Search NASA⌕ Search

SEARCH · Search NASA

Results for “BINARY MIXTURES”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Tuning Stoichiometry to Promote Formation of Binary Colloidal Superlattices

The self-assembly of binary nanoparticle superlattices from colloidal mixtures is a promising method for the fabrication of complex colloidal cocrystal structures. However, binary mixtures often form amorphous or metastable phases instead of the thermodynamically stable phase. Here we show that in binary mixtures of differently sized spherical particles, an excess of the smaller component can promote—and, in some cases, may be necessary for—the self-assembly of a binary cocrystal. Using computer simulations, we identify two mechanisms responsible for this phenomenon. First, excess small particles act like plasticizers and enable systems to reach a greater supersaturation before kinetic arrest occurs. Second, they can disfavor competing structures that may interfere with the growth of the target structure. We find the phase behavior of simulated mixtures of nearly hard spheres closely matches published experimental results. We demonstrate the generality of our findings for mixtures of particles of arbitrary shape by presenting a binary mixture of hard shapes that only self-assembles with an excess of the smaller component.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Heat Capacity Anomaly Near the Lower Critical Consolute Point of Triethylamine-Water

The heat capacity of the binary liquid mixture triethylamine-water has been measured near its lower critical consolute point using a scanning, adiabatic calorimeter. Two data runs are analyzed to provide heat capacity and enthalpy data that are fitted by equations with background terms and a critical term that includes correction to scaling. The critical exponent a was determined to be 0.107 +/- 0.006, consistent with theoretical predictions. When alpha was fixed at 0.11 to determine various amplitudes consistently, our values of A(+) and A(-) agreed with a previous heat capacity measurement, but the value of A(-) was inconsistent with values determined by density or refractive index measurements. While our value for the amplitude ratio A(+)/ A(-) = 0.56 +/- 0.02 was consistent with other recent experimental determinations in binary liquid mixtures, it was slightly larger than either theoretical predictions or recent experimental values in liquid-vapor systems. The correction to scaling amplitude ratio D(+)/D(-) = 0.5 +/- 0.1 was half of that predicted. As a result of several more precise theoretical calculations and experimental determinations, the two-scale-factor universality ratio X, which we found to be 0.019 +/- 0.003, now is consistent among experiments and theories. A new 'universal' amplitude ratio R(sup +/-)(sub Bcr) involving the amplitudes for the specific heat was tested. Our determination of R(sup +/-)(sub Bcr) = -0.5 +/- 0.1 and R(sup -)(sub Bcr) = 1.1 +/- 0.1 is smaller in magnitude than predicted and is the first such determination in a binary fluid mixture.

Flewelling, Anne C.↗
DOE OSTI2020

Mechanochemical Synthesis of High-Purity Anhydrous Binary Alkali and Alkaline Earth Chloride Mixtures

A direct synthesis route for high-purity, anhydrous binary salt mixtures has been developed. This atom efficient, solvent-free process is easily scalable, with the potential to produce salt mixtures that meet the purity standards required for industrial heat transfer and nuclear applications. The essence of the methodology lies in mechanochemical synthesis of carnallite precursors that can mitigate the hydrolysis of MgCl 2 ·6H 2 O under direct heating. Each dehydrated salt carnallite was then analyzed for purity and oxide content through subsequent powder X-ray diffraction, and strong acid titration. In conclusion, this process presents a more effective alternative route compared to previous methods for obtaining low-oxide, high-purity chloride salt mixtures.

Alkali↗
DOE OSTI2021

Comprehensive Assessment of the Accuracy of the Ideal Adsorbed Solution Theory for Predicting Binary Adsorption of Gas Mixtures in Porous Materials

Quantifying the adsorption of chemical mixtures in porous adsorbents is critical to developing these materials for useful separation applications. The ideal adsorbed solution theory (IAST) is the most widely applied mixing theory for predicting mixture adsorption using single-component adsorption data, but a perceived lack of experimental data has limited previous efforts to explore the accuracy of IAST in a systematic way. In this paper, we take advantage of a large collection of binary experimental data for gas adsorption that became available recently to tackle this issue. Specifically, we identify more than 400 examples in which binary adsorption data and single-component data are available in the same publication and apply IAST to all these examples. This analysis includes experimental data from 63 gas mixtures of 37 different molecular species and 174 different adsorbents. In addition to being the most systematic evaluation to date of the accuracy of IAST for gas adsorption, these data will be valuable for future efforts to test or develop mixing theories that improve upon IAST.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thermodynamic modeling of adsorption at the liquid-solid interface

Adsorptive separation techniques are significantly energy efficient in comparison to conventional thermal separation techniques such as distillation. Despite extensive research and development activities undertaken for mixed-gas adsorption, the use of adsorption techniques for the separation of multicomponent liquid mixtures is still limited. A major barrier is the lack of accurate adsorption thermodynamic models, which form the scientific foundation of process simulation of such systems, making the translation to industrial scale challenging. In this work, we have rigorously computed the surface excess of adsorption for six binary liquid mixtures on silica gel at 303 K using the frameworks of the generalized Langmuir isotherm (gL) and the adsorbed solution theory (AST). The six binary liquid mixtures were formed by the pair-wise combinations of four components: benzene, 1,2-dichloroethane, cyclohexane, and n-heptane. We have based our calculations by considering simultaneous equilibria of three phases: saturated vapor phase, bulk liquid phase, and adsorbed phase. Further, the composition of the corresponding saturated vapor phase was estimated by the Nonrandom Two-Liquid activity coefficient model and experimental vapor-liquid equilibria data. The activity coefficients of the adsorbed phase, the central issue of multicomponent adsorption thermodynamics, were calculated using the adsorption Nonrandom Two-Liquid activity coefficient model. Devoid of simplifying assumptions, gL and AST provide rigorous thermodynamic frameworks for adsorption equilibria of multicomponent liquid mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Solvent Processing and Ionic Liquid-Enabled Long-Range Vertical Ordering in Block Copolymer Films with Enhanced Film Stability

Rapid and reliable processing methods for forming ordered block copolymer (BCP) materials with low defect density in a thin film geometry are required for many nanotechnology applications. Vertically aligned BCP structures, in particular, have applications ranging from nanolithography for electronics and photonics to nanoporous membranes for water remediation and novel batteries for flexible electronics. However, the attainment of nearly complete vertical orientational order of the BCP ordered phase remains challenging. Solvent-based techniques, such as direct immersion annealing (DIA) and solvent vapor annealing (SVA), have immense potential for these applications of BCP films, as it allows for tuning of their thermodynamic, structural, and chain mobility driven kinetic properties. We first demonstrate that DIA, using a judicious choice of binary solvent mixtures along with a relatively hydrophobic ionic liquid (IL), induces the rapid vertical ordering in polystyrene-b-polymethylmethacrylate (PS-PMMA) block copolymer in lamellar films. The IL establishes synergy to the binary solvent mixture of toluene and heptane to 1 create a near-neutral solvent environment for attaining the vertical microstructure of the BCP. Next, we show that IL can suppress the de-wetting of the PS-PMMA films to achieve long-range order using SVA in cylindrical films for long annealing times. Both vertical and horizontal morphology is attained in these films by selecting different solvent environments. Furthermore, attaining enhanced vertical and horizontal BCP structure with long-range defect-free order by tuning solvent quality and using additives like IL can render them useful for many nanotech applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Performance enhancement of aqueous ionic liquids with lower critical solution temperature (LCST) behavior through ternary mixtures

Thermally responsive ionic liquids (ILs) exhibit liquid–liquid phase separation when mixed with water and heated above a lower critical solution temperature (LCST), resulting in a water-rich (WR) and an IL-rich (ILR) phase. These binary IL–water mixtures can be employed in a variety of thermodynamic processes such as forward osmosis (FO) desalination, for which two solution properties are desirable: low phase separation temperature and high osmotic strength (osmolality). However, these two properties are interlinked, with ILs that exhibit higher osmotic strengths typically requiring higher phase separation temperatures. This behavior tends to arise from the hydrophilicity of the IL cations, which enhances osmotic strength while also elevating the phase separation temperature. In this work, we highlight a pathway to overcome this tradeoff by developing ternary IL mixtures (two ILs with varying cation hydrophilicity mixed with water), which lowers the phase separation temperature while maintaining and even enhancing the osmotic strength of the solution. We characterize the mixing behavior (osmolality, phase separation temperature, WR phase purity, and WR to ILR phase mass ratio) of four ILs as a function of their concentration in solution. We find that an enhancement of up to 81.6% in the osmolality with a concomitant reduction of up to 15.4% in the phase separation temperature can be achieved using this approach. The ternary mixture is also shown to improve the phase separation kinetics by nearly 95% compared to the binary mixture. Overall, this work highlights a new pathway to improve the performance of LCST ILs for water and energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1967

Kinetic theory of dense-fluid mixtures. IV.

Kinetic prediction theory for viscosity, thermal conductivity and diffusivity of binary liquid mixtures composed of molecules interacting with square-well potential

VISCOUS FLUID↗
NASA NTRS1990

Coarsening in binary solid-liquid mixtures

A theory of Ostwald ripening has been developed for a solid-liquid mixture cosisting of a low volume fraction array of spherical solid particles in a liquid wherein the coarsening process proceeds via the transport of both heat and mass. It is found that the simultaneous transport of heat and mass during ripening does not alter the exponents of the temporal power laws governing the ripening process from their classical values but does alter the amplitudes of these power laws. The growth rate of the cube of the average particle radius, the rate constant, is found to depend both on the alloy solute concentration and the ratio of the thermal to solutal diffusivities. In most metallic systems, a large decrease in the rate constant can be expected with small additions of solute to a pure metal. Possible extensions of this theory to the analogous problem of ripening in isothermal ternary alloys are also discussed.

Voorhees, P. W.↗
DOE OSTI2020

Benchmark Solutions for Radiation Transport in Stochastic Media with Inhomogeneous Material Statistics

Accurately solving implicit Monte Carlo (IMC) thermal photon transport problems with mixed material cells is important in realistic applications. The production IMC package at LLNL treats mixed material cells arising from ALE remap and hydrodynamics using the same approximate model. The new Imp IMC thermal photon transport package currently under development has both a material interface reconstruction (MIR) algorithm and a Levermore-Pomraning (LP) stochastic medium algorithm for treating mixed material cells. Existing stochastic medium algorithms for treating mixed material cells in IMC lack a complete theoretical basis. The IMC LP algorithm implementation has been demonstrated to reproduce published deterministic LP solutions for the particular case of spatially homogeneous material statistics. Realistic simulations will include spatially inhomogeneous material statistics (material mean chord lengths). In a previous investigation, the LP-model for transport in binary stochastic media in rod geometry was generalized to accommodate spatially varying material chord lengths, i.e., the mixing statistics were allowed to be nonhomogeneous. Analytical solutions were obtained and used to produce a verifi cation suite for the Imp IMC Levermore-Pomraning implementation for different spatial variations of the chord lengths. However, the accuracy of the LP model when the mixing statistics are nonhomogeneous has not been assessed and leaves open the question of whether local accuracy is improved or further degraded when chord lengths are not uniform. This shortcoming is rectifi ed here by developing benchmark analytic solutions for transport in binary Markovian stochastic mixtures in rod geometry with nonhomogeneous mixing statistics, using spatially varying chord lengths considered in the previous investigation based on the LP model. Methods for sampling a nonhomogeneous Poisson process (NHPP) are first described and used to construct individual realizations of the binary mixtures in rod geometry. Analytic solutions are then obtained for the forward and backward directed fluxes on a given realization, now viewed as a deterministic medium with alternating layers of the two materials with known interface locations. Finally, material averaged scalar fluxes are obtained using these sampling schemes with spatially linear and quadratic chord lengths and used to assess the accuracy of the previously obtained LP-model results.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2019

Computational screening of metal–organic frameworks for biogas purification

Biogas, which involves methane as the combustible compound, is an abundant and renewable energy resource that produces less harmful gases than conventional fossil-based liquid and solid energy sources. Although biogas is of primary interest due to its methane content, it may also include other gases, such as CO 2 , N 2 , H 2 S, and NH 3 . Studies investigating biogas purification often assume that biogas is a binary 50%/50% mixture of methane and carbon dioxide. However, together with N 2 , the toxic contaminants, H 2 S and NH 3 should be accounted for in the biogas mixture for a more realistic separation application. In this study, the computation-ready experimental metal–organic framework (CoRE-MOF) database is screened to identify a shortlist of potentially high-performing MOFs for multi-component biogas purification. Our hierarchical screening process involves (i) removal of MOFs with sub-3 Å pore limiting diameter and uncommon metal nodes, (ii) removal of MOFs that do not selectively capture the four undesired compounds, as determined from grand canonical Monte Carlo (GCMC) simulations for the binary mixtures of CH 4 /(CO 2 or N 2 or H 2 S or NH 3 ), and (iii) ranking of the remaining structures based on various performance metrics determined from GCMC for a five-component mixture. Finally, the relations between some of these metrics and structural properties are discussed to reveal favorable structural characteristics for biogas upgrading.

42 ENGINEERING↗
NASA NTRS1990

Critical exponent for viscosity

The critical exponent y characterizing the divergence of the viscosity for carbon dioxide and xenon has been measured. The values of y for both fluids fall within the range y = 0.041 + or - 0.001 and are consistent with the range y = 0.042 + or - 0.002 spanned by earlier data for four binary liquid mixtures. This agreement is the strongest evidence that pure fluids and binary liquids are in the same dynamic universality class; however, the results for y are inconsistent with the recent theoretical value of 0.032.

Berg, Robert F.↗
NASA NTRS2008

Gaseous Surrogate Hydrocarbons for a Hifire Scramjet that Mimic Opposed Jet Extinction Limits for Cracked JP Fuels

This paper describes, first, the top-down methodology used to define simple gaseous surrogate hydrocarbon (HC) fuel mixtures for a hypersonic scramjet combustion subtask of the HiFIRE program. It then presents new and updated Opposed Jet Burner (OJB) extinction-limit Flame Strength (FS) data obtained from laminar non-premixed HC vs. air counterflow diffusion flames at 1-atm, which follow from earlier investigations. FS represents a strain-induced extinction limit based on cross-section-average air jet velocity, U(sub air), that sustains combustion of a counter jet of gaseous fuel just before extinction. FS uniquely characterizes a kinetically limited fuel combustion rate. More generally, Applied Stress Rates (ASRs) at extinction (U(sub air) normalized by nozzle or tube diameter, D(sub n or t) can directly be compared with extinction limits determined numerically using either a 1-D or (preferably) a 2-D Navier Stokes simulation with detailed transport and finite rate chemistry. The FS results help to characterize and define three candidate surrogate HC fuel mixtures that exhibit a common FS 70% greater than for vaporized JP-7 fuel. These include a binary fuel mixture of 64% ethylene + 36% methane, which is our primary recommendation. It is intended to mimic the critical flameholding limit of a thermally- or catalytically-cracked JP-7 like fuel in HiFIRE scramjet combustion tests. Our supporting experimental results include: (1) An idealized kinetically-limited ASR reactivity scale, which represents maximum strength non-premixed flames for several gaseous and vaporized liquid HCs; (2) FS characterizations of Colket and Spadaccini s suggested ternary surrogate, of 60% ethylene + 30% methane + 10% n-heptane, which matches the ignition delay of a typical cracked JP fuel; (3) Data showing how our recommended binary surrogate, of 64% ethylene + 36% methane, has an identical FS; (4) Data that characterize an alternate surrogate of 44% ethylene + 56% ethane with identical FS and nearly equal molecular weights; this could be useful when systematically varying the fuel composition. However, the mixture liquefies at much lower pressure, which limits on-board storage of gaseous fuel; (5) Dynamic Flame Weakening results that show how oscillations in OJB input flow (and composition) can weaken (extinguish) surrogate flames up to 200 Hz, but the weakening is 2.5x smaller compared to pure methane; and finally, (6) FS limits at 1-atm that compare with three published 1-D numerical OJB extinction results using four chemical kinetic models. The methane kinetics generally agree closely at 1-atm, whereas, the various ethylene models predict extinction limits that average ~ 45% high, which represents a significant problem for numerical simulation of surrogate-based flameholding in a scramjet cavity. Finally, we continue advocating the FS approach as more direct and fundamental for assessing idealized scramjet flameholding potentials than measurements of "unstrained" premixed laminar burning velocity or blowout in a Perfectly Stirred Reactor.

Pellett, Gerald L.↗
DOE OSTI2020

Machine Learning-Based Upscaling of Finite-Size Molecular Dynamics Diffusion Simulations for Binary Fluids

Molecular diffusion coefficients calculated using molecular dynamics (MD) simulations suffer from finite-size (i.e., finite box size and finite particle number) effects. Results from finite-sized MD simulations can be upscaled to infinite simulation size by applying a correction factor. For self-diffusion of single-component fluids, this correction has been well-studied by many researchers including Yeh and Hummer (YH); for binary fluid mixtures, a modified YH correction was recently proposed for correcting MD-predicted Maxwell–Stephan (MS) diffusion rates. In this study we use both empirical and machine learning methods to identify improvements to the finite-size correction factors for both self-diffusion and MS diffusion of binary Lennard-Jones (LJ) fluid mixtures. Using artificial neural networks (ANNs), the error in the corrected LJ fluid diffusion is reduced by an order of magnitude versus existing YH corrections, and the ANN models perform well for mixtures with large dissimilarities in size and interaction energies where the YH correction proves insufficient.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Soot formation during combustion of unsupported methanol/toluene mixture droplets in microgravity

Results are reported of an experimental study tracing the influence of liquid composition on soot formation and the burning rate of a droplet composed of a binary miscible mixture of liquids. The mixture components represented a highly sooting fuel, toluene, and a nonsooting fuel, methanol. The toluene concentration in methanol was shown to dramatically influence flame luminosity and soot production. Neither burning rates nor a propensity for flame extinction appeared to be significantly affected by toluene mixture fractions. Five-percent toluene mixture droplets behaved like pure methanol droplets in terms of burning rate, lack of flame luminosity, and extinction. Increasing the toluene concentration in the droplets to 25 percent increased flame luminosity, yet no visible soot agglomerates were observed. The 50-percent-mixture droplets burned with highly luminous flames and large amounts of soot agglomerates collecting inside the flame. All the mixture droplets showed burning rates similar to those of pure methanol and likewise exhibited flame extinction before complete droplet vaporization.

Jackson, G. S.↗