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At least 91 records · Page 5

Dynamics of coupled ice-ocean system in the marginal ice zone: Study of the mesoscale processes and of constitutive equations for sea ice

This study is aimed at the modelling of mesoscale processed such as up/downwelling and ice edge eddies in the marginal ice zones. A 2-dimensional coupled ice-ocean model is used for the study. The ice model is coupled to the reduced gravity ocean model (f-plane) through interfacial stresses. The constitutive equations of the sea ice are formulated on the basis of the Reiner-Rivlin theory. The internal ice stresses are important only at high ice concentrations (90-100%), otherwise the ice motion is essentially free drift, where the air-ice stress is balanced by the ice-water stress. The model was tested by studying the upwelling dynamics. Winds parallel to the ice edge with the ice on the right produce upwilling because the air-ice momentum flux is much greater that air-ocean momentum flux, and thus the Ekman transport is bigger under the ice than in the open water. The upwelling simulation was extended to include temporally varying forcing, which was chosen to vary sinusoidally with a 4 day period. This forcing resembles successive cyclone passings. In the model with a thin oceanic upper layer, ice bands were formed.

Hakkinen, S.↗

Enigmatic Moisture Effects on Al2O3 Scale and TBC Adhesion

Alumina scale adhesion to high temperature alloys is known to be affected primarily by sulfur segregation and reactive element additions. However adherent scales can become partially compromised by excessive strain energy and cyclic cracking. With time, exposure of such scales to moisture can lead to spontaneous interfacial decohesion, occurring while the samples are maintained at ambient conditions. Examples of this Moisture-Induced Delayed Spallation (MIDS) are presented for NiCrAl and single crystal superalloys, becoming more severe with sulfur level and cyclic exposure conditions. Similarly, delayed failure or Desk Top Spallation (DTS) results are reviewed for TBC s, culminating in the water drop failure test. Both phenomena are discussed in terms of moisture effects on bulk alumina and bulk aluminides. A mechanism is proposed based on hydrogen embrittlement and is supported by a cathodic hydrogen charging experiment. Hydroxylation of aluminum from the alloy interface appears to be the relevant basic reaction.

Smialek, James L.↗

Chemical Bonding Technology: Direct Investigation of Interfacial Bonds

This is the third Flat-Plate Solar Array (FSA) Project document reporting on chemical bonding technology for terrestrial photovoltaic (PV) modules. The impetus for this work originated in the late 1970s when PV modules employing silicone encapsulation materials were undergoing delamination during outdoor exposure. At that time, manufacturers were not employing adhesion promoters and, hence, module interfaces in common with the silicone materials were only in physical contact and therefore easily prone to separation if, for example, water were to penetrate to the interfaces. Delamination with silicone materials virtually vanished when adhesion promoters, recommended by silicone manufacturers, were used. The activities related to the direct investigation of chemically bonded interfaces are described.

Koenig, J. L.↗

Enigmatic Moisture Effects on Al2O3 Scale and TBC Adhesion

Alumina scale adhesion to high temperature alloys is known to be affected primarily by sulfur segregation and reactive element additions. However, adherent scales can become partially compromised by excessive strain energy and cyclic cracking. With time, exposure of such scales to moisture can lead to spontaneous interfacial decohesion, occurring while the samples are maintained at ambient conditions. Examples of this Moisture-Induced Delayed Spallation (MIDS) are presented for NiCrAl and single crystal superalloys, becoming more severe with sulfur level and cyclic exposure conditions. Similarly, delayed failure or Desk Top Spallation (DTS) results are reviewed for thermal barrier coatings (TBCs), culminating in the water drop failure test. Both phenomena are discussed in terms of moisture effects on bulk alumina and bulk aluminides. A mechanism is proposed based on hydrogen embrittlement and is supported by a cathodic hydrogen charging experiment. Hydroxylation of aluminum from the alloy interface appears to be the relevant basic reaction.

Smialek, James L.↗

The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

Parthasarathy, Arvind↗

Improved aqueous scrubber for collection of soluble atmospheric trace gases

A new concentration technique for the extraction and enrichment of water-soluble atmospheric trace gases has been developed. The gas scrubbing technique efficiently extracts soluble gases from a large volume flow rate of air sample into a small volume of refluxed trapping solution. The gas scrubber utilizes a small nebulizing nozzle that mixes the incoming air with an aqueous extracting solution to form an air/droplet mist. The mist provides excellent interfacial surface areas for mass transfer. The resulting mist sprays upward through the reaction chamber until it impinges upon a hydrophobic membrane that virtually blocks the passage of droplets but offers little resistance to the existing gas flow. Droplets containing the scrubbed gases coalesce on the membrane and drip back into the reservoir for further refluxing. After a suitable concentration period, the extracting solution containing the analyte can be withdrawn for analysis. The nebulization-reflex concentration technique is more efficient (maximum flow of gas through the minimum volume of extractant) than conventional bubbler/impinger gas extraction techniques and is offered as an alternative method.

Cofer, W. R., III↗

Early events in the folding of an amphipathic peptide: A multinanosecond molecular dynamics study

Folding of the capped LQQLLQQLLQL peptide is investigated at the water-hexane interface by molecular dynamics simulations for 161.5 ns. Initially placed in the aqueous phase as a beta-strand, the peptide rapidly adsorbs to the interface, where it adopts an amphipathic conformation. The marginal presence of nonamphipathic structures throughout the complete trajectory indicates that the corresponding conformations are strongly disfavored at the interface. It is further suggestive that folding in an interfacial environment proceeds through a pathway of successive amphipathic intermediates. The energetic and entropic penalties involved in the conformational changes along this pathway markedly increase the folding time scales of LQQLLQQLLQL, explaining why the alpha-helix, the hypothesized lowest free energy structure for a sequence with a hydrophobic periodicity of 3.6, has not been reached yet. The formation of a type I beta-turn at the end of the simulation confirms the importance of such motifs as initiation sites allowing the peptide to coalesce towards a secondary structure. Proteins 1999;36:383-399. Copyright 1999 Wiley-Liss, Inc.

NASA Center ARC↗

Predictions of nucleation theory applied to Ehrenfest thermodynamic transitions

A modified nucleation theory is used to determine a critical nucleus size and a critical activation-energy barrier for second-order Ehrenfest thermodynamic transitions as functions of the degree of undercooling, the interfacial energy, the heat-capacity difference, the specific volume of the transformed phase, and the equilibrium transition temperature. The customary approximations of nucleation theory are avoided by expanding the Gibbs free energy in a Maclaurin series and applying analytical thermodynamic expressions to evaluate the expansion coefficients. Nonlinear correction terms for first-order-transition calculations are derived, and numerical results are presented graphically for water and polystyrene as examples of first-order and quasi-second-order transitions, respectively.

Barker, R. E., Jr.↗

Early Events in the Folding of an Amphipathic Peptide A Multi- Nanosecond Molecular Dynamics Study

Folding of the capped LQQLLQQLLQL peptide is investigated at the water-hexane interface by molecular dynamics simulations over 161.5 nanoseconds. Initially placed in the aqueous phase as a beta-strand, the peptide rapidly adsorbs to the interface, where it adopts an amphipathic conformation. The marginal presence of non-amphipathic structures throughout the complete trajectory indicate- that the corresponding conformations are strongly disfavored at the interface. It is further suggestive that folding in an interfacial environment proceeds through a pathway of successive amphipathic intermediates. The energetic and entropic penalties involved in the conformational changes along this pathway markedly increase the folding time-scales of LQQLLQQLLQL, explaining why the alpha-helix, the hypothesized lowest free energy structure for a sequence with a hydrophobic periodicity of 3.6, has not been reached yet. The formation of a type I beta-turn at the end of the simulation confirms the importance of such motifs as initiation sites allowing the peptide to coalesce towards a secondary structure.

Chipot, Christophe↗

Molecular dynamics of phenol at the liquid-vapor interface of water

Results of molecular dynamics calculations on phenol at the water liquid-vapor interface are presented. The density profile of the center of mass of phenol exhibits a maximum 1 A from the Gibbs surface toward the vapor phase, indicating that the molecule is surface-active. Changes in the profile caused by the interface extend 6 A from the Gibbs surface into the liquid, significantly more than change in the density profile of water. The most probable orientation of the solute at the surface is such that its symmetry axis is perpendicular to the interface with the OH substituent pointing toward the liquid. An additional simulation with benzene shows that this molecule at the surface most often adopts orientations parallel to the interface. Deeper in the liquid all the solutes are preferentially ordered perpendicular to the surface. In the interfacial region the orientational preferences of the solute are primarily determined by cavity formation needed to accommodate the hydrophobic portion of the dissolved molecule.

Pohorille, Andrew↗

Measurement of the Surface Dilatational Viscosity of an Insoluble Surfactant Monolayer at the Air/Water Interface Using a Pendant Drop Apparatus

When a fluid interface with surfactants is at rest, the interfacial stress is isotropic (as given by the equilibrium interfacial tension), and is described by the equation of state which relates the surface tension to the surfactant surface concentration. When surfactants are subjected to shear and dilatational flows, flow induced interaction of the surfactants; can create interfacial stresses apart from the equilibrium surface tension. The simplest relationship between surface strain rate and surface stress is the Boussinesq-Scriven constitutive equation completely characterized by three coefficients: equilibrium interfacial tension, surface shear viscosity, and surface dilatational viscosity Equilibrium interfacial tension and surface shear viscosity measurements are very well established. On the other hand, surface dilatational viscosity measurements are difficult because a flow which change the surface area also changes the surfactant surface concentration creating changes in the equilibrium interfacial tension that must be also taken into account. Surface dilatational viscosity measurements of existing techniques differ by five orders of magnitude and use spatially damped surface waves and rapidly expanding bubbles. In this presentation we introduce a new technique for measuring the surface dilatational viscosity by contracting an aqueous pendant drop attached to a needle tip and having and insoluble surfactant monolayer at the air-water interface. The isotropic total tension on the surface consists of the equilibrium surface tension and the tension due to the dilation. Compression rates are undertaken slow enough so that bulk hydrodynamic stresses are small compared to the surface tension force. Under these conditions we show that the total tension is uniform along the surface and that the Young-Laplace equation governs the drop shape with the equilibrium surface tension replaced by the constant surface isotropic stress. We illustrate this technique using DPPC as the insoluble surfacant monolayer and measured for it a surface dilatational viscosity in the LE phase that is 20 surface poise.

Lorenzo, Jose↗

Ionic migration and weathering in frozen Antarctic soils

Soils of continental Antarctica are forming in one of the most severe terrestrial environments. Continuously low temperatures and the scarcity of water in the liquid state result in the development of desert-type soils. In an earlier experiment to determine the degree to which radioactive Na(Cl-36) would migrate from a shallow point source in permafrost, movement was observed. To confirm this result, a similar experiment involving (Na-22)Cl was conducted. Significantly less movement of the Na-22 ion was observed. Ionic movement in the unfrozen interfacial films at mineral surfaces in frozen ground is held to be important in chemical weathering in Antarctic soils.

Ugolini, F. C.↗

Coupled ice-ocean dynamics in the marginal ice zones Upwelling/downwelling and eddy generation

This study is aimed at modeling mesoscale processes such as upwelling/downwelling and ice edge eddies in the marginal ice zones. A two-dimensional coupled ice-ocean model is used for the study. The ice model is coupled to the reduced gravity ocean model through interfacial stresses. The parameters of the ocean model were chosen so that the dynamics would be nonlinear. The model was tested by studying the dynamics of upwelling. Wings parallel to the ice edge with the ice on the right produce upwelling because the air-ice momentum flux is much greater than air-ocean momentum flux; thus the Ekman transport is greater than the ice than in the open water. The stability of the upwelling and downwelling jets is discussed. The downwelling jet is found to be far more unstable than the upwelling jet because the upwelling jet is stabilized by the divergence. The constant wind field exerted on a varying ice cover will generate vorticity leading to enhanced upwelling/downwelling regions, i.e., wind-forced vortices. Steepening and strengthening of vortices are provided by the nonlinear terms. When forcing is time-varying, the advection terms will also redistribute the vorticity. The wind reversals will separate the vortices from the ice edge, so that the upwelling enhancements are pushed to the open ocean and the downwelling enhancements are pushed underneath the ice.

Hakkinen, S.↗

Development of a 12-Thrust Chamber Kerosene /Oxygen Primary Rocket Sub-System for an Early (1964) Air-Augmented Rocket Ground-Test System

Airbreathing/Rocket combined-cycle, and specifically rocket-based combined- cycle (RBCC), propulsion systems, typically employ an internal engine flow-path installed primary rocket subsystem. To achieve acceptably short mixing lengths in effecting the "air augmentation" process, a large rocket-exhaust/air interfacial mixing surface is needed. This leads, in some engine design concepts, to a "cluster" of small rocket units, suitably arrayed in the flowpath. To support an early (1964) subscale ground-test of a specific RBCC concept, such a 12-rocket cluster was developed by NASA's Marshall Space Flight Center (MSFC). The small primary rockets used in the cluster assembly were modified versions of an existing small kerosene/oxygen water-cooled rocket engine unit routinely tested at MSFC. Following individual thrust-chamber tests and overall subsystem qualification testing, the cluster assembly was installed at the U. S. Air Force's Arnold Engineering Development Center (AEDC) for RBCC systems testing. (The results of the special air-augmented rocket testing are not covered here.) While this project was eventually successfully completed, a number of hardware integration problems were met, leading to catastrophic thrust chamber failures. The principal "lessons learned" in conducting this early primary rocket subsystem experimental effort are documented here as a basic knowledge-base contribution for the benefit of today's RBCC research and development community.

Pryor, D.↗

Solidification phenomena of binary organic mixtures

The coalescence rates and motion of liquid bubbles in binary organic mixtures were studied. Several factors such as temperature gradient, composition gradient, interfacial tension, and densities of the two phases play important roles in separation of phases of immiscible liquids. An attempt was made to study the effect of initial compositions on separation rates of well-dispersed organic mixtures at different temperatures and, ultimately, on the homogeneity of solidification of the immiscible binary organic liquids. These organic mixtures serve as models for metallic pseudo binary systems under study. Two specific systems were investigated: ethyl salicylate - diethyl glycol and succinonitrile - water.

Chang, K.↗

Development of a torsion balance for adhesion measurements

A new torsion balance for study of adhesion in ceramics is discussed. A torsion wire and a linear variable differential transformer are used to monitor load and to measure pull-off force (adhesion force). The investigation suggests that this torsion balance is valuable in studying the interfacial properties of ceramics in controlled environments such as in ultrahigh vacuum. The pull-off forces measured in dry, moist, and saturated nitrogen atmosphere demonstrate that the adhesion of silicon nitride contacts remains low at humidities below 80 percent but rises rapidly above that. The adhesion at saturation is 10 times or more greater than that below 80 percent relative humidity. The adhesion in a saturated atmosphere arises primarily from the surface tension effects of a thin film of water adsorbed on the surface. The surface tension of the water film was 58 x 10 to the minus 5 to 65 x 10 to the minus 5 power. The accepted value for water is 72.7 x 10 to the minus 5 power N/cm. Adhesion characteristics of silicon nitride in contact with metals, like the friction characteristics of silicon carbide to metal contacts, can be related to the relative chemical activity of metals in ultrahigh vacuum. The more active the metal, the higher the adhesion.

Miyoshi, Kazuhisa↗

The development of an alternative thermoplastic powder prepregging technique

An alternative powder prepregging technique is discussed that is based on the deposition of powder onto carbon fibers that have been moistened using an ultrasonic humidifier. The dry fiber tow is initially spread to allow a greater amount of the fiber surface to be exposed to the powder, thus ensuring a significant amount of intimate contact between the fiber and the matrix. Moisture in the form of ultrafine water droplets is then deposited onto the spread fiber tow. The moisture promotes adhesion to the fiber until the powder can be tacked to the fibers by melting. Powdered resin is then sieved onto the fibers and then tacked onto the fibers by quick heating in a convective oven. This study focuses on the production of prepregs and laminates made with LaRC-TPI (thermoplastic polyimide) using this process. Although the process appears to be successful, early evaluation was hampered by poor interfacial adhesion. The adhesion problem, however, seems to be the result of a material system incompatibility, rather than being influenced by the process.

Ogden, A. L.↗

Moisture-temperature degradation in module encapsulants: The general problem of moisture in photovoltaic encapsulants

A general research approach was outlined toward understanding water-module interactions and the influence of temperature involving the need to: quantify module performance loss versus level of accumulated degradation, establish the dependence of the degradation reaction rate on module moisture and temperature levels, and determine module moisture and temperature levels in field environments. These elements were illustrated with examples drawn from studies of the now relatively well understood module electrochemical degradation process. Research data presented include temperature and humidity-dependent equilibrium leakage current values for multiparameter module material and design configurations. The contributions of surface, volume, and interfacial conductivities was demonstrated. Research directions were suggested to more fully understand the contributions to overall module conductivity of surface, volume, and interfacial conductivities over ranges of temperature and relative humidity characteristic of field environments.

Mon, G. R.↗