain

    2013-01-01

    We present a study of dynamic properties of liquid aluminum using density-functional theory within the local-density (LDA) and generalized gradient (GGA) approximations. We determine the temperature dependence of the self-diffusion coefficient as well the viscosity using direct methods. Comparisons with experimental data favor the LDA approximation to compute dynamic properties of liquid aluminum. We show that the GGA approximation induce more important backscattering effects due to an enhancement of the icosahedral short range order (ISRO) that impact directly dynamic properties like the self-diffusion coefficient. All these results are then used to test the Stokes-Einstein relation and the universal scaling law relating the diffusion coefficient and the excess entropy of a liquid. PMID:24190311

  1. A molecular dynamics study of ethanol-water hydrogen bonding in binary structure I clathrate hydrate with CO2

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Ohmura, Ryo; Ripmeester, John A.

    2011-02-01

    Guest-host hydrogen bonding in clathrate hydrates occurs when in addition to the hydrophilic moiety which causes the molecule to form hydrates under high pressure-low temperature conditions, the guests contain a hydrophilic, hydrogen bonding functional group. In the presence of carbon dioxide, ethanol clathrate hydrate has been synthesized with 10% of large structure I (sI) cages occupied by ethanol. In this work, we use molecular dynamics simulations to study hydrogen bonding structure and dynamics in this binary sI clathrate hydrate in the temperature range of 100-250 K. We observe that ethanol forms long-lived (>500 ps) proton-donating and accepting hydrogen bonds with cage water molecules from both hexagonal and pentagonal faces of the large cages while maintaining the general cage integrity of the sI clathrate hydrate. The presence of the nondipolar CO2 molecules stabilizes the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The distortions of the large cages from the ideal form, the radial distribution functions of the guest-host interactions, and the ethanol guest dynamics are characterized in this study. In previous work through dielectric and NMR relaxation time studies, single crystal x-ray diffraction, and molecular dynamics simulations we have observed guest-water hydrogen bonding in structure II and structure H clathrate hydrates. The present work extends the observation of hydrogen bonding to structure I hydrates.

  2. A molecular dynamics study of ethanol-water hydrogen bonding in binary structure I clathrate hydrate with CO2.

    PubMed

    Alavi, Saman; Ohmura, Ryo; Ripmeester, John A

    2011-02-07

    Guest-host hydrogen bonding in clathrate hydrates occurs when in addition to the hydrophilic moiety which causes the molecule to form hydrates under high pressure-low temperature conditions, the guests contain a hydrophilic, hydrogen bonding functional group. In the presence of carbon dioxide, ethanol clathrate hydrate has been synthesized with 10% of large structure I (sI) cages occupied by ethanol. In this work, we use molecular dynamics simulations to study hydrogen bonding structure and dynamics in this binary sI clathrate hydrate in the temperature range of 100-250 K. We observe that ethanol forms long-lived (>500 ps) proton-donating and accepting hydrogen bonds with cage water molecules from both hexagonal and pentagonal faces of the large cages while maintaining the general cage integrity of the sI clathrate hydrate. The presence of the nondipolar CO(2) molecules stabilizes the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The distortions of the large cages from the ideal form, the radial distribution functions of the guest-host interactions, and the ethanol guest dynamics are characterized in this study. In previous work through dielectric and NMR relaxation time studies, single crystal x-ray diffraction, and molecular dynamics simulations we have observed guest-water hydrogen bonding in structure II and structure H clathrate hydrates. The present work extends the observation of hydrogen bonding to structure I hydrates.

  3. Dual-central-wavelength passively mode-locked diffusion-bonded Nd:YVO4/Nd:GdVO4 laser with a semiconductor saturable absorber mirror

    NASA Astrophysics Data System (ADS)

    Chang, F. L.; Sung, C. L.; Huang, T. L.; Wu, T. W.; Cho, H. H.; Liang, H. C.; Chen, Y. F.

    2017-08-01

    A dual-central-wavelength passively mode-locked laser with full modulation in the 0.31 THz optical beating is achieved by using a diffusion-bonded Nd:YVO4/Nd:GdVO4 crystal and a semiconductor saturable absorber mirror. The output power of the dual-band emission is well balanced by tuning the focal position of the pump waist. At a pump power of 13 W, the total output power is up to 2.7 W with a repetition rate of 297.9 MHz. The autocorrelation traces clearly reveal the synchronization of the dual-band emission. Moreover, an analytical model is developed to manifest the multi-pulse structure caused by the etalon effect of the gain medium. More important, we experimentally verify that the etalon effect can be completely eliminated by using the wedge-cut diffusion-bonded Nd:YVO4/Nd:GdVO4 crystal.

  4. Hydrogen Bonding and Dielectric Spectra of Ethylene Glycol–Water Mixtures from Molecular Dynamics Simulations

    PubMed Central

    2016-01-01

    Mixtures of ethylene glycol with water are a prominent example of media with variable viscosity. Classical molecular dynamics simulations at room temperature were performed for mixtures of ethylene glycol (EG) and water with EG mole fractions of xE = 0.0, 0.1, 0.2, 0.4, 0.6, 0.9, 1.0. The calculated dielectric loss spectra were in qualitative agreement with experiment. We found a slightly overestimated slowdown of the dynamics with increasing EG concentration compared to experimental data. Statistics of the hydrogen bond network and hydrogen bond lifetimes were derived from suitable time correlation functions and also show a slowdown in the dynamics with increasing xE. A similar picture is predicted for the time scales of EG conformer changes and for molecular reorientation. A slight blue shift was obtained for the power spectra of the molecular center of mass motion. The results were used to give a qualitative interpretation of the origin of three different relaxation times that appear in experimental complex dielectric spectra and of their change with xE. PMID:27649083

  5. Dynamical tunneling versus fast diffusion for a non-convex Hamiltonian.

    PubMed

    Pittman, S M; Tannenbaum, E; Heller, E J

    2016-08-07

    This paper attempts to resolve the issue of the nature of the 0.01-0.1 cm(-1) peak splittings observed in high-resolution IR spectra of polyatomic molecules. One hypothesis is that these splittings are caused by dynamical tunneling, a quantum-mechanical phenomenon whereby energy flows between two disconnected regions of phase-space across dynamical barriers. However, a competing classical mechanism for energy flow is Arnol'd diffusion, which connects different regions of phase-space by a resonance network known as the Arnol'd web. The speed of diffusion is bounded by the Nekhoroshev theorem, which guarantees stability on exponentially long time scales if the Hamiltonian is steep. Here we consider a non-convex Hamiltonian that contains the characteristics of a molecular Hamiltonian, but does not satisfy the Nekhoroshev theorem. The diffusion along the Arnol'd web is expected to be fast for a non-convex Hamiltonian. While fast diffusion is an unlikely competitor for longtime energy flow in molecules, we show how dynamical tunneling dominates compared to fast diffusion in the nearly integrable regime for a non-convex Hamiltonian, as well as present a new kind of dynamical tunneling.

  6. Dynamical Symmetry Breaking and Phase Transitions in Driven Diffusive Systems

    NASA Astrophysics Data System (ADS)

    Baek, Yongjoo; Kafri, Yariv; Lecomte, Vivien

    2017-01-01

    We study the probability distribution of a current flowing through a diffusive system connected to a pair of reservoirs at its two ends. Sufficient conditions for the occurrence of a host of possible phase transitions both in and out of equilibrium are derived. These transitions manifest themselves as singularities in the large deviation function, resulting in enhanced current fluctuations. Microscopic models which implement each of the scenarios are presented, with possible experimental realizations. Depending on the model, the singularity is associated either with a particle-hole symmetry breaking, which leads to a continuous transition, or in the absence of the symmetry with a first-order phase transition. An exact Landau theory which captures the different singular behaviors is derived.

  7. Dynamical behavior of a dangling bond dimer on a hydrogenated semiconductor: Ge(001):H

    NASA Astrophysics Data System (ADS)

    Godlewski, Szymon; Kolmer, Marek; Lis, Jakub; Zuzak, Rafal; Such, Bartosz; Gren, Wojciech; Szymonski, Marek; Kantorovich, Lev

    2015-09-01

    We show that a dangling bond (DB) dimer on Ge(001):H exhibits a dynamical behavior when the empty states are imaged with scanning tunneling microscopy (STM) at liquid helium temperature. Large amplitude Ge atom vibrations are decisive in facilitating a specific appearance of the structure in the STM images. The underlying mechanism is unraveled using a theoretical model and calculations within the density functional theory framework. Furthermore, we demonstrate the ability to induce controlled switching of the DB dimer with noncontact atomic force microscope and the stabilizing role of the dimer-dimer interaction.

  8. Monte Carlos studies of critical and dynamic phenomena in mixed bond Ising model

    NASA Astrophysics Data System (ADS)

    Santos-Filho, J. B.; Moreno, N. O.; de Albuquerque, Douglas F.

    2010-11-01

    The phase transition of a random mixed-bond Ising ferromagnet on a cubic lattice model is studied both numerically and analytically. In this work, we use the Metropolis and Wolff algorithm with histogram technique and finite size scaling theory to simulate the dynamics of the system. We obtained the thermodynamic quantities such as magnetization, susceptibility, and specific heat. Our results were compared with those obtained using a new technique in effective field theory that employs similar probability distribution within the framework of two-site clusters.

  9. Molecular dynamics simulation with the charge response kernel: Diffusion dynamics of pyrazine and pyrazinyl radical in methanol

    NASA Astrophysics Data System (ADS)

    Morita, Akihiro; Kato, Shigeki

    1998-04-01

    The present study involves two themes. The first is to incorporate the charge response kernel (∂Qa/∂Vb) into the molecular dynamics simulation, where Qa denotes the partial charge at the site a and Vb the electrostatic potential at the site b. The response kernel was ab initio calculated in our previous study [A. Morita and S. Kato, J. Am. Chem. Soc. 119, 4021 (1997)], and it provides a useful way to describe the polarization effect in solution, with several advantages discussed in Sec. I. The second theme is to elucidate the anomalously slow diffusion of some aromatic radicals using the above procedure. It demonstrated that the difference in the polarization effect of pyrazinyl radical (product of hydrogen abstraction) and pyrazine (parent) manifests itself in the diffusion coefficients. The analysis of the frictional force revealed the different dynamics of diffusion.

  10. Using molecular dynamics to obtain Maxwell-Stefan diffusion coefficients in liquid systems

    NASA Astrophysics Data System (ADS)

    van de Ven-Lucassen Thijs, Irma M. J. J.; Vlugt Antonius, J. H.; van der Zanden Piet, J. J.; Kerkhof, J. A. M.

    Two methods are compared for the calculation of Maxwell-Stefan diffusion coefficients. The firs