Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Miscible”

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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

Combustion of Two-Component Miscible Droplets in Reduced Gravity

This paper presents recent theoretical and experimental results from an ongoing research program that deals with reduced-gravity combustion of bi-component droplets initially in the mm size range or larger. The primary objectives of the research are to study the effects of droplet internal flows, thermal and solutal Marangoni stresses, and species volatility differences on liquid species transport and overall combustion phenomena (e.g., gas-phase unsteadiness, burning rates, sooting, radiation, and extinction). The research program utilizes a reduced-gravity environment so that buoyancy effects are rendered negligible. Use of large droplets also facilitates visualization of droplet internal flows, which is important to this research. This program is a continuation of extensive ground based experimental and theoretical research on bi-component droplet combustion which has been ongoing for several years. The focal point of this research program is a flight experiment (Bi-Component Droplet Combustion Experiment, BCDCE). This flight experiment is still under development. However, supporting ground studies have been performed, and preliminary data have been obtained from flight experiments (Fiber Supported Droplet Combustion Experiment, FSDC-1 and FSDC-2). These flight experiments were performed during the STS-73/USML-2 and STS-94/MSL- I missions. In the experiments, droplets composed of low- and high-volatility species are burned. The low-volatility components are initially present in small amounts. As combustion of a droplet proceeds, the liquid surface mass fraction of the low-volatility component will increase with time, resulting in a sudden and temporary decrease in droplet burning rates as the droplet rapidly heats to temperatures close to the boiling point of the low-volatility component. This decrease in burning rates causes a sudden and temporary contraction of the flame. The decrease in burning rates and the flame contraction can be observed experimentally. Measurements of burning rates as well as the onset time for flame contraction allow effective liquid-phase species diffusivities to be calculated, e.g., using asymptotic theory. A goal of the research is to relate effective liquid species diffusivities to droplet internal flow characteristics. Droplet internal flows will be visualized in future flight and ground-based experiments.

Shaw, B. D.↗
NASA NTRS1999

The Dissolution of an Interfween Miscible Liquids

The disappearance of the surface tension of the interface of a binary mixture, measured using the dynamic surface light scattering technique, is slower for a binary mixture of higher density contrast. A comparison with a naive diffusion model, expected to provide a lower limit for the speed of dissolution in the absence of gravity shows that the interfacial surface tension disappears much slower than even by diffusion with the effect becoming much more pronounced when density contrast between the liquid phases is increased. Thus, the factor most likely to be responsible for this anomalously slow dissolution is gravity. A mechanism could be based on the competition between diffusive relaxation and sedimentation at the dissolving interface.

Vlad, D.H.↗
NASA NTRS2004

The formation of spikes in the displacement of miscible fluids

We report on experiments in which a more viscous fluid displaces a less viscous one in a vertical cylindrical tube. These experiments were performed using silicone oils in a vertical pipette of small diameter. The more viscous fluid also had a slightly larger density than the less viscous fluid. In the initial configuration, the fluids were at rest, and the interface was nominally flat. A dye was added to the more viscous fluid for ease of observation of the interface between the fluids. The flow was initiated by pumping the more viscous fluid into the less viscous one. The displacement velocity was such that the Reynolds number was smaller than unity and the Peclet number for mass transfer between the fluids was large compared to unity. For upward displacement of the more viscous fluid from an initially stable configuration, an axisymmetric finger was observed under all conditions. However, a needle-shaped spike was seen to propagate from the main finger in many cases, similar to that observed by Petitjeans and Maxworthy for the displacement of a more viscous fluid by a less viscous one.

Rheology/methods↗
DOE OSTI2022

Kinetic processes of phase separation and aggregation behaviors in slot-die processed high efficiency Y6-based organic solar cells

Morphological optimization has proved to be one crucial factor contributing to the 19% efficiency of Y6-based organic solar cells (OSCs). Although the relationship between component miscibility and film morphology has been established, it has not been clarified how the film formation processes proceed, especially for methods compatible with large-area fabrication, i.e. slot-die coating, which restricts the further optimization of the morphology. Herein, we comprehensively investigate the effect of miscibility and the film-formation kinetic process on film morphology during processing with different solvents. A highest power conversion efficiency (PCE) of 17.38% can be obtained in a D18:Y6 device processed with slot-die coating in an open-air environment. However, due to their relatively poor miscibility, incorporating a trace amount of chlorobenzene (CB) into CF can sufficiently promote Y6 aggregation, leading to increased phase separation and thus the average PCE drops to 15.16%. In contrast, a PM6:Y6 blend shows insensitive changes in the kinetic process as well as the final morphology, and thus in the comparable PCEs when cast with different solvents, which is ascribed to their relatively good miscibility. As a result, this work provides scientific guidelines for device optimization by combining the intermediate gap from miscibility to kinetic process and their impact on final morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Thermodynamic Properties and Molecular Packing Explain Performance and Processing Procedures of Three D18:NFA Organic Solar Cells

Abstract Organic solar cells (OSCs) based on D18:Y6 have recently exhibited a record power conversion efficiency of over 18%. The initial work is extended and the device performance of D18‐based OSCs is compared with three non‐fullerene acceptors, Y6, IT‐4F, and IEICO‐4Cl, and their molecular packing characteristics and miscibility are studied. The D18 polymer shows unusually strong chain extension and excellent backbone ordering in all films, which likely contributes to the excellent hole‐transporting properties. Thermodynamic characterization indicates a room‐temperature miscibility for D18:Y6 and D18:IT‐4F near the percolation threshold. This corresponds to an ideal quench depth and explains the use of solvent vapor annealing rather than thermal annealing. In contrast, D18:IEICO‐4Cl is a low‐miscibility system with a deep quench depth during casting and poor morphology control and low performance. A failure of ternary blends with PC 71 BM is likely due to the near‐ideal miscibility of Y6 to begin with and indicates that strategies for developing successful ternary or quaternary solar cells are likely very different for D18 than for other high‐performing donors. This work reveals several unique property–performance relations of D18‐based photovoltaic devices and helps guide design or fabrication of yet higher efficiency OSCs.

Wang, Zhen↗
DOE OSTI2024

New insights on the effects of chemistry and temperature on α’ precipitation during aging of FeCrAl alloys

Here, the effect of Al on α' precipitation in FeCrAl alloys was studied through thermal aging of several model binary FeCr and FeCrAl alloys with Cr content of 13 wt.%, 17 wt.%, and 25 wt.% with and without 5.5 wt.% Al. Aging was performed up to 1,000h at varying temperatures from 400-500°C. At 400°C no age hardening was observed due to slow kinetics at this temperature. For both the 17Cr and 25Cr alloys, the addition of Al shows a lowering of the miscibility gap, consistent with other reports in literature. Interestingly, however, for the 25Cr alloys the addition of Al in the FeCrAl ternary alloy accelerated α' precipitation below the miscibility gap. Such enhanced precipitation has also been predicted by our atomistic kinetic Monte Carlo (AKMC) simulations. While previous literature has often focused on Al suppressing α', here we show that while Al can lower the miscibility gap in the Fe-Cr ferritic system thermodynamically, it may also enhance the kinetics of precipitation.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Influence of grain size on α' Cr precipitation in an isothermally aged Fe-21Cr-5Al alloy

Cr-rich α' precipitation during aging typically leads to hardening and accordingly embrittlement of FeCrAl alloys, which needs to be suppressed. The influence of grain size on α' precipitation was studied by aging coarse-grained (CG), ultra-fine grained (UFG), and nanocrystalline (NC) ferritic Kanthal-D [KD; Fe-21Cr-5Al (wt.%) alloy] at 450, 500 and 550 °C for 500 h. After aging at 450 and 500 °C, less hardening was observed in the UFG KD than in CG KD. Atom probe tomography indicated a lower number density and larger sized intragranular α' in the UFG versus the CG alloy. The smaller grain size and higher defect (vacancy and dislocation) density in the UFG KD facilitated diffusion and accordingly enhanced precipitation kinetics, leading to coarsening of precipitates, as well as saturation of precipitation at lower temperatures, as compared to those in CG KD. No hardening occurred in UFG and CG KD after aging at 550 °C, indicating that the miscibility gap is between 500 and 550 °C. NC KD exhibited softening after aging owing to grain growth. α' precipitation occurred in NC KD aged at 450 °C but not at 500 °C, indicating that miscibility gap is between 450 and 500 °C. Thus, the significantly smaller grain size in NC KD decreased the miscibility gap, as compared to that in CG and UFG KD. Finally, this is attributed to the absorption of vacancies by migrating grain boundaries during aging, suppressing α' nucleation and enhancing Cr solubility.

36 MATERIALS SCIENCE↗
NASA NTRS1975

Investigation of immiscible systems and potential applications

The droplet coalescence kinetics at 0 g and 1 g were considered for two systems which contained liquid droplets in a host liquid. One of these (Al-In) typified a system containing a liquid phase miscibility gap and the order (oil-water) a mixture of two essentially insoluble liquids. A number of coalescence mechanisms potentially prominent at low g in this system were analyzed and explanations are presented for the observed unusual stability of the emulsion. Ground base experiments were conducted on the coalescence of In droplets in and Al-In alloy during cooling through the miscibility gap at different cooling rates. These were in qualitative agreement with the computer simulation. Potential applications for systems with liquid phase miscibility gaps were explored. Possibilities included superconductors, electrical contact materials, superplastic materials, catalysts, magnetic materials, and others. The role of space processing in their production was also analyzed.

Markworth, A. J.↗
NASA NTRS1980

Observations of homogeneous phase separation in liquid He3-He4 mixtures

The so-called miscibility gap that exists below the critical point in liquid He-3 - H-4 mixtures makes it possible to study binary phase composition, and the ensuing dispersions, in a system possessing an additional order parameter in one of the components. The physical behavior of a superfluid dispersion produced by pressure quenching an He-3 - He-4 mixture into the miscibility gap is described. The description applies both to quenches of homogeneous and phase-separated initial states in various regions of the miscibility gap.

Hoffer, J. K.↗
NASA NTRS1988

Structural properties of bismuth-bearing semiconductor alloys

The structural properties of bismuth-bearing III-V semiconductor alloys InPBi, InAsBi, and InSbBi were studied theoretically. Bond energies, bond lengths, and strain coefficients were calculated for pure AlBi, GaBi, and InBi compounds and their alloys, and predictions were made for the mixing enthalpies, miscibility gaps, and critical metastable-to-stable material transition temperatures. Miscibility calculations indicate that InSbBi will be the most miscible, and the InPBi will be the the most difficult to mix. However, calculations of the hardness of the Bi compounds indicate that, once formed, the InPBi alloy will be harder than the other Bi alloys and substantially harder than the currently favored narrow-gap semiconductor HgCdTe.

Berding, M. A.↗
NASA NTRS1999

Containerless, Low-Gravity Undercooling of Ti-Ce Alloys in the MSFC Drop Tube

Previous tests of the classical nucleation theory as applied to liquid-liquid gap miscibility systems found a discrepancy between experiment and theory in the ability to undercool one of the liquids before the L1-L2 separation occurs. To model the initial separation process in a two-phase liquid mixture, different theoretical approaches, such as free-energy gradient and density gradient theories, have been put forth. If there is a large enough interaction between the critical liquid and the crucible, both models predict a wetting temperature (T(sub w)) above which the minority liquid perfectly wets and layers the crucible interface, but only on one side of the immiscibility dome. Materials with compositions on the other side of the dome will have simple surface adsorption by the minority liquid before bulk separation occurs when the coexistence (i.e., binoidal) line in reached. If the interaction between the critical liquid and the crucible were to decrease, T(sub w) would increase, eventually approaching the critical consolute temperature (T(sub cc)). If this situation occurs, then there could be large regions of the miscibility gap where non-perfect wetting conditions prevail resulting in droplets of L1 liquid at the surface having a non-zero contact angle. The resulting bulk structure will then depend on what happens on the surface and the subsequent processing conditions. In the past several decades, many experiments in space have been performed on liquid metal binary immiscible systems for the purpose of determining the effects that different crucibles may have on the wetting and separation process of the liquids. Potard performed experiments that showed different crucible materials could cause the majority phase to preferentially wet the container and thus produce a dispersed microstructure of the minority phase. Several other studies have been performed on immiscibles in a semi-container environment using an emulsion technique. Only one previous study was performed using completely containerless processing of immiscible metals and the results of that investigation are similar to some of the emulsion studies. In all the studies, surface wetting was attributed as the cause for the similar microstructures or the asymmetry in the ability to undercool the liquid below the binoidal on one side of the immiscibility dome. By removing the container completely from the separation process, it was proposed that the loss of the crucible/liquid interaction would produce a large shift in T(sub w) and thus change the wetting characteristics at the surface. By investigating various compositions across the miscibility gap, a change in the type and amount of liquid wetting at the surface of a containerless droplet should change the surface nucleating behavior of the droplet - whether it be the liquid-liquid wetting or the liquid-to-solid transition. Undercooling of the liquid into the metastable region should produce significant differences in the separation process and the microstructure upon solidification. In this study, we attempt to measure these transitions by monitoring the temperature of the sample by optical pyrometry. Microstructural analysis will be made to correlate with the degree of undercooling and the separation mechanisms involved.

Robinson, M. B.↗
NASA NTRS1998

A Study of Undercooling Behavior Of Immiscible Metal Alloys in the Absence of Crucible-Induced Nucleation

The purpose of this study is to investigate the question: Would eliminating the crucible eliminate the wall-induced nucleation of one of the liquid phases in an immiscible alloy and result in undercooling of the liquid into the metastable region thereby producing significant differences in the separation process and the microstructure upon solidification. Another primary objective of this research is to study systems with a metastable miscibility gap and to directly determine the metastable liquid miscibility gap by undercooling experiments. Nucleation and growth of droplets in these undercooled metallic liquid-liquid mixtures is also being studied. Results of this investigation indicate that containerless processing of immiscibles may not promote the undercooling of the single-phase liquid into the metastable region. Although no recalescence event was observed for this liquid-liquid transition, undercooling did occur across the miscibility gap for the solidification of the Ti phase that eventually separated.

Robinson, Michael B.↗
DOE OSTI2022

Binary Blend All‐Polymer Solar Cells with a Record Efficiency of 17.41% Enabled by Programmed Fluorination Both on Donor and Acceptor Blocks

Abstract Despite remarkable breakthrough made by virtue of “polymerized small‐molecule acceptor (PSMA)” strategy recently, the limited selection pool of high‐performance polymer acceptors and long‐standing challenge in morphology control impede their further developments. Herein, three PSMAs of PYDT‐2F, PYDT‐3F, and PYDT‐4F are developed by introducing different fluorine atoms on the end groups and/or bithiophene spacers to fine‐tune their optoelectronic properties for high‐performance PSMAs. The PSMAs exhibit narrow bandgap and energy levels that match well with PM6 donor. The fluorination promotes the crystallization of the polymer chain for enhanced electron mobility, which is further improved by following n ‐doping with benzyl viologen additive. Moreover, the miscibility is also improved by introducing more fluorine atoms, which promotes the intermixing with PM6 donor. Among them, PYDT‐3F exhibits well‐balanced high crystallinity and miscibility with PM6 donor; thus, the layer‐by‐layer processed PM6/PYDT‐3F film obtains an optimal nanofibril morphology with submicron length and ≈23 nm width of fibrils, facilitating the charge separation and transport. The resulting PM6/PYDT‐3F devices realizes a record high power conversion efficiency (PCE) of 17.41% and fill factor of 77.01%, higher than the PM6/PYDT‐2F (PCE = 16.25%) and PM6/PYDT‐4F (PCE = 16.77%) devices.

Zhou, Dehong↗
DOE OSTI2024

Quasi-elastic neutron scattering study on dynamically asymmetric polymer blends

Compatibility between polymers with different glass transition temperatures controls the thermomechanical properties of blends. This work explores the segmental dynamics of poly(methyl acrylate) (PMA) chains when they are blended with polymers of different rigidities and miscibility. Inspired by the intriguing dynamic asymmetry of chains within the interfacial layer of nanoparticles, this study aims to understand dynamic heterogeneity in dynamically asymmetric blends of PMA/poly(methyl methacrylate) (PMMA), PMA/polystyrene (PS), and PMA/poly(ethylene oxide) (PEO) using the differential scanning calorimetry (DSC) and quasi-elastic neutron scattering (QENS) measurements below and above the glass transition temperature of PMMA or PS. Further, results revealed that the segmental jump distance of PMA increased on blending due to volume enhancement. The reduced effective diffusivity of PMA in PMMA is attributed to PMMA's enhanced flexibility (lower characteristic ratio, C ∞ ) and superior interaction (lower ) when compared with the PS environment. The results demonstrate that the chain rigidity and miscibility affect the free volume, interchain cooperativity, and segmental dynamics in dynamically asymmetric blends.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Nanofilm Composite Membranes of Bottlebrush Poly(1,3‐Dioxolane) Plasticized by Poly(Ethylene Glycol) for CO 2 /N 2 Separation

Abstract Poly(1,3‐dioxolane) has emerged as a leading membrane material for post‐combustion CO 2 capture due to its high ether oxygen content and strong affinity toward CO 2 . However, they are often cross‐linked to inhibit crystallization, which makes them impossible to fabricate into industrial thin‐film composite membranes. Herein, soluble and high molecular weight bottlebrush polymers ( b PDXLA) are synthesized using reversible addition‐fragmentation chain transfer polymerization and demonstrate the feasibility of fabricating nanofilm (≈100 nm) composite membranes (NCMs). Furthermore, b PDXLA can be plasticized using a miscible additive of poly(ethylene glycol) dimethyl ether (PEGDME) to improve CO 2 permeability while retaining good CO 2 /N 2 selectivity. For example, adding 20 mass% PEGDME improves CO 2 permeance from 930 to 1300 GPU and decreases CO 2 /N 2 selectivity from 74 to 53 at 25 °C; the membrane exhibits stable separation performance competitive with state‐of‐the‐art commercial membranes. This work unveils a practical approach to designing uncross‐linked, highly polar polymers for practical membrane gas separation and highlights a facile way to enhance performance by incorporating miscible plasticizers using industrial manufacturing processes.

Zhang, Gengyi [Department of Chemical and Biologic↗
DOE OSTI2022

Highly Efficient Layer-by-Layer Processed Quaternary Organic Solar Cells with Improved Charge Transport and Reduced Energy Loss

We report how to improve charge transport properties and reduce energy losses are the two main challenges of organic solar cells (OSCs). Herein, a new device fabrication strategy that combines the layer-by-layer (LBL) method and a quaternary active layer is demonstrated to realize highly efficient photovoltaic performance of the OSCs based on PM6:PM7/Y6:O1-2F. The introduction of the second donor, PM7,forms a cascade energy-level alignment with PM6 that facilitates effective charge transfer. The second acceptor, O1-2F, which is poorly miscible with the donors, helps to reduce the miscibility between the donors and acceptors, and thus delivers a more desirable vertical phase separation of the active layer. Furthermore, the alloy acceptor of O1-2F and Y6 can optimize the horizontal and vertical morphology of the active layer, forming an effective charge separation and continuous charge transport channel. As a result, the PM6:PM7/Y6:O1-2F system shows a distinct increase in charge mobility and a reduced nonradiative lossΔVnrof 0.231 V compared to the PM6/Y6 system, achieving a high-power conversion efficiency of18.23%. The results indicate that the quaternary LBL OSCs are promising for future large-scale and industrial manufacture of the OSCs.

14 SOLAR ENERGY↗
DOE OSTI2024

Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

Blending block copolymers (BCP) with additives is a useful approach for controlling BCP morphology and properties. In athermal systems, blends of BCPs with polymer additives having very high molecular (M n ) mass generally result in macrophase separation. Bottlebrush polymers, which consist of a linear backbone and grafted side chains, present an interesting alternative where the overall M n of the system can be very large but the low M n side chains may drive miscibility with the BCP. Here, in this study, a bottlebrush with a polynorbornene backbone and polystyrene (PS) side chains is blended with PS-b-poly(methyl methacrylate) (PS-b-PMMA) of varying M n , and the resulting morphologies are examined in both the bulk and thin films. Two different M n of PS-b-PMMA were used in the bulk study, and the analysis of small-angle X-ray scattering data shows that the blends were miscible and lamellar at all concentrations. This deviates from reference series of both low and high M n linear polymer additives, which either showed morphological transitions from lamellae to cylinders (low M n ) or were immiscible at all mass fractions studied (high M n ). The relative molecular mass of the side chain (N SC ) and the corresponding component in the BCP (N A ) dictate the distribution of the bottlebrush throughout the BCP, analogous to BCP/linear blends or grafted nanoparticles in a homopolymer matrix. The studies on thin films show a thickness dependence for bottlebrush mass fractions at or above 0.17, a behavior which may be driven by conformational changes of the bottlebrush upon confinement.

36 MATERIALS SCIENCE↗