Influence of Polymer Aggregation and Liquid Immiscibility on Morphology Tuning by Varying Composition in PffBT4T-2DT/Nonfullerene Organic Solar Cells
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99 GENERAL AND MISCELLANEOUS↗
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Reaction path model of the formation of abiotic immiscible hydrocarbon fluids in subducted carbonated serpentinites, Lanzo Massif (Western Italian Alps)
Fluids generated from subducted slabs participate in the cycling of deep carbon in the crust and upper mantle. In these fluids, aqueous carbon species vary in oxidation state between +IV and -IV depending on whether the fluids are oxidizing or reducing, respectively. Most studies of subduction-zone fluids have focused on oxidized carbon species. However, recent studies of natural samples have demonstrated the occurrence of deep, reducing fluids, generated in both subducted oceanic upper mantle and crustal rocks. CH 4 -H 2 -rich fluid inclusions in subducted carbonated serpentinites have demonstrated the existence of abiotic, immiscible, hydrocarbon fluids at upper mantle conditions. To investigate the formation of such immiscible hydrocarbon fluids during the evolution of subducted carbonated serpentinites, we used equilibrium constants from the Deep Earth Water model to carry out predictive chemical mass transfer modeling to simulate the alteration reactions. A novel feature of the models was the inclusion of an immiscible hydrocarbon fluid containing six components (CH 4,f , C 2 H 6,f , C 3 H 8,f , isoC 4 H 10,f , CO 2,f , H 2,f ). This feature enabled prediction of the formation of a separate immiscible fluid in equilibrium with aqueous species and minerals. We developed a predictive reaction path model of invasive H 2,f reacting with carbonated serpentinites and interstitial aqueous fluids for comparison with the natural samples from the Lanzo Massif, western Italian Alps. Over a range of temperatures and pressures, immiscible hydrocarbon fluids formed in association with altered mineral assemblages. Reaction progress caused the transformation of carbonated serpentinites and the formation of clinopyroxene, brucite, graphite, and hydrocarbon fluids, along with changes of pH, logfO 2 , and aqueous species. CH 4,f was the most abundant hydrocarbon species in all the models. The overall results at 2.0 GPa and 400 to 450 °C were consistent with the natural samples from the Lanzo Massif. Interestingly, large amounts of H 2 O formed due to oxidation of H 2 . More hydrocarbons and H 2 O formed in models with lower fluid/rock mass ratios or with more reactant H 2 . Models at different pressure and temperature conditions showed similar results with some variation in the relative stabilities of aragonite, graphite and olivine solid solution, and associated differences in mineral sequences, hydrocarbon fluids, values of aqueous species, and the final log fO 2 and pH. As a result, our models strongly support the laboratory and field evidence that reduction of carbonated serpentinites by infiltrating H 2 fluids can cause the formation of immiscible, abiotic hydrocarbon fluids in subduction zones.
58 GEOSCIENCES↗
Identification of Gravity-Related Effects on Crystal Growth From Melts With an Immiscibility Gap
This work involves an experimental-numerical approach to study the effects of natural and Marangoni convections on solidification of single crystals from a silicate melt with a liquid-liquid immiscibility gap. Industrial use of crystals grown from silicate melts is becoming increasingly important in electronic, optical, and high temperature structural applications. Even the simplest silicate systems like Al203-SiO2 have had, and will continue to have, a significant role in the development of traditional and advanced ceramics. A unique feature of crystals grown from the silicate systems is their outstanding linear electro-optic properties. They also exhibit exceptionally high optical rotativity. As a result, these crystals are attractive materials for dielectric, optical, and microwave applications. Experimental work in our laboratory has indicated that directional solidification of a single crystal mullite appears to be preceded by liquid-liquid phase separation in the melt. Disruption of the immiscible state results in crystallization of a two phase structure. There is also evidence that mixing in the melt caused by density-driven convection can significantly affect the stability of the immiscible liquid layers and result in poly-crystalline growth. On earth, the immiscible state has only been observed for small diameter crystals grown in float zone systems where natural convection is almost negligible. Therefore, it is anticipated that growth of large single crystals from silicate melts would benefit from microgravity conditions because of the reduction of the natural convective mixing. The main objective of this research is to determine the effects of transport processes on the phase separation in the melt during growth of a single crystal while addressing the following issues: (1) When do the immiscible layers form and are they real?; (2) What are the main physical characteristics of the immiscible liquids?; and (3) How mixing by natural or Marangoni convection affects the stability of the phase separated melt.
Kassemi, M.↗
Mass transport in a highly immiscible alloy on extended shear deformation
Forced mixing to a single phase or supersaturated solid solution (SSS) and its prerequisite microstructure evolution in immiscible systems has been a focus of research for both fundamental science and a variety of applications. Controlling the formation of SSS by shear deformation assisted processing could enable a material design beyond conventional equilibrium microstructure in immiscible systems. Here, a highly immiscible (mixing enthalpy of ~ 20 kJ·mol -1 ) Cu-50 at. % Cr binary alloy was employed to investigate the microstructure evolution and localized tendencies of SSS during severe shear deformation. The present results demonstrate distinctive microstructure refinement process in each phase and how they lead to localized SSS as a function of shear strain. Preferential dynamic recrystallization occurs in the softer Cu phase due to strain localization, leading to substantial grain refinement. The refinement of Cr phase in the top-most layer, however, is enabled by the progressive evolution of grain lamination, splitting, and fragmentation as a function of shear strain. The eventual SSS is found to be strongly dependent on the local environments that affect the dislocation activity, including the level of microstructure refinement, the interfacial orientation relationship, hardness difference, and supposed stability of oxidation. Ab initio simulations comfirm that it is more favorable to oxidize Cr than Cu at incoherent Cu/Cr interfaces which then limits the mass transport on an incoherent boundary. Our results shed light on the underpinning mechanism for non-equilibrium mass transport in immiscible systems upon severe deformation that can be applicable to a variety of processing techniques aimed at producing immiscible alloys with superior mechanical properties.
36 MATERIALS SCIENCE↗
Overcoming immiscibility toward bimetallic catalyst library
Bimetallics are emerging as important materials that often exhibit distinct chemical properties from monometallics. However, there is limited access to homogeneously alloyed bimetallics because of the thermodynamic immiscibility of the constituent elements. Overcoming the inherent immiscibility in bimetallic systems would create a bimetallic library with unique properties. Here, we present a nonequilibrium synthesis strategy to address the immiscibility challenge in bimetallics. As a proof of concept, we synthesize a broad range of homogeneously alloyed Cu-based bimetallic nanoparticles regardless of the thermodynamic immiscibility. The nonequilibrated bimetallic nanoparticles are further investigated as electrocatalysts for carbon monoxide reduction at commercially relevant current densities (>100 mA cm -2 ), in which Cu 0.9 Ni 0.1 shows the highest multicarbon product Faradaic efficiency of ~76% with a current density of ~93 mA cm -2 . The ability to overcome thermodynamic immiscibility in multimetallic synthesis offers freedom to design and synthesize new functional nanomaterials with desired chemical compositions and catalytic properties.
25 ENERGY STORAGE↗
Low gravity containerless processing of immiscible gold rhodium alloys
Under normal one-g conditions immiscible alloys segregate extensively during solidification due to sedementation of the more dense of the immiscible liquid phases. However, under low-g conditions it should be possible to form a dispersion of the two immiscible liquids and maintain this dispersed structure during solidification. Immiscible (hypermonotectic) gold-rhodium alloys were processed in the Marshall Space Flight Center 105 meter drop tube in order to investigate the influence of low gravity, containerless solidification on their microstructure. Hypermonotectic alloys composed of 65 atomic % rhodium exhibited a tendency for the gold rich liquid to wet the outer surface of the containerless processed samples. This tendency led to extensive segregation in several cases. However, well dispersed microstructures consisting of 2 to 3 micron diameter rhodium-rich spheres in a gold-rich matrix were produced in 23.4 atomic % rhodium alloys. This is one of the best dispersions obtained in research on immiscible alloy-systems to data.
Andrews, J. Barry↗
Solidification in immiscible systems: The influence of processing conditions on resulting microstructures
Research carried out over the past two decades in which attempts have been made to produce desirable microstructures in immiscible alloys is reviewed. Factors affecting the formation of desirable microstructures in immiscible alloys are addressed and some of the techniques that have been successful in controlling these factors in order to produce useful structures are discussed. Some of the intended applications of these alloys require a dispersion of one phase in the other, while other applications favor the use of aligned, fibrous microstructures with continuity of both phases. The microstructures obtained in immiscible alloys are often strongly influenced by processing conditions. Perhaps the most well known effect is gravity induced sedimentation of the denser immiscible phase during solidification. This difficulty with sedimentation led to low gravity processing in attempts to produce dispersed microstructures. However, experimentation under low gravity conditions soon revealed that many other factors, including wetting of the crucible walls and surface tension driven flows, often resulted in complete separation and coalescence of the two immiscible phases. The production of aligned fibrous microstructures in hypermonotectic alloys appears to be even more difficult than the formation of a dispersion. Here, in addition to sedimentation and crucible wetting, convective and interfacial instabilities must be considered as well. Calculation of the limits of stability during directional solidification were carried out but require experimental verification.
Andrews, J. Barry↗
On the importance of species immiscibility in mixing-layer dynamics at supercritical pressures
The mixing dynamics of injected propellants is a key factor in determining the ignition performance and combustion-instability response of rocket engines, internal combustion engines, and gas turbines. A key source of uncertainty in the prediction of phase-exchange dynamics is the immiscibility of the injected propellants at supercritical pressure conditions, which induces liquid/vapor phase separation and surface-tension dynamics. While experimental observations indicate the presence of liquid/vapor interfacial structures, this interfacial dynamics is typically neglected in numerical analyses. To address this issue, the objective of the present study is to systematically evaluate the importance of species immiscibility on the phase-exchange dynamics of cryogenic LOX/GH2 mixing layers at typical rocket engine injection conditions. This is accomplished by comparing simulations of (i) a recently developed interface-capturing Regularized-Interface Method (RIM) formulation, and (ii) the commonly employed Diffuse-Interface Method (DIM) formulation. Analysis shows that the interfacial dynamics significantly impact the atomization and mixing of the propellants in the near-injector region, which is not captured by the DIM formulation. The findings of this study extend to other immiscible injection systems, such as LOX/kerosene and hydrocarbon-fuel/air, thereby highlighting the importance of resolving species immiscibility in simulating high-pressure combustion engines.
diffused-interface method↗
Plagiogranites as late-stage immiscible liquids in ophiolite and mid-ocean ridge suites - An experimental study
A study of relationships between basic and acidic rocks was made by fractionating primitive basalt at low pressure anhydrous conditions at various fugacities. Fractionally crystallized basalt became increasingly enriched in iron which became silicate liquid immiscible, producing Fe-enriched basaltic and granitic liquids. The latter is similar to plagiogranites found in mid-oceanic rift (MOR) regions, showing that silicate liquid immiscibility could be the petrogenic process which produces plagiogranites in some MOR regions and ophiolites. The major problem in considering plagiogranites as products of silicate liquid immiscibility is absence of any description of the Fe-enriched conjugate liquid in the ophiolite or MOR literature, and the identification of this magma is essential for a definite case of silicate liquid immiscibility.
Dixon, S.↗
Effects of crucible wetting during solidification of immiscible Pb-Zn
Many industrial uses for liquid phase miscibility gap alloys are proposed. However, the commercial production of these alloys into useful ingots with a reasonable amount of homogeneity is arduous because of their immiscibility in the liquid state. In the low-g environment of space gravitational settling forces are abated, thus solidification of an immiscible alloys with a uniform distribution of phases becomes feasible. Elimination of gravitational settling and coalescence processes in low-g also makes possible the study of other separation and coarsening mechanisms. Even with gravitational separation forces reduced, many low-g experiments have resulted in severely segregated structures. The segregation in many cases was due to preferential wetting of the crucible by one of the immiscible liquids. The objective was to analyze the wetting behavior of Pb-Zn alloys on various crucible materials in an effort to identify a crucible in which the fluid flow induced by preferential wetting is minimized. It is proposed that by choosing the crucible for a particular alloy so that the difference in surface energy between the solid and two liqud phases is minimized, the effects of preferential wetting can be diminished and possibly avoided. Qualitative experiments were conducted and have shown the competitive wetting behavior of the immiscible Pb-Zn system and 13 different crucible materials.
Degroh, Henry C., III↗
Effects of crucible wetting during solidification of immiscible Pb-Zn alloys
Many industrial uses for liquid phase miscibility gap alloys are proposed. However, the commercial production of these alloys into useful ingots with a reasonable amount of homogeneity is arduous because of their immiscibility in the liquid state. In the low-g environment of space gravitational settling forces are abated, thus solidification of an immiscible alloy with a uniform distribution of phases becomes feasible. Elimination of gravitational settling and coalescence processes in low-g also makes possible the study of other separation and coarsening mechanisms. Even with gravitational separation forces reduced, many low-g experiments have resulted in severely segregated structures. The segregation in many cases was due to preferential wetting of the crucible by one of the immiscible liquids. The objective was to analyze the wetting behavior of Pb-Zn alloys on various crucible materials in an effort to identify a crucible in which the fluid flow induced by preferential wetting is minimized. It is proposed that by choosing the crucible for a particular alloy so that the difference in surface energy between the solid and two liquid phases is minimized, the effects of preferential wetting can be diminished and possibly avoided. Qualitative experiments were conducted and have shown the competitive wetting behavior of the immiscible Pb-Zn system and 13 different crucible materials.
De Groh, H. C., III↗
The nature and barium partitioning between immiscible melts - A comparison of experimental and natural systems with reference to lunar granite petrogenesis
Elemental partitioning between immiscible melts has been studied using experimental liquid-liquid Kds and those determined by analysis of immiscible glasses in basalt mesostases in order to investigate lunar granite petrogenesis. Experimental data show that Ba is partitioned into the basic immiscible melt, while probe analysis results show that Ba is partitioned into the granitic immiscible melt. It is concluded that lunar granite of significant size can only occur in a plutonic or deep hypabyssal environment.
Neal, C. R.↗
Wetting Characteristics of Immiscibles
Early microgravity experiments with immiscible alloys were usually carried out with the intent of forming dispersed microstructures. By processing under microgravity conditions, the main mechanism leading to gross phase separation could be eliminated. However, analysis of flight samples revealed a separated structure where the minor phase was present along the outer surface, while the major phase was present in the center. The Wetting Characteristics of Immiscibles (WCI) project, which flew aboard the USMP-4 (United States Microgravity Payload) mission in November of 1997, was designed to gain insight into the mechanisms causing segregation of these alloys. This investigation utilized an immiscible transparent organic alloy system and a transparent container in order to facilitate direct observation of the separation process. A range of immiscible alloy compositions was utilized in order to obtain variations in the minor and major phases present and observe the influence on the segregation processes. A small composition range was found where the minor liquid phase perfectly wet the cell gasket. Unexplained observations were made at the extremes of the composition range.
Andrews, J. B.↗
Thermodynamics of Liquid Immiscibility in Iron-Silicate Melt Systems: A Study of Nuclear Fallout Glass
In a ground-interacting nuclear explosion, elements derived from environmental and anthropogenic material, such as iron, silicon, and aluminum, can be incorporated into the fireball. When significant amounts of metals are entrained, the resulting melt may display immiscible textures. The composition of these textures is a record of the temperature of formation and cooling rates (or thermodynamic stability) of the melts and can provide unique constraints on the early cooling conditions of these events. Here, a thermodynamic approach using calculated phase diagrams, the CALPHAD method, is used to predict temperature and composition ranges where stable liquid immiscibility might result in the textures observed in nuclear fallout glass. Sensitivity of the immiscibility to the presence of relative Al, Ca, and Mg content is also explored and compared to fallout samples, and partition coefficients are introduced to understand the preferred distribution of components into each liquid phase.
36 MATERIALS SCIENCE↗
An extension of the localized artificial diffusivity method for immiscible and high density ratio flows
The localized artificial diffusivity (LAD) method is widely regarded as the preferred multi-material regularization scheme for the compact finite difference method, because it is conservative, easy to implement, and generally robust for a wide range of multi-material problems. However, traditional LAD methods face significant challenges when applied to flows with large density ratios and when maintaining thermodynamic equilibrium across material interfaces. These limitations arise from the formulation of the artificial diffusivity flux and the reliance on enthalpy diffusion for interface regularization. Additionally, traditional LAD methods struggle to ensure stability under large density ratio conditions, fail to maintain a finite interface thickness, and are therefore unsuitable for modeling immiscible interfaces. Here, in this work, we discuss the origins of these issues in traditional LAD methods and propose modifications which enable the simulation of large density ratio and immiscible flows. The proposed method targets the artificial diffusion fluxes at gradients and ringing in the volume fraction, rather than the mass fraction in traditional methods, to consistently regularize large density ratio interfaces. Furthermore, the proposed method introduces an artificial bulk density diffusion term to enforce equilibrium conditions across interfaces. To address the challenge of modeling immiscible flows, a conservative diffuse interface term is incorporated into the formulation to ensure a finite interface thickness. Specific consideration is taken in the design of the method to ensure that these crucial properties are maintained for N -material flows. The effectiveness of the proposed method is demonstrated through a series of canonical test cases, and its accuracy is validated by comparison with experimental data on micro-bubble collapse in water. These results highlight the method’s robustness and its ability to overcome the limitations of traditional LAD approaches.
Artificial diffusivity↗
Machine learning guided discovery of ternary compounds involving La and immiscible Co and Pb elements
Abstract Ternary compounds with an immiscible pair of elements are relatively unexplored but promising for novel quantum materials discovery. Exploring what third element and its ratio that can be added to make stable ternary compounds out of an immiscible pair of elements remains a great challenge. In this work, we combine a machine learning (ML) method with ab initio calculations to efficiently search for the energetically favorable ternary La-Co-Pb compounds containing immiscible elements Co and Pb. Three previously reported structures are correctly captured by our approach. Moreover, we predict a ground state La 3 CoPb compound and 57 low-energy La-Co-Pb ternary compounds. Attempts to synthesize La 3 CoPb via multiple techniques produce mixed or multi-phases samples with, at best, ambiguous signals of the predicted lowest-energy La 3 CoPb and the second lowest-energy La 18 Co 28 Pb 3 phases. The calculated results of Gibbs free energy are consistent with experiments, and will provide very useful guidance for further experimental synthesis.
36 MATERIALS SCIENCE↗
The electrical properties of low-g processed immiscible alloys
When dispersed or mixed immiscibles are solidified on earth, a large amount of separation of the constituents takes place due to differences in densities. However, when the immiscibles are dispersed and solidified in zero-gravity, density separation does not occur, and unique composite solids can be formed with many new and promising electrical properties. By measuring the electrical resistivity and superconducting critical temperature of zero-g processed Ga-Bi samples, it has been found that the electrical properties of such materials are entirely different from the basic constituents and the ground control samples. The finest dispersions are obtained only in a low-gravity environment. Our results indicate that space-processed immiscible materials may form an entirely new class of electronic materials. The interesting electrical properties of directionally solidified Al-Cu eutectic, a two-component alloy consisting of Al and Al2Cu which was processed on Skylab (M566) are briefly reviewed. The electrical resistivity of directionally solidified eutectics with a lamellar structure are highly anisotropic and have been studied both experimentally and theoretically. The local resistivity of the space-processed samples are compared to a ground control sample and to the expected theoretical results.
Otto, G. H.↗
The electrical properties of zero-gravity processed immiscibles
When dispersed or mixed immiscibles are solidified on earth, a large amount of separation of the constituents takes place due to differences in densities. However, when the immiscibles are dispersed and solidified in zero-gravity, density separation does not occur, and unique composite solids can be formed with many new and promising electrical properties. By measuring the electrical resistivity and superconducting critical temperature, Tc, of zero-g processed Ga-Bi samples, it has been found that the electrical properties of such materials are entirely different from the basic constituents and the ground control samples. Our results indicate that space processed immiscible materials may form an entirely new class of electronic materials.
Lacy, L. L.↗