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At least 253 records · Page 14

Role of Hf on Phase Formation in Ti45Zr(38-x)Hf(x)Ni17 Liquids and Solids

Hafnium and zirconium are very similar, with almost identical sizes and chemical bonding characteristics. However, they behave differently when alloyed with Ti and Ni. A sharp phase formation boundary near 18-21 at.% Hf is observed in rapidly-quenched and as-cast Ti45Zr38-xHfxNi17 alloys. Rapidly-quenched samples that contain less than 18 at.% Hf form the icosahedral quasicrystal phase, whiles samples containing more than 21 at.% form the 3/2 rational approximant phase. In cast alloys, a C14 structure is observed for alloys with Hf lower than the boundary concentration, while a large-cell (11.93 ) FCC Ti2Ni-type structure is found in alloys with Hf concentrations above the boundary. To better understand the role of Hf on phase formation, the structural evolution with supercooling and the solidification behavior of liquid Ti45Zr38-xHfxNi17 alloys (x=0, 12, 18, 21, 38) were studied using the Beamline Electrostatic Levitation (BESL) technique using 125keV x-rays on the 6ID-D beamline at the Advanced Photon Source, Argonne National Laboratory. For all liquids primary crystallization was to a BCC solid solution phase; interestly, an increase in Hf concentration leads to a decrease in the BCC lattice parameter in spite of the chemical similarity between Zr and Hf. A Reitveld analysis confirmed that as in the cast alloys, the secondary phase that formed was the C14 below the phase formation boundary and a Ti2Ni-type structure at higher Hf concentrations. Both the liquidus temperature and the reduced undercooling change sharply on traversing the phase formation boundary concentration, suggesting a change in the liquid structure. Structural information from a Honeycutt-Anderson index analysis of reverse Monte Carlo fits to the S(q) liquid data will be presented to address this issue.

Wessels, V.↗

Neutron Spin–Echo Studies of the Structural Relaxation of Network Liquid ZnCl 2 at the Structure Factor Primary Peak and Prepeak

Using neutron spin-echo spectroscopy, we studied the microscopic structural relaxation of a prototypical network ionic liquid ZnCl 2 at the structure factor primary peak and pre-peak. The results show that the relaxation at the primary peak is faster than the pre-peak and the activation energy is ≈33% higher. Stretched exponential relaxation is observed even at temperatures well above the melting point T m . Surprisingly, the stretching exponent shows a rapid increase upon cooling, especially at the primary peak, where it changes from stretched exponential to simple exponential on approaching T m . Furthermore, these results suggest that the appearance of glassy dynamics typical of the supercooled state even in the equilibrium liquid state of ZnCl 2 as well as the difference of activation energy at the two investigated length scales are related to the formation of network structure on cooling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evidence for liquid-phase cirrus cloud formation from volcanic aerosols - Climatic implications

Supercooled droplets in cirrus uncinus cell heads between -40 and -50 C are identified from the First International Satellite Cloud Climatology Project Regional Experiment polarization lidar measurements. Although short-lived, complexes of these small liquid cells seem to have contributed importantly to the formation of the cirrus. Freezing-point depression effects in solution droplets, apparently resulting from relatively large cloud condensation nuclei of volcanic origin, can be used to explain this rare phenomenon. An unrecognized volcano-cirrus cloud climate feedback mechanism is implied by these findings.

Sassen, Kenneth↗

Nucleation of (He-3)-B from the A phase - A cosmic-ray effect?

When He-3 is liquified and subsequently cooled, it undergoes, at a temperature of approximately 2.0-2.5 mK, a second-order transition into the so-called A phase. On further cooling, a first-order transition occurs, and the liquid passes into the B phase. Supercooling occurs with respect to the second transition, and the problem of nucleation arises. In connection with the experimental interest in studying metastable (He-3)-A down to the lowest temperatures in weak magnetic fields, the understanding of the mechanism of this transition and the feasibility of its inhibition is of some importance. The present investigation is concerned with the possibility that the transition is nucleated by the passage of a cosmic ray through the sample cell.

Leggett, A. J.↗

An Initial Study of the Fundamentals of Ice Crystal Icing Physics in the NASA Propulsion Systems Laboratory

This presentation shows results from an initial study of the fundamental physics of ice-crystal ice accretion using the NASA Propulsion Systems Lab (PSL). Ice accretion due to the ingestion of ice-crystals is being attributed to numerous jet-engine power-loss events. The NASA PSL is an altitude jet-engine test facility which has recently added a capability to inject ice particles into the flow. NASA is evaluating whether this facility, in addition to full-engine and motor-driven-rig tests, can be used for more fundamental ice-accretion studies that simulate the different mixed-phase icing conditions along the core flow passage of a turbo-fan engine compressor. The data from such fundamental accretion tests will be used to help develop and validate models of the accretion process. The present study utilized a NACA0012 airfoil. The mixed-phase conditions were generated by partially freezing the liquid-water droplets ejected from the spray bars. This presentation shows data regarding (1) the freeze out characteristics of the cloud, (2) changes in aerothermal conditions due to the presence of the cloud, and (3) the ice accretion characteristics observed on the airfoil model. The primary variable in this test was the PSL plenum humidity which was systematically varied for two duct-exit-plane velocities (85 and 135 ms) as well as two particle size clouds (15 and 50 m MVDi). The observed clouds ranged from fully glaciated to fully liquid, where the liquid clouds were at least partially supercooled. The air total temperature decreased at the test section when the cloud was activated due to evaporation. The ice accretions observed ranged from sharp arrow-like accretions, characteristic of ice-crystal erosion, to cases with double-horn shapes, characteristic of supercooled water accretions.

upwind schemes↗

An Initial Study of the Fundamentals of Ice Crystal Icing Physics in the Nasa Propulsion Systems Laboratory

This paper presents results from an initial study of the fundamental physics of ice-crystal ice accretion using the NASA Propulsion Systems Lab (PSL). Ice accretion due to the ingestion of ice-crystals is being attributed to numerous jet-engine power-loss events. The NASA PSL is an altitude jet-engine test facility which has recently added a capability to inject ice particles into the flow. NASA is evaluating whether this facility, in addition to full-engine and motor-driven-rig tests, can be used for more fundamental ice-accretion studies that simulate the different mixed-phase icing conditions along the core flow passage of a turbo-fan engine compressor. The data from such fundamental accretion tests will be used to help develop and validate models of the accretion process. The present study utilized a NACA0012 airfoil. The mixed-phase conditions were generated by partially freezing the liquid-water droplets ejected from the spray bars. This paper presents data regarding (1) the freeze out characteristics of the cloud, (2) changes in aerothermal conditions due to the presence of the cloud, and (3) the ice accretion characteristics observed on the airfoil model. The primary variable in this test was the PSL plenum humidity which was systematically varied for two duct-exit-plane velocities (85 and 135 ms) as well as two particle size clouds (15 and 50 m MVDi). The observed clouds ranged from fully glaciated to fully liquid, where the liquid clouds were at least partially supercooled. The air total temperature decreased at the test section when the cloud was activated due to evaporation. The ice accretions observed ranged from sharp arrow-like accretions, characteristic of ice-crystal erosion, to cases with double-horn shapes, characteristic of supercooled water accretions.

Evaporative Cooling↗

Understanding supercooling mechanism in sodium sulfate decahydrate phase-change material

Salt hydrate-based phase-change materials are considered promising for future heat storage applications in residential heating/cooling systems. Smooth phase transition from the liquid to solid phase and vice versa is essential for effective heat exchanger; however, supercooling in salt hydrates delays the onset of liquid–solid phase transition. We investigate the molecular level mechanism of supercooling in sodium sulfate decahydrate (SSD). SSD is a complex salt hydrate whose properties are governed by electrostatic forces that include pure Coulombic interactions as well as hydrogen bonds. Experimentally, we examine the importance of a nucleator in reducing supercooling temperatures. We investigated the effect of various mass concentrations of a borax nucleator on a decrease of supercooling temperatures. Molecular dynamics simulation techniques are used to obtain a basic understanding of supercooling in SSD. We observe that by introducing borax as a nucleator, there is a decrease in the supercooling temperature before nucleation. Our molecular dynamics simulations show that long-range electrostatics between sodium and sulfate ion pairs and that with polar water molecules is responsible for delayed nucleation in SSD that results in supercooling, and also, dynamics of charged molecules slows down. The lack of crystallization leads to amorphous structures in supercooled SSD.

36 MATERIALS SCIENCE↗

Measurement of Thermal Conductivity in a Supercooled Hydrogel-Salt Complex Near Its Phase Transition

Solid-liquid phase transitions, i.e. solidification processes, have applications in data storage, development of novel thermoelectric materials, cooling of microelectronic substrates and air conditioning condensers. Standard analyses of solidification (Stefan problem) assume constant thermal properties of the solid and liquid sides. It is not known how these properties change across the spatial transition interface, though most studies report a discontinuity in the solid and liquid properties through the transition temperature [1]. When the phase transition releases enthalpy, recent research has shown if the phonon or electron transport time is of the same order of magnitude as the time scale of the atomic transformation, this increases the heat capacity of the solid material at temperatures near the phase transition temperature [2]. A fundamental understanding of the phase transition may help shed light on the molecular origins of supercooling and spontaneous nucleation, which will help with applications involving them. We report studies of supercooling and nucleation of sodium sulfate decahydrate, a salt hydrate which is of recent interest in thermal storage, and of a hydrogel-sodium sulfate complex which shows limited supercooling. We will also report the measurement of their thermal properties during the phase transition process. This will be done with a hot-wire setup which produces small temperature changes of the order of ~1 C.

crystallization, phase transformation, thermal con↗

Influence of Melt Convection on Solid-Liquid Interface Under Terrestrial and Reduced Gravity Environments

Solidification and crystal growth processes involve thermal and solutal gradients within a molten phase. In the presence of gravity, such gradients result in convective flows which interact with diffusion fields at the solid-liquid interface. Dendritic growth kinetics was studied in transparent model systems which freeze similarily to most metals. Succinonitrile shows a strong influence of convection at supercoolings below about 1K. Fluid flows adjacent to solid-liquid interfaces and the behavior of shear flows in vertical annular geometries are studied. Novel low-frequency eigenstates were discovered and classified as coupled modes, for their involvement with interfacial deformation coupled to the fluid flow, and are unknown in systems without deformable interfaces. The dependence of coupled convection modes on interfacial geometry, gravity, fluid properties, and transformation characteristics studied for several annual flow arrangements with nominally pure solid-liquid systems.

Glicksman, M. E.↗

Coupled Growth in Hypermonotectics

The overall objective of this project is to obtain a fundamental understanding of the physics controlling solidification processes in immiscible alloy systems. The investigation involves both experimentation and the development of a model describing solidification in monotectic systems. The experimental segment was designed to first demonstrate that it is possible to obtain interface stability and steady state coupled growth in hypermonotectic alloys through microgravity processing. Microgravity results obtained to date have verified this possibility. Future flights will permit experimental determination of the limits of interface stability and the influence of alloy composition and growth rate on microstructure. The objectives of the modeling segment of the investigation include prediction of the limits of interface stability, modeling of convective flow due to residual acceleration, and the influence of surface tension driven flows at the solidification interface. The study of solidification processes in immiscible alloy systems is hindered by the inherent convective flow that occurs on Earth and by the possibility of sedimentation of the higher density immiscible liquid phase. It has been shown that processing using a high thermal gradient and a low growth rate can lead to a stable macroscopically planar growth front even in hypermonotectic alloys. Processing under these growth conditions can avoid constitutional supercooling and prevent the formation of the minor immiscible liquid phase in advance of the solidification front. However, the solute depleted boundary layer that forms in advance of the solidification front is almost always less dense than the liquid away from the solidification front. As a result, convective instability is expected. Ground based testing has indicated that convection is a major problem in these alloy systems and leads to gross compositional variations along the sample and difficulties maintaining interface stability. Sustained low gravity processing conditions are necessary in order to minimize these problems and obtain solidification conditions which approach steady state.

Andrews, J. Barry↗

Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry

Knowledge of the temperature dependence of the isobaric specific heat (C p ) upon deep supercooling can give insights regarding the anomalous properties of water. If a maximum in C p exists at a specific temperature, as in the isothermal compressibility, it would further validate the liquid–liquid critical point model that can explain the anomalous increase in thermodynamic response functions. The challenge is that the relevant temperature range falls in the region where ice crystallization becomes rapid, which has previously excluded experiments. Here, we have utilized a methodology of ultrafast calorimetry by determining the temperature jump from femtosecond X-ray pulses after heating with an infrared laser pulse and with a sufficiently long time delay between the pulses to allow measurements at constant pressure. Evaporative cooling of ~15-µm diameter droplets in vacuum enabled us to reach a temperature down to ~228 K with a small fraction of the droplets remaining unfrozen. We observed a sharp increase in C p , from 88 J/mol/K at 244 K to about 218 J/mol/K at 229 K where a maximum is seen. The C p maximum is at a similar temperature as the maxima of the isothermal compressibility and correlation length. From the C p measurement, we estimated the excess entropy and self-diffusion coefficient of water and these properties decrease rapidly below 235 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Activated relaxation in supercooled monodisperse atomic and polymeric WCA fluids: Simulation and ECNLE theory

Here, we combine simulation and Elastically Collective Nonlinear Langevin Equation (ECNLE) theory to study the activated relaxation in monodisperse atomic and polymeric Weeks–Chandler–Andersen (WCA) liquids over a wide range of temperatures and densities in the supercooled regime under isochoric conditions. By employing novel crystal-avoiding simulations, metastable equilibrium dynamics is probed in the absence of complications associated with size polydispersity. Based on a highly accurate structural input from integral equation theory, ECNLE theory is found to describe well the simulated density and temperature dependences of the alpha relaxation time of atomic fluids using a single system-specific parameter, a c , that reflects the nonuniversal relative importance of local cage and collective elastic barriers. For polymer fluids, the explicit dynamical effect of local chain connectivity is modeled at the fundamental dynamic free energy trajectory level based on a different parameter, N c , that quantifies the degree of intramolecular correlation of bonded segment activated barrier hopping. For the flexible chain model studied, a physically intuitive value of N c ≈ 2 results in good agreement between simulation and theory. A direct comparison between atomic and polymeric systems reveals that chain connectivity can speed up activated segmental relaxation due to weakening of equilibrium packing correlations but can slow down relaxation due to local bonding constraints. The empirical thermodynamic scaling idea for the alpha time is found to work well at high densities or temperatures but fails when both density and temperature are low. The rich and subtle behaviors revealed from simulation for atomic and polymeric WCA fluids are all well captured by ECNLE theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructure development during rapid alloy solidification

Abstract Solidification processing of structural alloys can take place over an extremely wide range of solid–liquid interface velocities spanning six orders of magnitude, from the low-velocity constitutional supercooling limit of microns/s to the high-velocity absolute stability limit of m/s. In between these two limits, the solid–liquid interface is morphologically unstable and typically forms cellular-dendritic microstructures, but also other microstructures that remain elusive. Rapid developments in additive manufacturing have renewed the interest in modeling the high-velocity range, where approximate analytical theories provide limited predictions. In this article, we discuss recent advances in phase-field modeling of rapid solidification of metallic alloys, including a brief description of state-of-the-art experiments used for model validation. We describe how phase-field models can cope with the dual challenge of carrying out simulations on experimentally relevant length- and time scales and incorporating nonequilibrium effects at the solid–liquid interface that become dominant at rapid rates. We present selected results, illustrating how phase-field simulations have yielded unprecedented insights into high-velocity interface dynamics, shedding new light on both the absolute stability limit and the formation of banded microstructures that are a hallmark of rapid alloy solidification near this limit. We also discuss state-of-the-art experiments used to validate those insights. Graphical abstract

36 MATERIALS SCIENCE↗

Effects of Hydrogen Bonding and Molecular Chain Flexibility of Substituted n-Alkyldimethylsilanes On Impact Ice Adhesion Shear Strength

The effects of hydrogen bonding and molecular flexibility upon ice adhesion shear strength were investigated using aluminum substrates coated with substituted n-alkyldimethylalkoxysilanes. The location of the chemical group substitution was on the opposing end of the linear n-alkyl chain with respect to silicon. Three hydrogen-bonding characteristics were evaluated: 1) non-hydrogen bonding, 2) donor/acceptor, and 3) acceptor. Varying the length of the n-alkyl chain provided an assessment of molecular chain flexibility. Coated and uncoated aluminum surfaces were characterized by receding water contact angle and surface roughness. Ice adhesion shear strength was determined in the Adverse Environment Rotor Test Stand facility from -16 to -8°C that simulated aircraft in-flight icing conditions within the FAR Part 25/29 Appendix C icing envelope. Surface roughness of the coatings was similar allowing for comparison of the test results. An adhesion reduction factor, based on the ice adhesion shear strength data with respect to uncoated aluminum obtained at the same temperature, was calculated to compare the data. The results revealed complex interactions with impacting supercooled water droplets that were interdependent upon ice accretion temperature, surface energy characteristics of water and ice, hydrogen bonding characteristic of the substituent, and length of the n-alkyl chain. To aid in explaining the results, 1) changes in the surface energy component (i.e., non-polar and polar) values that water undergoes during its’ phase change from liquid to solid that arise from the freezing of impacting supercooled water droplets on the surface depended upon the temperature during accretion were taken into account and 2) the physical properties (i.e., water solubility and melting point) of small compounds analogous to the substituted n-alkyldimethylalkoxysilanes used in this study were compared.

Smith, Joseph G.↗

Isokinetic Probe Total Water Content Measurements in the NASA Icing Research Tunnel with Supercooled Large Drop Conditions

An Isokinetic Total Water Content Evaporator (IKP2) was used to measure liquid water content (LWC) in the NASA Icing Research Tunnel (IRT) with spray conditions that ranged in LWC and cloud drop size spectra as characterized by the median volumetric diameter (MVD). The IKP2 measurements were made as part of an international collaborative effort to investigate the measurement of supercooled large drop (SLD) conditions in several icing wind tunnels. This report focuses on the IKP2 and background water vapor (BWV) measurements made within the NASA IRT during the October 2017 test entry. The IKP2 TWC results are compared to the IRT LWC calibration values for a range of LWC and MVD values. The IRT LWC calibration is based on measurements from a multi-element hot-wire probe. In general, the IKP2 TWC values were approximately 9% greater than the IRT LWC calibration values over a range of LWC from 0.4 g/m3 to 3.0 g/m3. The ratio of IKP2 TWC to IRT LWC calibration ranged from approximately 0.9 to 1.27 over a range of MVD from 15µm to 460 µm. Comparisons of this data set to IKP2 data from a 2014 IRT test entry show similar results in the regions where overlaps occurred. The results support the theory and observations of water mass loss from hot-wire TWC sensors when subjected to large MVD conditions.

Icing cloud instruments↗

Isokinetic Probe Total Water Content Measurements in the NASA Icing Research Tunnel with Supercooled Large Drop Conditions

An Isokinetic Total Water Content Evaporator (IKP2) was used to measure liquid water content (LWC) in the NASA Icing Research Tunnel (IRT) with spray conditions that ranged in LWC and cloud drop size spectra as characterized by the median volumetric diameter (MVD). The IKP2 measurements were made as part of an international collaborative effort to investigate the measurement of supercooled large drop (SLD) conditions in several icing wind tunnels. This report focuses on the IKP2 and background water vapor (BWV) measurements made within the NASA IRT during the October 2017 test entry. The IKP2 TWC results are compared to the IRT LWC calibration values for a range of LWC and MVD values. The IRT LWC calibration is based on measurements from a multi-element hot-wire probe. In general, the IKP2 TWC values were approximately 9% greater than the IRT LWC calibration values over a range of LWC from 0.4 g/m3 to 3.0 g/m3. The ratio of IKP2 TWC to IRT LWC calibration ranged from approximately 0.9 to 1.27 over a range of MVD from 15m to 460 m. Comparisons of this data set to IKP2 data from a 2014 IRT test entry show similar results in the regions where overlaps occurred. The results support the theory and observations of water mass loss from hot-wire TWC sensors when subjected to large MVD conditions.

o Aircraft Icing↗

Isokinetic Probe Total Water Content Measurements in the NASA Icing Research Tunnel with Supercooled Large Drop Conditions

An Isokinetic Total Water Content Evaporator (IKP2) was used to measure liquid water content (LWC) in the NASA Icing Research Tunnel (IRT) with spray conditions that ranged in LWC and cloud drop size spectra as characterized by the median volumetric diameter (MVD). The IKP2 measurements were made as part of an international collaborative effort to investigate the measurement of supercooled large drop (SLD) conditions in several icing wind tunnels. This report focuses on the IKP2 and background water vapor (BWV) measurements made within the NASA IRT during the October 2017 test entry. The IKP2 TWC results are compared to the IRT LWC calibration values for a range of LWC and MVD values. The IRT LWC calibration is based on measurements from a multi-element hot-wire probe. In general, the IKP2 TWC values were approximately 9% greater than the IRT LWC calibration values over a range of LWC from 0.4 g/m3 to 3.0 g/m3. The ratio of IKP2 TWC to IRT LWC calibration ranged from approximately 0.9 to 1.27 over a range of MVD from 15um to 460 um. Comparisons of this data set to IKP2 data from a 2014 IRT test entry show similar results in the regions where overlaps occurred. The results support the theory and observations of water mass loss from hot-wire TWC sensors when subjected to large MVD conditions.

o Aircraft Icing↗

Habit–Dependent Vapor Growth Modulates Arctic Supercooled Water Occurrence

We present an analysis of long-term data collected at Utqiagvik, Alaska, to explore the impacts of cloud processes on the probability of finding supercooled water given cloud temperature, P(L|T), in the topmost unseeded liquid-bearing layers. P(L|T) has local minima at temperatures around –6°C and –15°C. Simulations using habit-evolving ice microphysics models suggest that these minima are the result of efficient vapor growth by non-isometric habits found at these temperatures. Here, we conclude that habit-dependent vapor growth of ice crystals modulates the macrophysical occurrence of supercooled water in polar clouds, the effect of which should be included in model parametrizations to avoid biases and/or error compensation. Our methodology is adaptable for spherical ice treatments implemented in models (example parametrizations provided), amenable for use with satellite measurements to give global impartial observational targets for model evaluations, and may allow empirical characterization of bulk responses to seeding and possibly secondary ice effects.

54 ENVIRONMENTAL SCIENCES↗