Chemically induced ignition in aircraft and spacecraft electrical circuitry by glycol/water solutions
Flammability hazards chemically induced in aircraft and spacecraft electrical circuitry by glycol/water solutions
Downs, W. R.↗
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Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study
The chemical expansion of Pr 0.1 Ce 0.9 O 2-δ (PCO) and CeO 2-δ thin films is investigated in the temperature range between 600 °C and 800 °C by laser Doppler vibrometry (LDV). It enables non-contact determination of nanometer scale changes in film thickness at high temperatures. The present study is the first systematic and detailed investigation of chemical expansion of doped and undoped ceria thin films at temperatures above 650 °C. The thin films were deposited on yttria stabilized zirconia substrates (YSZ), operated as an electrochemical oxygen pump, to periodically adjust the oxygen activity in the films, leading to reversible expansion and contraction of the film. This further leads to stresses in the underlying YSZ substrates, accompanied by bending of the overall devices. Film thickness changes and sample bending are found to reach up to 10 and several hundred nanometers, respectively, at excitation frequencies from 0.1 to 10 Hz and applied voltages from 0–0.75 V for PCO and 0–1 V for ceria. At low frequencies, equilibrium conditions are approached. As a consequence maximum thin-film expansion of PCO is expected due to full reduction of the Pr ions. The lower detection limit for displacements is found to be in the subnanometer range. At 800 °C and an excitation frequency of 1 Hz, the LDV shows a remarkable resolution of 0.3 nm which allows, for example, the characterization of materials with small levels of expansion, such as undoped ceria at high oxygen partial pressure. As the correlation between film expansion and sample bending is obtained through this study, a dimensional change of a free body consisting of the same material can be calculated using the high resolution characteristics of this system. A minimum detectable dimensional change of 5 pm is estimated even under challenging high-temperature conditions at 800 °C opening up opportunities to investigate electro-chemo-mechanical phenomena heretofore impossible to investigate. The expansion data are correlated with previous results on the oxygen nonstoichiometry of PCO thin films, and a defect model for bulk ceria solid solutions is adopted to calculate the cation and anion radii changes in the constrained films during chemical expansion. The constrained films exhibit anisotropic volume expansion with displacements perpendicular to the substrate plane nearly double that of bulk samples. The PCO films used here generate high total displacements of several 100 nm’s with high reproducibility. Consequently, PCO films are identified to be a potential core component of high-temperature actuators. They benefit not only from high displacements at temperatures where most piezoelectric materials no longer operate while exhibiting, low voltage operation and low energy consumption.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Quantum mechanical calculations to chemical accuracy
The accuracy of current molecular-structure calculations is illustrated with examples of quantum mechanical solutions for chemical problems. Two approaches are considered: (1) the coupled-cluster singles and doubles (CCSD) with a perturbational estimate of the contribution of connected triple excitations, or CCDS(T); and (2) the multireference configuration-interaction (MRCI) approach to the correlation problem. The MRCI approach gains greater applicability by means of size-extensive modifications such as the averaged-coupled pair functional approach. The examples of solutions to chemical problems include those for C-H bond energies, the vibrational frequencies of O3, identifying the ground state of Al2 and Si2, and the Lewis-Rayleigh afterglow and the Hermann IR system of N2. Accurate molecular-wave functions can be derived from a combination of basis-set saturation studies and full configuration-interaction calculations.
Bauschlicher, Charles W., Jr.↗
Chemical complexity suppresses interstitial solute segregation to screw dislocation cores in the bcc NbTaTiHfZr high-entropy alloy
Recent reports suggest that interstitial solute additions to body-centered cubic (bcc) high-entropy alloys (HEAs) may enhance their mechanical properties. However, details of interactions between interstitial atoms and dislocations in these HEAs remain incompletely understood. Using first-principles calculations, we examine the energetics of C, N, and O interstitial solutes in elemental bcc metals and NbTaTiHfZr, focusing on their segregation in screw dislocation cores. We examine two types of core sites and show that the low-energy configuration and associated segregation energy depend on the transition metal group. In NbTaTiHfZr, we find that chemical complexity substantially suppresses interstitial segregation in dislocation cores, as fluctuations in bulk solute energies induce energetically favorable sites that disfavor segregation to core sites. Local chemical order further enhances this effect by promoting solute clustering away from dislocation cores. These findings reveal fundamental differences between the behavior of interstitial atoms in elemental metals and HEAs, with implications for high-temperature plasticity and dynamic strain aging.
Body-centered cubic transition metals↗
Applications of the Method of Space-Time Conservation Element and the Solution Element to Unsteady Chemically Reactive Flows
This document reports the conclusion and findings of our research activities for this grant. The goal of the project is the development and application of the method of Space-Time Conservation Element and Solution Element, or the CE/SE method, to simulate chemically reacting flows. The product of this project will be a high-fidelity, time-accurate flow solver analyzing unsteady flow fields advanced propulsion concepts, including the low-emission turbojet engine combustion and flow fields of the Pulse Detonation Engines (PDE). Based on the documents and computer software of the CE/SE method that we have received from the CE/SE working group at NASA Lewis, we have focused our research effort on addressing outstanding technical issues related to the extension of the CE/SE method for unsteady, chemically reactive flows. In particular, we have made progresses in the following three aspects: (1) Derivation of the governing equations for reacting flows; (2) Numerical treatments of stiff source terms; and (3) Detailed simulations of ZND detonation waves.
Yu, Sheng-Tao↗
Supersonic flow of chemically reacting gas-particle mixtures. Volume 1: A theoretical analysis and development of the numerical solution
A numerical solution for chemically reacting supersonic gas-particle flows in rocket nozzles and exhaust plumes was described. The gas-particle flow solution is fully coupled in that the effects of particle drag and heat transfer between the gas and particle phases are treated. Gas and particles exchange momentum via the drag exerted on the gas by the particles. Energy is exchanged between the phases via heat transfer (convection and/or radiation). Thermochemistry calculations (chemical equilibrium, frozen or chemical kinetics) were shown to be uncoupled from the flow solution and, as such, can be solved separately. The solution to the set of governing equations is obtained by utilizing the method of characteristics. The equations cast in characteristic form are shown to be formally the same for ideal, frozen, chemical equilibrium and chemical non-equilibrium reacting gas mixtures. The particle distribution is represented in the numerical solution by a finite distribution of particle sizes.
Penny, M. M.↗
Accelerating the computation of steady state solutions for non-equilibrium, chemically reacting flow fields
The objective of the study is to develop a technique for accelerating the computation of steady state solutions for nonequilibrium chemically reacting flow fields using the time marching method. To achieve this, a better initial condition is introduced for the time marching scheme to achieve a faster convergence to the steady state solution. This is done by replacing the source terms of the original system of equations, which are responsible for the sitffness, by approximate source terms. It is shown that the saving in computation time increases in direct proportion to the stiffness of the flow model, with a factor of 10 increase in convergence rate observed for the models tested in this study.
Krispin, Jacob↗
Computer program for calculation of complex chemical equilibrium compositions
Computer program is described for numerical solution of chemical equilibria in complex systems by using nonlinear algebraic equations. Free-energy minimization technique is used.
Gordon, S.↗
Potentials of mean force fail to describe chemical bond-breaking in solution
Many liquid phase studies assume that the potential energy surfaces of reacting molecules are the same as in the gas phase, neglecting complex solvent dynamics that can completely alter the nature of chemical reactivity. Even studies that include solvent effects typically only consider them in an average, equilibrium way as part of a potential of mean force (PMF). In this work, we use mixed quantum/classical simulations to compare how equilibrium and non-equilibrium solvent motions affect the photodissociation of a simple diatomic molecule, NaK + , in liquid tetrahydrofuran. A PMF analysis shows that as the excited-state molecule dissociates with the solvent at equilibrium, the bonding electron remains associated with K + at short bond distances but eventually localizes on Na + at the end of dissociation. When we examine non-equilibrium dynamical photodissociation trajectories, however, we find that they fall into three distinct categories: about a quarter of them have the bonding electron mainly associated with Na + , another quarter stay mainly associated with K + , and about half have the bonding electron shared roughly equally between the two ions. The results show that equilibrium PMFs cannot accurately describe the dynamics of bond-breaking chemical reactions in solution because there is insufficient time for the solvent to reach equilibrium on the time scale over which bond dissociation occurs. Furthermore, our analysis shows that the solvent coupling between the electronic energy surfaces is similar at and away from equilibrium, suggesting that other factors, such as solute velocity-driven solvent memory effects, play a more important role in explaining the failure of the equilibrium PMF to predict the non-equilibrium dynamics.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ionomer Optimization for Water Uptake and Swelling in Anion Exchange Membrane Electrolyzer: Hydrogen Evolution Electrode
Green hydrogen produced through anion exchange membrane water electrolysis is a promising, low-cost chemical storage solution for intermittent renewable energy sources. Low-temperature electrolysis using anion exchange membranes (AEM) combines the benefits of established water electrolysis technologies based on alkaline electrolysis and proton exchange membrane electrolysis. The anion conductive ionomers (ACI) used in the AEM electrolyzer (AEMEL) electrodes has been investigated. The ACI serves two primary purposes: (i) facilitate hydroxide conduction between the catalyst and bulk electrolyte and (ii) bind the catalyst to the porous transport layer and membrane. High ion exchange capacity (IEC) ACIs are desired, however, high IEC can cause excessive water uptake (WU) and detrimental ACI swelling. Proper water management is a key factor in obtaining maximum performance in AEM-based devices. In this study, a series of poly(norbornene)-based ACIs were synthesized and deployed in hydrogen evolving AEMEL cathode electrodes. A balance between ionic conductivity, WU and ionomer swelling was achieved in the ACI by varying the IEC and degree of polymer cross-linking. It was found that higher IEC ACIs with light crosslinking are preferred in the HER electrode. Furthermore, such a configuration fine-tuned the WU and ionomer swelling to achieve optimum cell performance and reduce cell operating voltages.
08 HYDROGEN↗
Over 11% Efficient Eco-Friendly Kesterite Solar Cell: Effects of S-Enriched Surface of Cu2ZnSn(S,Se)4 Absorber and Band Gap Controlled (Zn,Sn)O Buffer
For high efficiency kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cell, CdS thin film was usually used as a buffer layer. However, due to the toxicity of Cd and pollution problems involved from the solution-based chemical bath deposition, eco-friendly high efficiency CZTSSe solar cell with Cd-free buffer is necessary. As an Cd-free buffer layer, we investigated (Zn,Sn)O (ZTO) film deposited by sputtering method. In order to achieve high power conversion efficiency, we controlled energy band gaps of CZTSSe absorber as well as ZTO buffer, which was required to optimize conduction band offset (CBO) between the absorber and the buffer and to increase open circuit voltage (Voc) and fill factor (FF). The CBO was optimized by controlling the band gap of ZTO. By varying the Sn/(Zn + Sn) ratio and its deposition temperature, band gap of ZTO was successfully adjusted. Experimental and computational calculation results showed that solar cell performance was strongly affected by the CBO between absorber and buffer. Besides CBO matching, larger band gap of ZTO improved short circuit current density (Jsc) with enhanced external quantum efficiency value in blue photon spectrum range. As an additional way to improve power conversion efficiency of solar cell, band graded CZTSSe absorber was developed by using spray-based two-step process. The sprayed CZTSSe film was engineered to have S-enriched surface, which makes surface band gap widened and surface passivated, and resultantly increases Voc, Jsc and fill factor (FF). By controlling band gaps of both CZTSSe absorber and ZTO buffer, we obtained 11.22% environment-friendly CZTSSe solar cell without MgF2 anti-reflection coating.
(Zn↗
Infrared compatible rapid mixer to probe millisecond chemical kinetics
Fast microfluidic mixers are a valuable tool for studying solution-phase chemical reaction kinetics and molecular processes with spectroscopy. However, microfluidic mixers that are compatible with infrared vibrational spectroscopy have seen only limited development due to the poor infrared transparency of the current microfabrication material. We describe the design, fabrication, and characterization of CaF2-based continuous flow turbulent mixers, which are capable of measuring kinetics in the millisecond time window with infrared spectroscopy, when integrated into an infrared microscope. Kinetics measurements demonstrate the ability to resolve relaxation processes with 1 millisecond time resolution, and straightforward improvements are described that should result in sub-100 µs time-resolution.
Instruments & Instrumentation↗
Hypersonic low-density solutions of the Navier-Stokes equations with chemical nonequilibrium and multicomponent surface slip
Solutions of the Navier-Stokes equations with chemical nonequilibrium and multicomponent surface slip are presented along the stagnation streamline under low-density hypersonic flight conditions. The conditions analyzed are those encountered by the nose region of the Space Shuttle Orbiter during reentry. A detailed comparison of the Navier-Stokes (NS) results is made with the viscous shock-layer (VSL) and Direct Simulation Monte Carlo (DSMC) predictions. With the inclusion of surface-slip boundary conditions in NS calculations, the surface heat transfer and other flow field quantities adjacent to the surface are predicted favorably with the DSMC calculations from 75 km to 115 km in altitude. Therefore, the practical range for the applicability of Navier-Stokes solutions is much wider than previously thought. This is appealing because the continuum (NS and VSL) methods are commonly used to solve the fluid flow problems and are less demanding in terms of computer resource requirements than the noncontinuum (DSMC) methods. The NS solutions agree well with the VSL results for altitudes less than 92 km. An assessment is made of the frozen flow approximation employed in the VSL calculations.
Gupta, R. N.↗
Deciphering the Solvent Effect for the Solvation Structure of Ca 2+ in Polar Molecular Liquids
Although the crystal structures for many inorganic compounds are readily available, researchers are still working hard to understand the relations between the structures and chemical properties of solutions because most of the chemical reactions take place in solutions. A huge amount of effort has been put toward modeling the ion solvation structure from the perspectives of both experiments and theories. In this study, the solvation structures of Ca 2+ ions in aqueous and alcoholic solutions at different concentrations were carefully evaluated by Ca K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses. Further, density functional theory (DFT) calculations were also performed to correlate the results with the experimental data and then further extended to other similar systems. It was found that the number of coordinating solvent molecules decreases with increasing Ca 2+ concentration and increasing solvent molecule sizes. From the EXAFS data, it was observed that the first solvation shell of Ca 2+ splits into two Ca-O distances in a methanol solution and the counter ion Cl - might also be within the first shell at high concentrations. For the first time, the effects of solvents with different polarities and sizes on the ion solvation environment were systematically evaluated.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chemical nonequilibrium Navier-Stokes solutions for hypersonic flow over an ablating graphite nosetip
The general boundary conditions including mass and energy balances of chemically equilibrated or nonequilibrated gas adjacent to ablating surfaces have been derived. A computer procedure based on these conditions was developed and interfaced with the Navier-Stokes solver for predictions of the flow field, surface temperature, and surface ablation rates over re-entry space vehicles with ablating Thermal Protection Systems (TPS). The Navier-Stokes solver with general surface thermochemistry boundary conditions can predict more realistic solutions and provide useful information for the design of TPS. A test case with a proposed hypersonic test vehicle configuration and associated free stream conditions was developed. Solutions with various surface boundary conditions were obtained, and the effect of nonequilibrium gas as well as surface chemistry on surface heating and ablation rate were examined. The solutions of the GASP code with complete ablating surface conditions were compared with those of the ASC code. The direction of future work is also discussed.
Chen, Y. K.↗
Optically tunable mesoscale CdSe morphologies via inorganic phototropic growth
Inorganic phototropic growth using only spatially conformal illumination generated Se–Cd films that exhibited precise light-defined mesoscale morphologies including highly ordered, anisotropic, and periodic ridge and trench nanotextures over entire macroscopic substrates. Growth was accomplished via a light-induced electrochemical method using an optically and chemically isotropic solution, an unpatterned substrate, and unstructured, incoherent, low-intensity illumination in the absence of chemical directing agents or physical templates and masks. The morphologies were defined by the illumination inputs: the nanotexture long axes aligned parallel to the optical E-field vector, and the feature sizes and periods scaled with the wavelength. Optically based modeling of the growth closely reproduced the experimental results, confirming the film morphologies were fully determined by the light–matter interactions during growth. Solution processing of the Se–Cd films resulted in stoichiometric, crystalline CdSe films that also exhibited ordered nanotextures, demonstrating that inorganic phototropic growth can effect tunable, template-free generation of ordered CdSe nanostructures over macroscopic length scales.
36 MATERIALS SCIENCE↗
Zeolite crystal growth in space - What has been learned
Three zeolite crystal growth experiments developed at WPI have been performed in space in last twelve months. One experiment, GAS-1, illustrated that to grow large, crystallographically uniform crystals in space, the precursor solutions should be mixed in microgravity. Another experiment evaluated the optimum mixing protocol for solutions that chemically interact ('gel') on contact. These results were utilized in setting the protocol for mixing nineteen zeolite solutions that were then processed and yielded zeolites A, X and mordenite. All solutions in which the nucleation event was influenced produced larger, more 'uniform' crystals than did identical solutions processed on earth.
Sacco, A., Jr.↗