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Recently, a semiempirical method for alloys based on equivalent crystal theory was introduced. The method successfully predicts the concentration dependence of the heat of formation and lattice parameter of binary alloys. A study of the parameters of the method is presented, along with new results for (gamma)Fe-Pd and (gamma)Fe-Ni alloys.
We present the characterization of several atmospheric aerosol analogs in a tabletop chamber and an analysis of how the concentration of NaCl present in these aerosols influences their bulk optical properties. Atmospheric aerosols (e.g., fog and haze) degrade optical signal via light–aerosol interactions causing scattering and absorption, which can be described by Mie theory. This attenuation is a function of the size distribution and number concentration of droplets in the light path. These properties are influenced by ambient conditions and the droplet’s composition, as described by Köhler theory. It is therefore possible to tune the wavelength-dependent bulk optical properties of an aerosol by controlling droplet composition. We present experimentation wherein we generated multiple microphysically and optically distinct atmospheric aerosol analogs using salt water solutions with varying concentrations of NaCl. The results demonstrate that changing the NaCl concentration has a clear and predictable impact on the microphysical and optical properties of the aerosol.
Metal - superconductor (YBCO) systems have been prepared and characterized by resistivity, ac susceptibility and dc SQUID magnetic moment measurements. The silver composites showed superconducting transition for all the composites processed and the superconducting transition temperature tends to depend upon the concentration of the silver in the composite. Aluminum composites showed an unusual resistivity results with two transitions around 90 K and 120 K. The superconducting property of silver composites can be explained qualitatively in terms of the proximity theory that has been suggested for the low temperature superconductors.
In order to study the role of CMSX2 single crystal microstructure on the combined stress-hydrogen environment effects, hydrogen was introduced by cathodic charging. Concentration measurements were carried out to investigate the dependence of hydrogen solubility and trapping on microstructure. Mechanical properties were measured at room temperature on smooth tensile specimens as a function of heat treatment, crystal orientation and H charging conditions. SEM and TEM allow to study H induced cracks initiation and propagation. A large amount of hydrogen can be dissolved and trapped in CMSX2 single crystals when exposed to a high hydrogen fugacity environment. The strong H trapping evidenced in voids explains the predominant role of these defects as crack initiation sites. The strong detrimental effect of hydrogen on the material tenacity is discussed.
The evolution of solid particles in the solar nebula (or other circumstellar disk) is described. Motions of bodies less than about 1 km in size were dominated by gas drag rather than gravity. An original population of microscopic grains had to produce greater than km-sized planetesimals before gravitational accretion of planets could begin. Planetesimals probably formed by coagulation of grain aggregates that collided due to differential settling, turbulence, and drag-induced orbital decay. Growth of such aggregates depended on sticking mechanisms and their mechanical properties, which are poorly understood. Their growth was aided by concentration of larger bodies toward the central plane of the disk. The nebula could remain optically thick during this process. It is unlikely that a particle layer formed by settling would undergo gravitational instability, as a small amount of turbulence would keep the particle layer from reaching the critical density. This conclusion is independent of the particle size, as even large bodies do not effectively decouple from the gas. Even in a laminar disk, shear in the particle layer would generate enough turbulence to keep it stirred up.
Properties of supersaturated solutions such as the density, viscosity, and solute diffusivity are dependent on the solute concentration. The diffusion-boundary-layer equations are derived and solved for the natural convection case with the viscosity and density dependent on the solute concentration. The solution obtained demonstrates that, at the vicinity of the saturation concentration c(sub s), there is a non-trivial dependence of the solution viscosity eta on its density rho: eta(c(sub s)) = eta(rho(sub s)) varies as rho(sub s)(exp 1/2), where rho(sub s) = rho(c(sub s)). This result has been verified in experiments with aqueous solutions of inorganic and organic salts.
The possibility of an accidental fire in space-based facilities is a primary concern of space exploration programs. Spacecraft environments generally present low velocity air currents produced by ventilation and heating systems (of the order of 0.1 m/s), and fluctuating oxygen concentrations around that of air due to CO2 removal systems. Recent experiments of flame spread in microgravity show the spread rate to be faster and the limiting oxygen concentration lower than in normal-gravity. To date, there is not a material flammability-testing protocol that specifically addresses issues related to microgravity conditions. The present project (FIST) aims to establish a testing methodology that is suitable for the specific conditions of reduced gravity. The concepts underlying the operation of the LIFT apparatus, ASTM-E 1321-93, have been used to develop the Forced-flow Ignition and flame-Spread Test (FIST). As in the LIFT, the FIST is used to obtain the flammability diagrams of the material, i.e., graphs of ignition delay time and flame spread rate as a function of the externally applied radiant flux, but under forced flow rather than natural convection conditions, and for different oxygen concentrations. Although the flammability diagrams are similar, the flammability properties obtained with the FIST are found to depend on the flow characteristics. A research program is currently underway with the purpose of implementing the FIST as a protocol to characterize the flammability performance of solid materials to be used in microgravity facilities. To this point, tests have been performed with the FIST apparatus in both normal-gravity and microgravity conditions to determine the effects of oxidizer flow characteristics on the flammability diagrams of polymethylmethacrylate (PMMA) fuel samples. The experiments are conducted at reduced gravity in a KC- 135 aircraft following a parabolic flight trajectory that provides up to 25 seconds of low gravity. The objective of the experiments is to obtain data of ignition delay and flame spread rate at low flow velocities (0.1 to 0.2 m/s), which cannot be obtained under normal gravity because of the natural convection induced flows (approx. 0.5 m/s). Due to the limited reduced gravity time, the data can only be obtained for high radiant fluxes, and are consequently limited in scope. These tests do, however, provide insight into the flammability diagram characteristics at low velocity and reduced gravity, and also into the implications of the flow-dependence of the flammability properties under environments similar to those encountered in space facilities.
Brief Course Description: In 2 hours only the most basic principles of cryogenics can be presented. I will concentrate on the differences between a room temperature thermal analysis and cryogenic thermal analysis, namely temperature dependent properties. I will talk about practical materials for thermal contact and isolation. I will finish by describing the verification process and instrumentation used that is unique to cryogenic (in general less than 100K) systems.
Hg sub 1-xZn sub xSe alloys of composition x=0.10 were grown in a Bridgman-Stockbarger growth furnace at translation rates of 0.3 and 0.1 micron sec. The axial and radial composition profiles were determined using precision density measurements and IR transmission-edge-mapping, respectively. A more radially homogeneous alloy was produced at the slower growth rate, while the faster growth rate produced more axially homogeneous alloys. A determination of the electrical properties of the Hg sub 1-xZn sub xSe samples in the temperature range 300K-20K was also made. Typical carrier concentrations were on the order of magnitude of 10 to the 18th power cu/cm, and remained fairly constant as a function of temperature. A study was also made of the temperature dependence of the resistivity and Hall mobility. The effect of annealing in a selenium vapor on both the IR transmission and the electrical properties was determined. Annealing was effective in reducing the number of native donor defects and at the resulting lower carrier concentrations, charge carrier concentration was shown to be a function of temperature. Annealing caused the mobility to increase, primarily at the lower temperature, and the room temperature resistivity to increase. Annealing was also observed to greatly enhance the % IR transmittance of the samples. This was due primarily to the effect of annealing on decreasing the charge carrier concentration.
Lead-free piezoelectric ceramics of (1 − x)K0.5Na0.5NbO3-xCaTiO3 were fabricated, and their crystal structure, microstructure, and electrical properties were systematically studied. Rietveld refinement of the x-ray diffraction data and Raman spectroscopic analyses revealed a composition-dependent structural phase transition: three phase transitions, namely, from a pure orthorhombic phase for x ≤ 0.02 to a mixed phase of orthorhombic and tetragonal phases (0.03 ≤ x ≤ 0.08) and finally another mixed phase of tetragonal + cubic for x = 0.10 and 0.15 at room temperature (RT). The morphological study reveals a decrease in grain size along with a more uniform distribution of grains as the concentration of CaTiO3 (CT) increases; notably, a homogeneous distribution of grains is observed for x = 0.05. The temperature-dependent dielectric properties show two phase transitions, from orthorhombic to tetragonal (TO-T) and tetragonal to cubic (TC), for unmodified K0.5Na0.5NbO3 (KNN). However, both the phase transition temperatures (TO-T and TC) decrease, and the transition peaks broaden with an increase in CT substitution, and for x > 0.06, the TO-T shifted below RT. The broadening of the transition peak at TO-T may be due to the relaxation behavior. Among the prepared samples, the 5 mol. % CT-modified KNN shows the optimum electrical properties (d33 = 114 pC/N, ɛr = 412, and 2Pr = 15.25 μC/cm2) at RT. The enhanced electrical properties for x = 0.05 are due to the coexistence of orthorhombic and tetragonal phases, facilitating easy polarization rotation and flattening of the free energy profile. A phase diagram has been constructed based on the information gathered from the temperature-dependent dielectric measurements, RT x-ray diffraction, and Raman spectroscopy data and is discussed in detail.
We report our ongoing research on polyamide aerogels made by step growth polymerization using a combination of terephthaloyl chloride, isophthaloyl chloride and m-phenylenediamine. Crosslinking of the amine capped polymer chains with 1,3,5-benzenetricarbonyl trichloride causes gelation in as little as two to five minutes. Removing the reaction solvent is accomplished through solvent exchange, followed by drying using supercritical CO2 extraction to give colorless aerogels with densities ranging from 0.07 to 0.33 grams per cubic centimeter and surface areas as high as 440 square meters per gram. Statistical experimental design methodology has been utilized to investigate dependence of properties of these aerogels, such as density, compressive modulus, and surface area, on changes in fabrication parameters including formulated number of amide oligomer repeat units (n-value), acid chloride (meta, para or combination), and solids concentration of solution used for gelation. For example, the density of these materials was found to be dependent on the acid chloride type and the solids concentration, but n was not a significant variable. However, surface area was significantly influenced by all three parameters. The polyamide aerogels represent a potential cost savings over previously reported polyimide aerogels, since monomers are all inexpensive and commercially available. Surface area and density were both highest when 100 terephthaloyl chloride was used but a combination of 5 solid concentration, 100 terephthaloyl chloride and n of 20 gave the best combination of properties.
Here, in this study, we performed an experimental and computational investigation into the feasibility of utilizing photoionization to enhance the electrical conductivity of seeded oxy-fuel combustion products and improve the performance of magnetohydrodynamic (MHD) power generators. We applied a variety of optical and microwave diagnostics to study the ionization and recombination processes of potassium excited by an excimer laser in a high-velocity oxy-fuel free jet. Computational fluid dynamic (CFD) simulations were performed to model the thermophysical properties and species densities of the free jet. The CFD results were validated with position-dependent potassium concentration measurements. Electron recombination exponential lifetimes were measured through time-resolved microwave transmission. The experimental electron lifetimes were compared with lifetimes calculated from CFD-predicted species densities and literature recombination rates. It was determined that K + or O 2 are the most likely recombination partners for photoionized electrons. Time-resolved fluorescence measurements provided evidence of an ionization pathway involving a two-photon ionization of KOH . Finally, a zero-dimensional chemical kinetic model was developed to assess the fundamental viability of inducing a non-equilibrium electron population to provide a net energy return in combustion-driven MHD power generators. We determined that a high energy return is feasible for targeting electrode boundary layers with ultraviolet photoionization. We also found that photoionization could potentially lower the required temperature of the bulk gas flow.
Abstract. Cloud condensation nuclei (CCN) spectrum and the CCN activated fraction of size-resolved aerosols (SR-CCN) were measured at a rural site on Long Island during the Department of Energy (DOE) aerosol life cycle intensive operational period (ALC-IOP) from 15 July to 15 August 2011. During the last week of the ALC-IOP, the dependence of the activated fraction on aerosol volatility was characterized by sampling downstream of a thermodenuder (TD) operated at temperatures up to 100 ∘C. Here we present aerosol properties, including aerosol total number concentration, CCN spectrum, and the CCN hygroscopicity, for air masses of representative origins during the ALC-IOP. The hygroscopicity of organic species in the aerosol is derived from CCN hygroscopicity and chemical composition. The dependence of organic hygroscopicity on the organic oxidation level (e.g., atomic O:C ratio) agrees well with theoretical predictions and results from previous laboratory and field studies. The derived κorg and O:C ratio first increase as TD temperature increases from 20 ∘C (i.e., ambient temperature) to 50 or 75 ∘C and then decrease as TD temperature further increases to 100 ∘C. The initial increases of O:C and κorg with TD temperature below 50 ∘C are likely due to evaporation of more volatile organics with relatively lower O:C and hygroscopicity such as primary organic aerosol. At the high TD temperatures, the decreases of O:C and κorg indicate that evaporated organics were more oxygenated and had lower molecular weights. These trends are different from previous laboratory experiments and field observations, which reported that organic O:C increased monotonically with increasing TD temperature, whereas κorg decreased with the TD temperature. One possible reason is that previous studies were either focused on laboratory-generated secondary organic aerosol (SOA) or based on field observations at locations more dominated by SOA.
A mechanism involving compositional fluctuations at certain frequencies is examined by which the heterogeneity of a composite solid propellant may contribute directly to the combustion response function of combustion instability theory. A combustion model appropriate to ammonium perchlorate (AP) is used to derive the combustion response to compositional fluctuations, and the properties of the combustion response are discussed in terms of the theoretical results obtained. The concentration exponent, i.e., the dependence of the burn rate on AP concentration, is found to be a signficant combustion parameter and to have a tremendous range of variability. It is suggested that the combustion response to compositional fluctuations may be a dominating factor in driving combustion instability.
Detailed elemental analysis is essential for a successful development and optimization of material systems and synthesis methods. This is especially relevant for Li- and Na-containing compounds, found in state-of-the-art and next-generation battery systems. Their materials’ properties and thus the final device performance strongly depend on the crystal structure, the stoichiometry, and defect chemistry, e.g., influencing charge carrier concentration and activation energies for vacancy transport. However, a detailed quantitative analysis of light elements in a heavy matrix, featuring a broad range of solubilities and vapor pressures, is often difficult and associated with large uncertainties and thus neglected in favor of just reporting the stoichiometry as “weighed in.” Here, in this work, we report several approaches to digest and dissolve various oxide and sulfide-based materials, used in next-generation Li batteries, for elemental analysis via optical emission spectroscopy. These include the most common solid electrolytes Li-La-Ti–O, a perovskite material (LLTO), and Li-La-Zr-O which has garnet structure (LLZO). Additionally, a facile thermal digestion process is reported for a surrogate sulfide solid electrolyte (Na 2 S). The digestion procedures reported here are suitable for almost any laboratory environment and, when applied, will improve understanding of the synthesis-structure–property correlations needed to advanced batteries with all solid-state configurations.
The primary objective of this project is to develop reliable and standardized spectroscopic measurement techniques to determine radiative properties, specifically the emittance and reflectance, of materials relevant for the next generation (Gen3) concentrated solar power (CSP) technologies. Experimental measurements will span near- and mid-infrared wavelengths (1–20 µm) with emphasis on quantifying the influences of: (1) operating temperatures of 25–1000 °C, (2) thermal cycling, and (3) environmental exposure of materials during operation (vacuum/air). A secondary goal is to develop open-access and digitized databases to host and share experimental data, together with standardized measurement protocols and operating procedures to determine optical properties of materials. This project will also include reasonable emphasis on developing predictive modeling tools to augment experimental data to extract more fundamental and material-specific radiative properties.
Understanding the irradiation-induced defects in oxides is of interest for a wide range of applications. ZnO is an interesting oxide with mixed ionic and covalent bonding that contains a variety of point defect structures—making it an excellent model for studying irradiation-induced defects and their impact on properties. Here, we investigate the effects of neutron irradiation on the formation of defects and on the structural, optical, and electrical properties of ZnO single crystals. We observe the formation of vacancies and voids via positron annihilation spectroscopy. Neutron irradiation led to a significant deterioration of the ZnO structure and formed a high concentration of point defects, vacancy clusters, and voids with large disparities in their structure across variable irradiation times. It also led to significant changes in the optical properties and sample color. Irradiation for 444 h induced a high concentration of Cu acceptors as well as a high concentration of Ga donors. Additionally, temperature-dependent Hall effect measurements revealed the competing production of donors and acceptors and showed an increase in the slope of the carrier freeze-out curve with increasing irradiation dose. This work demonstrates the combined effects of neutron irradiation in producing a wide range of structural defects, impurities, and dopants in oxides and their enormous impact on modifying the oxide structure and both the optical and electronic properties. It particularly emphasizes the importance of considering the production of new impurities and dopants during the neutron irradiation of oxides.
We investigate the site substitution scheme of specific alloying elements in ordered compounds and the dependence of site occupancy on compound stoichiometry, alloy concentration. This basic knowledge, and the interactions with other alloying additions are necessary in order to predict and understand the effect of various alloying schemes on the physical properties of a material, its response to various temperature treatments, and the resulting mechanical properties. Many theoretical methods can provide useful but limited insight in this area, since most techniques suffer from constraints in the type of elements and the crystallographic structures that can be modeled. With this in mind, the Bozzolo-Ferrante-Smith (BFS) method for alloys was designed to overcome these limitations, with the intent of providing an useful tool for the theoretical prediction of fundamental properties and structure of complex systems. After a brief description of the BFS method, its use for the determination of site substitution schemes for individual as well as collective alloying additions to intermetallic systems is described, including results for the concentration dependence of the lattice parameter. Focusing on B2 NiAl, FeAl and CoAl alloys, the energetics of Si, Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Hf, Ta and W alloying additions are surveyed. The effect of single additions as well as the result of two simultaneous additions, discussing the interaction between additions and their influence on site preference schemes is considered. Finally, the BFS analysis is extended to ternary L1(sub 2) (Heusler phase) alloys. A comparison between experimental and theoretical results for the limited number of cases for which experimental data is available is also included.