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At least 325 records · Page 18

The vapor pressures of solid and liquid ozone

Vapor pressures of solid and liquid ozone have been measured over a temperature range 87 to below 66 K. The experiment was performed under flow conditions, and the gas was analyzed by a precision mass spectrometer system. In the range of solid ozone two forms, supercooled and crystalline ozone, were found. A least-square fit of the data for crystalline ozone resulted in the equation log P(torr) = A + B/T, where A = 10.460 and B = -1021.6. The estimated uncertainty of the data is + or - 1.0 percent. A triple-point temperature of 79.6 + or - 0.3 K was found where supercooled and crystalline ozone data intersect.

Hanson, David↗

Structural relaxation and crystallization in supercooled water from 170 to 260 K

The structural relaxation and crystallization of deeply supercooled water are investigated in transiently-heated nanoscale water films using infrared spectroscopy for temperatures between 170 and 260 K. For temperatures above ~230 K, the relaxation kinetics can be fit with a simple exponential decay which is characteristic of normal liquids. At lower temperatures, increasingly non-exponential decay is observed indicating the onset of heterogeneous dynamics. Water’s relaxation rate depends on its initial structure with hyper-quenched glassy water (HQW) typically relaxing more quickly than low-density amorphous solid water (LDA). At all temperatures, the relaxation time, trel is faster than the crystallization time, txtal. For HQW, the ratio, txtal/trel, goes through a minimum at ~198 K where it is about 60. The research was designed and supervised by GAK and BDK. LK and WAT conducted the experiments and analyzed the data. LK and GAK wrote the manuscript, with input from all authors.

Kringle, Loni M.↗

Wind Tunnel PSD and MVD Characterization Using New 1D2D Optical Array Probes

This work explores characterization of the liquid clouds using a combination of a forward scattering probe and two Optical Array Probes. Current OAP probes provide particle shape, size, and number concentration from two-dimensional shadow images. However, past studies have shown that such images are subject to distortion when outside of the focal plane. This affects the retrieval of particle size distributions, particularly in the Supercooled Large Droplet size range. In this article, the use of a Droplet Measurement Technologies Cloud Droplet Probe and two new OAPs produced by Science Engineering Associates, is examined using wind tunnel data, to assess suitability for use in a wind tunnel calibration in SLD conditions. The new OAP probes exploit a flexible and simple grey scale imaging method to eliminate some present shortcomings of commonly used OAPs, and to reduce correction factors. Spinning disk measurements were used to specify probe depth of field, and average size errors. Composite spectra covering the nominal 2-3200 µm size range were formed by crossing over from the CDP to 1D2D-X at 48 µm, and then to the 1D2D-Y at about 400 µm. A good overlap was found at the crossover points without any artificial scaling. Composite spectra adequately closed the liquid water content distribution, and provided integrated LWCs within about 35% of the hot-wire LWCs used for tunnel calibration. This discrepancy was at least partially attributed to LWC underestimation by the hot-wire at high MVD. A model of probe performance was used to show an example of expected accuracy of ideal probes subject to the same OAP distortions and using the same mitigating procedures and corrections, predicting PSD Median Volume Diameter and integrated LWC errors of less than 10%.

Aircraft Icing↗

Isotope effects in supercooled H 2 O and D 2 O and a corresponding-states-like rescaling of the temperature and pressure

Water shows anomalous properties that are enhanced upon supercooling. The unusual behavior is observed in both H 2 O and D 2 O, however, with different temperature dependences for the two isotopes. It is often noted that comparing the properties of the isotopes at two different temperatures (i.e., a temperature shift) approximately accounts for many of the observations—with a temperature shift of 7.2 K in the temperature of maximum density being the most well-known example. However, the physical justification for such a shift is unclear. Motivated by recent work demonstrating a “corresponding-states-like” rescaling for water properties in three classical water models that all exhibit a liquid–liquid transition and critical point, the applicability of this approach for reconciling the differences in the temperature- and pressure-dependent thermodynamic properties of H 2 O and D 2 O is investigated here. Utilizing previously published data and equations-of-state for H 2 O and D 2 O, we show that the available data and models for these isotopes are consistent with such a low temperature correspondence. These observations provide support for the hypothesis that a liquid–liquid critical point, which is predicted to occur at low temperatures and high pressures, is the origin of many of water’s anomalies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new capability for investigating the structure and dynamics of liquids at high pressures

Water and aqueous solutions are critical to many areas of science and technology. As a result, tremendous effort has been devoted to understanding them in detail. Despite over a century of research, fundamental questions about water and aqueous solutions remain unanswered. However, an intriguing possibility – that liquid water can exist in two thermodynamically distinct states – has emerged as the most likely explanation. The problem is that experimental confirmation of this hypothesis requires experiments on water at high pressures and low temperatures, conditions in which liquid water only exists briefly before turning into crystalline ice. This project investigated the feasibility of developing a new capability for study water and aqueous solutions under these challenging conditions. The physical constraints, such as the timescales for crystallization and thermal diffusion in supercooled water, were evaluated along with their impact on the design criteria for the instrument. Several basic design options were considered that could meet the technical requirements. The options were also evaluated with respect to their use of commercially available equipment versus the need for custom designs or in-house development. The project identified two viable options to pursue. The first option would use a high-pressure syringe pump in conjunction with fused silica (or sapphire) capillaries. The second option would use a diamond anvil cell. These options can both be used with optical spectroscopies, such as Raman or Infrared.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Boundary layer description of directional polymer crystallisation

Nearly fifty years ago Lovinger and Gryte suggested that the directional crystallization of a polymer was analogous to the quiescent isothermal crystallization experiment but at a supercooling where the crystal growth velocity was equal to the velocity of the moving front. Our experiments showed that this equivalence holds in a detailed manner at low directional velocities. To understand the underlying physics of these situations, we modeled the motion of a crystallization front in a liquid where the left side boundary is suddenly lowered below the melting point (Stefan's problem) but with the modification that the crystallization kinetics follow a version of the Avrami model. Our numerical results surprisingly showed that the results of the polymer analog track with the Stefan results which were derived for a simple liquid that crystallizes completely at its melting point; in particular, the position of the crystal growth-front evolved with time exactly as in the Stefan problem. The numerical solution also showed that the temperature in the immediate vicinity of the growth-front decreased with increasing front velocity, which is in line with Lovinger and Gryte's ansatz. To provide a clear theoretical understanding of these numerical results we derive a boundary layer solution to the governing coupled differential equations of the polymer problem. The analytical results are in agreement with our observations from experiments and numerical computations but show that this equivalence between the small molecule and polymer analog only holds in the limit where the crystallization enthalpy is much larger than the rate at which heat is conducted away in the polymer. In particular, in the context of the temperature profile, the enthalpy generated by the crystallisation process which is spread out over a narrow spatial region can be approximated as a point source whose location and temperature correspond to the Lovinger–Gryte ansatz.

36 MATERIALS SCIENCE↗

Creating a Bimodal Drop-Size Distribution in the NASA Glenn Icing Research Tunnel

The Icing Research Tunnel at NASA Glenn has demonstrated that they can create a drop-size distribution that matches the FAA Part 25 Appendix O FZDZ, MVD40 m normalized cumulative volume within 10. This is done by simultaneously spraying the Standard and Mod1 nozzles at the same nozzle air pressure and different nozzle water pressures. It was also found through these tests that the distributions that are measured when the two nozzle sets are sprayed simultaneously closely matched what was found by combining the two individual distributions analytically. Additionally, distributions were compared between spraying all spraybars and also by spraying only every-other spraybar, and were found to match within 4. The cloud liquid water content uniformity for this condition has been found to be excellent: 10. It should be noted, however, that the liquid water content for this condition in the IRT is much higher than the requirement specified in Part 25 Appendix O.

drop-size↗

Direct observation of interface instability during crystal growth

The general aim of this investigation was to study interface stability and solute segregation phenomena during crystallization of a model system. Emphasis was to be placed on direct observational studies partly because this offered the possibility at a later stage of performing related experiments under substantially convection-free conditions in the space shuttle. The major achievements described in this report are: (1) the development of a new model system for fundamental studies of crystal growth from the melt and the measurement of a range of material parameters necessary for comparison of experiment with theory. (2) The introduction of a new method of measuring segregation coefficient using absorption of a laser beam by the liquid phase. (3) The comparison of segregation in crystals grown by gradient freezing and by pulling from the melt. (4) The introduction into the theory of solute segregation of an interface field term and comparison with experiment. (5) The introduction of the interface field term into the theories of constitutional supercooling and morphological stability and assessment of its importance.

Tiller, W. A.↗

Cooling and solidification of liquid-metal drops in a gaseous atmosphere

The free fall of a liquid-metal drop, heat transfer from the drop to its environment, and solidification of the drop are described for both gaseous and vacuum atmospheres. A simple model, in which the drop is assumed to fall rectilinearly, with behavior like that of a rigid particle, is developed to describe cooling behavior. Recalescence of supercooled drops is assumed to occur instantaneously when a specified temperature is passed. The effects of solidification and experimental parameters on drop cooling are calculated and discussed. Major results include temperature as a function of time, and of drag, time to complete solidification, and drag as a function of the fraction of the drop solidified.

Mccoy, J. K.↗

Study of the water dynamics near hydrophilic, nanostructured CuO surfaces by quasielastic and inelastic neutron scattering

We have used quasielastic and inelastic neutron scattering to investigate the structure, dynamics, and phase transitions of water interacting with superhydrophilic CuO surfaces that not only possess a strong affinity for water but also a “grass-like” topography that is rough on both micro- and nanoscales. Here, we report quasielastic neutron scattering (QENS) measurements on two samples differing in water content at five temperatures below 280 K. The QENS spectra show water undergoing two different types of diffusive motion near the CuO surfaces: a “slow” translational diffusion occurring on a nanosecond time scale and a faster rotational motion. Further from the surfaces, there is “fast” translational diffusion comparable in rate to that of bulk supercooled water and the rotational motion occurring in the interfacial water. Analysis of the QENS spectra supports wetting of water to the CuO blades as seen in electron microscopy images. In addition, we observe an anomalous temperature dependence of the QENS spectra on cooling from 270 to 230 K with features consistent with a liquid–liquid phase transition. We suggest that the solvent-like properties of the coexisting bulk-like water in our CuO samples are a significant factor in determining the temperature dependence of the interfacial water’s dynamics. Our results are compared with those obtained from two well-studied substrate classes: (1) silicas that contain ordered cylindrical nanopores but have weaker hydrophilicity and (2) nanoparticles of other transition-metal oxides, such as TiO 2 , which share the strong hydrophilicity of our samples but lack their porosity.

36 MATERIALS SCIENCE↗

Phase diagram of KHF2 and non-equilibrium effects

The equilibrium diagram for the KHF2-H2O system was constructed from cooling and heating curves for the compositions between 5 wt% and 40 wt% KHF2 and the results are shown. The phase diagrams shown is typical of that of a two component system with miscible liquid phases and whole solid phases consist of pure components. A eutectic point was found at approximately 15% KHF2 which remains completely liquid down to a temperature of -9.0 C. No hydrate formation was observed and no anomalous behavior such as the occurrence of solid transitions or metastable states was observed. The effect of rapid freezing on the equilibrium diagram did not appear, and cooling curves exhibited only one halt. Also, at rapid freezing rates, the supercooling of the solutions was smaller than those observed at the slow cooling rates. The existence of a eutectic composition and the slow rate of dissolution of the salt are used to interpret heat absorption behavior in practical applications of the KHF2-H2O system.

Hobson, M. C.↗

Creating a Bimodal Drop-Size Distribution in the NASA Glenn Icing Research Tunnel

The Icing Research Tunnel at NASA Glenn has demonstrated that they can create a drop-size distribution that matches the FAA Part 25 Appendix O FZDZ, MVD <40 microns normalized cumulative volume within 10%. This is done by simultaneously spraying the Standard and Mod1 nozzles at the same nozzle air pressure and different nozzle water pressures. It was also found through these tests that the distributions that are measured when the two nozzle sets are sprayed simultaneously closely matched what was found by combining the two individual distributions analytically. Additionally, distributions were compared between spraying all spraybars and also by spraying only every-other spraybar, and were found to match within 4%. The cloud liquid water content uniformity for this condition has been found to be excellent. It should be noted, however, that the liquid water content for this condition in the IRT is much higher than the requirement specified in Part 25 Appendix O.

bimodal distribution↗

A study of Type I polar stratospheric cloud formation

Mechanisms for the formation of Type I (nitric acid-based) polar stratospheric clouds (PSCs) are discussed. If the pre-existing sulfate aerosols are liquid prior to PSC formation, then nitric acid particles (Type Ib) form by HNO3 dissolution in aqueous H2SO4 solution droplets. This process does not require a nucleation step for the formation of HNO3 aerosols, so most pre-existing aerosols grow to become relatively small HNO3-containing particles. At significantly lower temperatures, the resulting supercooled solutions (Type Ib) may freeze to form HNO3 ice particles (Type Ia). If the pre-existing sulfate aerosols are initially solid before PSC formation, then HNO3 vapor can be deposited directly on the frozen sulfate particles. However, because an energy barrier to the condensation exists a nucleation mechanism is involved. Here, we suggest a unique nucleation mechanism that involves formation of HNO3/H20 solutions on the sulfate ice particles. These nucleation processes may be highly selective, resulting in the formation of relatively small number of large particles.

Tabazadeh, A.↗

The Effect of Stainless Steel 304 Surface Roughness on Ice Adhesion Shear Strength of Accreted Impact Ice

Aircraft in-flight icing is problematic due to the ad-verse effect on vehicle performance. It occurs when supercooled water droplets (SCWD) present in clouds, under the appropriate environmental conditions, col-lide with the aircraft surface resulting in accretion of ice (i.e., impact icing). Impact ice can range from clear/glaze to rime or a combination of the two (i.e., mixed) with the type determined by the air temperature (0 to -20°C), liquid water content (LWC, 0.3-0.6 g/cu.m), and droplet size [median volumetric diameter (MVD) of 15-40 µm] present during accretion.1 These impact icing events generally occur at temperatures ranging from 0 to -20°C. Below -20°C, ice crystals dominate the environment and typically do not adhere to the aircraft surface. A main difference between an impact icing occurrence and a slow growth icing (i.e., freezer ice) one is the speed of the icing event. Besides environmental conditions, ice adhesion strength (IAS) to a metallic substrate depends upon surface roughness. It is known that increasing surface roughness and decreasing temperature lead to in-creases in IAS.

Smith, Joseph G., Jr.↗

Morphological Stability of Faceted Interfaces

The major focus of this investigation is to study the fundamentals of layer spreading mechanisms during growth of doped Ge (a facet forming material), and to determine the conditions for morphological instability of vicinal solid-liquid interfaces. The investigation will also lead to the determination of the effect of dopants on the layer growth kinetics, step free energy, and dopant capture by the advancing ledges. The theoretical treatment of growth of faceted interfaces indicates that the kinetics of a step on a growing vicinal interface considerably depends on its angle of inclination, the melt concentration, and characteristics of flow currents in the melt. The morphological stability of the interface also depends on these parameters, as well as on the density and spreading velocity of the steps. However, the treatment of the instability of the interface by the layer growth mechanism is rather difficult because it requires exact knowledge of the thermal and solutal fields, hydrodynamics of the melt, and supercooling at the interface. The results of recent space experiments of the principal investigator involving directional solidification of faceted Bi-Sn alloys have shown that the morphological stability of various crystallographic orientations is significantly affected by the anistropy in interfacial properties of the faceted alloy in general, and the interface kinetics in particular. These findings have also raised many important and fundamental questions, particularly with respect to the behavior of interfacial steps, which need to be addressed via additional groundbased and microgravity experiments. For the present investigation we will use a novel crystal growth technique which provides axial heat flux close to the solid-liquid boundary. The Axial Heat Processing (AHP) technique allows for precise control and determination of the heat and mass transfer close to the crystallization front, and the establishment of a planar interface over the entire cross-section of the growing crystal.

Abbaschian, Reza↗

Review of Low-Cost Organic and Inorganic Phase Change Materials with Phase Change Temperature between 0°C and 65°C

Phase change materials (PCMs) that undergo a phase transition may be used to provide a nearly isothermal latent heat storage at the phase change temperature. This work reports the energy storage material cost ($/kWh) of various PCMs with phase change between 0-65°C. Four PCM classes are analyzed for their potential use in building systems: 1) inorganic salt hydrates, 2) organic fatty acids, 3) organic fatty alcohols, and 4) organic paraffin waxes. Many salt hydrates have low material costs (0.09 - 2.53 $-kg-1), high latent heat of fusion (100-290 J-g-1), and high densities (1.3-2.6 g-cm-3), leading to favorable volumetric storage density and low energy storage costs, 50-130 kWh-m3 and 0.90-40 $-kWh-1, respectively. Some salts are notably more expensive due to their scarcity or pressures from competing industries such as lithium-based salts. Fatty acids have the lowest energy storage cost in the temperature range 8-17°C at 6.50 – 40 $-kWh-1. Despite favorable latent heat (125 – 250 J-g-1) their low density gives (0.9 g-cm3) gives poor volumetric storage capacity, 32 – 80 kWh-m3. Fatty alcohols generally have high material costs 2.50 – 200 $-kg-1 which leads to high energy storage costs, 40-3000 $/kWh. With latent heat and density similar to fatty acids, fatty alcohols have poor volumetric energy storage, 43 – 55 kWh-m-3.Paraffin waxes containing only a single length carbon chain have a higher energy cost (15 – 500 $-kWh-1) than generic paraffin waxes containing many lengths of carbon chains (7 – 30 $-kWh-1). Pure waxes have a discrete phase change temperature due to their homogeneity. In contrast, a less refined generic wax with several carbon chain lengths is more likely to have a pronounced temperature glide during its phase change. Pure single carbon chain waxes are generally required for applications <45°C as generic paraffin waxes melt between 45-70°C. For many waxes, a solid-solid transition occurs at temperatures below the solid-liquid phase change. For pure paraffins with carbon content ≥22 C atoms, these transitions may appear near the same temperature resembling a temperature glide.The challenges with fatty acids, fatty alcohols, and waxes are low thermal conductivity, low density, some flammability concerns, and compatibility issues with some common engineering materials such as polymers. Challenges with salt hydrates are pronounced supercooling (>5°C), incongruent melting, and corrosiveness. All PCMs may degrade if exposed to ambient conditions and therefore require proper sealing.

Hirschey, Jason↗

Ice Roughness in Short Duration SLD Icing Events

Ice accretion codes depend on models of roughness parameters to account for the enhanced heat transfer during the ice accretion process. While mitigating supercooled large droplet (SLD or Appendix O) icing is a significant concern for manufacturers seeking future vehicle certification due to the pending regulation, historical ice roughness studies have been performed using Appendix C icing clouds which exhibit mean volumetric diameters (MVD) much smaller than SLD clouds. Further, the historical studies of roughness focused on extracting parametric representations of ice roughness using multiple images of roughness elements. In this study, the ice roughness developed on a 21-in. NACA 0012 at 0deg angle of attack exposed to short duration SLD icing events was measured in the Icing Research Tunnel at the NASA Glenn Research Center. The MVD's used in the study ranged from 100 micrometer to 200 micrometers, in a 67 m/s flow, with liquid water contents of either 0.6 gm/cubic meters or 0.75 gm/cubic meters. The ice surfaces were measured using a Romer Absolute Arm laser scanning system. The roughness associated with each surface point cloud was measured using the two-dimensional self-organizing map approach developed by McClain and Kreeger (2013) resulting in statistical descriptions of the ice roughness.

Icing↗

Magnesium fluoride as energy storage medium for spacecraft solar thermal power systems

MgF2 was investigated as a phase-change energy-storage material for LEO power systems using solar heat to run thermal cycles. It provides a high heat of fusion per unit mass at a high melting point (1536 K). Theoretical evaluation showed the basic chemical compatibility of liquid MgF2 with refractory metals at 1600 K, though transient high pressures of H2 can occur in a closed container due to reaction with residual moisture. The compatibility was tested in two refractory metal containers for over 2000 h. Some showed no deterioration, while there was evidence that the fluoride reacted with hafnium in others. Corollary tests showed that the MgF2 supercooled by 10-30 K and 50-90 K.

Lurio, Charles A.↗