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At least 37 records · Page 2

Direct Measurement of Cl − Activity in Metal Chloride Molten Salts using a Cl 2 /Cl − Electrode

Molten metal chloride salts are promising candidates for advanced heat transfer fluids in generation IV nuclear reactors and beyond. The activity of the chloride ion in the salt has a large influence on the redox characteristics of the corresponding molten salt. There exists a knowledge gap for the direct measurement of chlorobasicity (Lewis basicity) in molten-salt mixtures. Here, the focus of this work was to develop a Cl 2 /Cl − electrode for the direct measurement of chloride activity in molten metal-chloride salt mixtures. The LiCl–KCl eutectic system was utilized as the reference melt to determine the change in chloride ion activity as increasing concentrations of MgCl 2 are added to the LiCl–KCl eutectic working electrode. The results of the measurements indicated a reduction in chloride ion activity as the concentration of magnesium chloride increased, consistent with the complexation of free chlorides by Lewis acidic magnesium cationic species. The Temkin model was used to estimate the thermodynamic properties of MgCl 4 2− complex.

Chloride↗

Influence of convection on rod spacing of eutectics

This paper describes a three-dimensional numerical model to study the influence of convection on the rod-like microstructure of an eutectic system. This model is based on a central finite difference approach. By applying it, the average concentration near the solid/liquid interface of a growing rod-like eutectic was determined for eutectic compositions C(e) of 0.03, 0.05, and 0.10. Following Jackson and Hunt (1966), the average interfacial composition was converted to a change of undercooling at the interface and, finally, to spacing between the rods. The change in rod spacing with increasing intensity of convection was calculated assuming the eutectic grows at minimum interfacial undercooling. It was confirmed that an increase in convection should coarsen the microstructure (i.e., the rod spacing increases with increasing intensity of stirring).

Caram, R.↗

A Real Time Investigation of Morphological Evolution During Solidification of Different Alloy Systems

Solidification phenomenon which occur at the solid/liquid (s/I) interface play a major role in the determination of structure and hence the technologically important properties of a casting. However, metals being opaque, conclusions related to several important phenomenon such as boundary layer thickness, morphological evolution, and eutectic and cell spacing are deduced from quenching experiments and subsequent post solidification metallographic analysis. Consequently, limited information is obtained about the dynamics of the process. This paper will discuss the recent efforts at the Space Science Laboratory, NASA Marshall Space Flight Center, to view and quantify in-situ and in real time the dynamics of the solidification process and to measure interfacial undercooling. First, a high resolution x-ray transmission microscope (XTM) has been developed to monitor fundamental interfacial phenomena during directional solidification of metals and alloys. The XTM operates in the range of 10-100 KeV and through projection is capable of achieving magnification of up to 16OX. Secondly, an innovative collapsible furnace has been designed to quantify interfacial undercooling by measuring the temperature of a moving s/I interface in reference to a fixed s/l interface. This measurement technique is non-intrusive in nature and is based on the Seebeck principle. In this paper real time results obtained to characterize the dynamics of irregular eutectic spacing will be presented. As an example fiber to lamella or plate transition in the Al-Al2Au eutectic system will be discussed. Further, a resolution limit of 25 micron has permitted viewing in real time morphological instability and cellular growth in Al-Au and Al-Ag systems. Simultaneously, a systematic investigation has been carried out to measure interfacial undercooling for Pb-1 wt.% Sn at and near the marginal stability regime. In conjunction with the XTM observations this study attempts to validate existing relationships between undercooling and growth velocity during plane front growth, marginal stability regime, and stable cellular growth.

Sen, S.↗

Effect of Growth Rate on Elevated Temperature Plastic Flow and Room Temperature Fracture Toughness of Directionally Solidified NiAl-31Cr-3Mo

The eutectic system Ni-33Al-31Cr-3Mo was directionally solidified at rates ranging from 7.6 to 508 mm/h. Samples were examined for microstructure and alloy chemistry, compression tested at 1200 and 1300 K, and subjected to room temperature fracture toughness measurements. Lamellar eutectic grains were formed at 12.7 mm/h; however cellular structures with a radial eutectic pattern developed at faster growth rates. Elevated temperature compression testing between 10(exp -4) to 10(exp -7)/s did not reveal an optimum growth condition, nor did any single growth condition result in a significant fracture toughness advantage. The mechanical behavior, taken together, suggests that Ni-33Al-31Cr-3Mo grown at rates from 25.4 to 254 mm/h will have nominally equivalent properties.

Whittenberger, J. Daniel↗

Coordination and thermophysical properties of select trivalent lanthanides in LiCl–KCl

The coordination chemistry of various fission and decay products, such as actinides and lanthanides, are crucial to the commercial deployment of molten salt reactors as they can affect the thermophysical properties. In this report we examined the structure, coordination environment, and physical properties such as the density and the vibrational density of states for three lanthanide species, namely Ce, Eu, and Sm in the LiCl–KCl eutectic system using a combination of quantum mechanics simulations and spectroscopic experiments. Quantum mechanics molecular dynamics (QM-MD) modelling was employed to determine the physical properties of each system resulting in accurate local coordination of each species. Then, the vibrational density of states (DOS) was determined using a two-phase thermodynamic modelling which was then compared to the experimentally obtained Raman spectra of the species in molten LiCl–KCl having the eutectic composition. We find that Ce 3+ , Eu 3+ and Sm 3+ all adopt octahedral local coordination environments in the eutectic salt composition in good agreement with experimental results. Ce3+ is found to fluctuate between an octahedral six-coordinated and a seven-coordinated structure due to the increased local proximity of Cl in the eutectic salt, resulting in a lower fluidicity/diffusivity than the other trivalent lanthanides studied. The thermophysical properties of the eutectic composition with trivalent lanthanides were not significantly different from the pure eutectic salt composition, but several changes were noted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The solidification of monotectic alloys - Microstructures and phase spacings

The microstructures of directionally grown monotectic alloys in metallic and organic systems fall into two categories those which can form aligned fibrous composite structures with even phase spacings and fiber sections, and those in which the phase distribution is coarser and less regular. This division appears to relate to the form of the phase diagram and has been rationalized by Cahn (1977, 1979) in terms of the relative surface energies between solid and two liquids to give steady state or nonsteady state profiles. The transition in growth behavior occurs when the ratio of the monotectic temperature to that of the upper consolute temperature is approximately 0.9. Differences in phase spacings between a range of monotectic and eutectic systems are discussed in terms of the expected growth interface shapes and the factors which will influence them.

Grugel, R. N.↗

Zero-gravity growth of NaF-NaCl eutectics in the NASA Skylab program

Continuous and discontinuous NaF fibers, embedded in a NaCl matrix, were produced in space and on earth. The production of continuous fibers in a eutectic mixture is attributed to the absence of convection current in the liquid during solidification in space. Image transmission and optical transmittance measurements of transverse sections of the space-grown and earth-grown ingots were made with a light microscope and a spectrometer. It is shown that better optical properties were obtained from samples grown in space. This was attributed to a better alignment of NaF fibers along the ingot axis. A new concept is advanced to explain the phenomenon of transmittance versus far infrared wavelength of the directionally solidified NaCl-NaF eutectic in terms of the two-dimensional Bragg Scattering and the polarization effect of Rayleigh scattering. This concept can be applied to other eutectic systems as long as the index of refraction of the matrix over a range of wavelengths is known. Experimental data are in agreement with the theoretical prediction.

Yue, A. S.↗

Optical properties of NaCl-NaF eutectics

A new concept is advanced to explain the phenomenon of transmittance versus far-field infrared wavelength of the directionally solidified NaCl-NaF eutectic in terms of the two-dimensional Bragg Scattering and the polarization effect of Rayleigh scattering. This concept can be applied to other eutectic systems as long as the index of refraction of the matrix over a range of wavelength is known. Experimental data are in excellent agreement with the theoretical prediction.

Yue, A. S.↗

Composite strengthening

The mechanical behavior of unidirectionally reinforced metals is examined, with particular attention to fabrication techniques for artificial composites and eutectic alloys and to principles of fiber reinforcement. The properties of artificial composites are discussed in terms of strength of fiber composites, strength of ribbon-reinforced composites, crack initiation, crack propagation, and creep behavior. The properties of eutectic composites are examined relative to tensile strength, compressive strength, fracture, high-temperature strength, and fatigue. In the case of artificial composites, parallelism of fibers, good bonding between fibers and matrix, and freedom of fibers from damage are all necessary to ensure superior performance. For many eutectic systems there are stringent boundary conditions relative to melt purity and superheat, atmosphere control, temperature gradient, and growth rate in order to provide near-perfect alignment of the reinforcements with a minimum of growth defects.

Stoloff, N. S.↗

Scientific results from the materials processing in space program

Scientific experiments conducted in a low-gravity environment make it possible to study effects, such as surface tension-driven flows, which are often masked by buoyancy-driven flows. A summary is provided of several early experiments which demonstrate that unwanted convective flows can be effectively suppressed in experiments conducted in orbiting spacecraft. Possible applications of low-G processing are discussed, taking into account Bridgman growth of solid solution alloy-type semiconductors, Bridgman growth of eutectic systems, and float-zone crystal growth. The control of macrosegregation and phase separation in castings is considered, giving attention also to containerless melting and solidification. A description of experiment facilities and opportunities is provided.

Naumann, R.↗

C.A.D. representation of ternary and quaternary phase diagrams

This work is concerned with the utilization of C.A.D. solid-modeling software for the computer representation of three-dimensional phase diagrams. The work was undertaken in two parts. First, the C.A.D. software (I-DEAS, by Structural Dynamics Research Corp.) was integrated with a variety of auxiliary Fortran 77 and I-DEAS language programs which were written specifically for the purpose of phase diagram representation. The capabilities of the resulting suite of software for three-dimensional phase diagram representation were developed and illustrated by the construction, display and manipulation of solid-model phase diagrams for a hypothetical quaternary eutectic system. The results of this work are discussed in some detail in the attached publication ('Solid-modeling: a C.A.D. Alternative for Three-dimensional Phase Diagram Representation'). Such a technique is of general applicability, having utility in both research and education. Secondly, using the C.A.D. technique, data from the literature (gleaned from some 70 separate publications), which represent experimentally determined phase boundaries, were combined to form solid-model representations of the CMS2-M2S-S ternary space diagram and the CMS2-CAS2-M2S-S quaternary liquidus projection (where C=CaO, M=MgO, A=Al2O3, and S=SiO2). These diagrams were utilized in a concurrent study of solidification in the CMAS system.

Delao, James D.↗

Crystallography of Alumina-YAG-Eutectic

Multiple descriptions of the alumina-YAG eutectic crystallography appear in the ceramic literature. The orientation between two phases in a eutectic system has direct impact on residual stress, morphology, microstructural stability, and high temperature mechanical properties. A study to demonstrate that the different crystallographic relationships can be correlated with different growth constraints was undertaken. Fibers produced by Laser-Heated Float Zone (LHFZ) and Edge-defined Film-fed Growth (EFG) were examined. A map of the orientation relationship between Al2O3 and Y3Al5O12 and their relationship to the fiber growth axis as a function of pull rate are presented. Regions in which a single orientation predominates are identified.

Farmer, Serene C.↗

Minimizing Segregation during the Controlled Directional Solidification of Dendric Alloys

Gravity-driven convection induced in the liquid by density gradients of temperature or composition disrupts uniform dendritic growth during controlled directional solidification and promotes severe macrosegregation. The solute-rich region about the dendrite tip appears to play a pivotal role in channel initiation. Allen and Hunt referred to this region as an "initial transient" or dynamic region constituting steep concentration gradients. Experimental investigation also point to the role the tip region plays in developing microstructure. Hellawell and co-workers showed that flow-through dendritic channels could be effectively disrupted, and segregation minimized, during the gradient freezing of bulk castings by rotating the melt through a slight angle with respect to Earth's gravity vector. Adapting this principle to controlled directional solidification, it has been shown" that segregation in dendritic alloys can be minimized, and properties improved, by processing the sample near horizontal in conjunction with a slow axial rotation of the crucible. It is postulated that the observed microstructural uniformity arises by maintaining the developing solute field about the dendrite tip. Solute rejected during vertical directional solidification will rise or sink parallel to the primary dendrite arms during axial rotation setting the stage for accumulation, instabilities, and segregation. In contrast, during horizontal growth, the rejected solute will sink or rise perpendicular to the primary dendrite. Now, in the presence of a slight axial rotation, solute that was initially sinking (or rising) will find itself above (or below) its parent dendrite, i.e., still about the tip region. The following is intended to experimentally demonstrate the viability of this concept in coordination with a model that gives predictive insight regarding solute distribution about growing dendrites. Alloys based on the lead-tin eutectic system were used in this study. The system is well characterized, the constituent metals are available in a very pure form, and the thermophysical properties are well known. During solidification of hypoeutectic alloys, e.g., 55 wt pct Pb, the primary dendrites reject the less dense tin, and for the hypereutectic alloys, e.g., 75 wt pct Sn, the primary dendrites reject denser lead. Alloys were prepared by melting appropriate amounts of lead and tin in a glass crucible after which the homogeneous liquid was sucked directly into 5-mm i.d. glass tubes. The sample tube, containing approximately 30 cm of alloy, was then mechanically driven into the directional solidification furnace assembly and positioned such that approx. 20 cm of the sample was remelted. Subsequently, directional solidification was initiated by withdrawing the sample through a water-cooled jacket at a constant growth velocity of 2 ,microns/s. After 5 to 6 cm of growth, the sample was quickly removed from the furnace and quenched in a water bath to preserve the solid-liquid interface. Samples were directionally solidified vertically upward, nearly horizontally, and some in conjunction with an applied axial rotation of the crucible. Temperature gradients at the solid-liquid interface were measured with an in-siru K-type thermocouple. Solidified samples were cut perpendicular and parallel to the growth direction and conventionally prepared for microscopic examination.

Grugel, Richard N.↗

Phase-Selective Fractionation of Lignocellulosic Biomass Using a Lignin-Based Hydrophobic Deep Eutectic Solvent Biphasic System

Lignocellulose fractionation is a critical step in biomass valorization. Herein, we report a hydrophobic deep eutectic solvent (HDES)-mediated biphasic fractionation strategy that enables the simultaneous and selective separation of cellulose, hemicellulose, and lignin in a single process. Lignin-derived HDESs composed of thymol and 2,6-dimethoxyphenol (syringol) were combined with an acidic aqueous phase to create a water-HDES biphasic system, in which lignin was preferentially extracted into the HDES phase, hemicellulose-derived sugars were selectively solubilized in the aqueous phase, and cellulose was retained in the solid residue. Using wheat straw and poplar wood as representative herbaceous and woody biomass feedstocks, the HDES-acid system exhibited strong synergistic effects, achieving delignification up to 69.8% and xylan removal up to 93.6%. Structural characterization confirmed effective disruption of the lignocellulosic matrix and increased cellulose accessibility, resulting in markedly enhanced enzymatic saccharification, with glucose yields up to 96.2% for wheat straw. This work demonstrates a sustainable and efficient HDES-based biphasic fractionation platform that enables phase-selective separation of major lignocellulosic components and provides a foundation for further development of closed-loop biorefinery processes.

09 BIOMASS FUELS↗

Experimental investigation of flow distribution in enhanced geothermal systems with deep eutectic solvent

Geothermal energy has been recognized as a valuable alternative to fossil fuels and nuclear power, as it is renewable and reliable. Enhanced Geothermal Systems (EGSs) have the potential to expand geothermal energy production by enabling access to previously untapped geothermal resources. Geothermal short-circuiting poses a significant challenge to EGS development, leading to reduced heat extraction. Deep Eutectic Solvent (DES) exhibits favorable thermal and rheological properties, making it a candidate for geothermal applications. Here, this paper examines Choline Chloride-Based Deep Eutectic Solvent (DES) as a working fluid in geothermal applications and its potential to mitigate geothermal short-circuiting. Hydraulic experiments using a dual fracture flow loop were conducted at high temperatures. The results showed that DES exhibited higher differential pressure behavior compared to water. Flow distribution results revealed that DES enhances flow allocation within the small fracture, particularly when a temperature difference exists between fractures. Specifically, DES increased flow distribution by an average of 11% when the temperature difference was 85°C, and by 13% when the difference was 45°C, relative to water. These findings suggest that DES responds to thermal fracture differences, making it a potential remedy to address geothermal short-circuiting.

15 GEOTHERMAL ENERGY↗

NiAl-based Polyphase in situ Composites in the NiAl-Ta-X (X = Cr, Mo, or V) Systems

Polyphase in situ composites were generated by directional solidification of ternary eutectics. This work was performed to discover if a balance of properties could be produced by combining the NiAl-Laves phase and the NiAl-refractory metal phase eutectics. The systems investigated were the Ni-Al-Ta-X (X = Cr, Mo, or V) alloys. Ternary eutectics were found in each of these systems and the eutectic composition, temperature, and morphology were determined. The ternary eutectic systems examined were the NiAl-NiAlTa-(Mo, Ta), NiAl-(Cr, Al) NiTa-Cr, and the NiAl-NiAlTa-V systems. Each eutectic consists of NiAl, a C14 Laves phase, and a refractory metal phase. Directional solidification was performed by containerless processing techniques in a levitation zone refiner to minimize alloy contamination. Room temperature fracture toughness of these materials was determined by a four-point bend test. Preliminary creep behavior was determined by compression tests at elevated temperatures, 1100-l400 K. Of the ternary eutectics, the one in the NiAl-Ta-Cr system was found to be the most promising. The fracture toughness of the NiAl-(Cr, Al)NiTa-Cr eutectic was intermediate between the values of the NiAl-NiAlTa eutectic and the NiAl-Cr eutectic. The creep strength of this ternary eutectic was similar to or greater than that of the NiAl-Cr eutectic.

Johnson, D. R.↗

An Innovative Zero-Liquid Discharge Intermediate-Cold-Liquid Eutectic-Freeze Desalination System

A novel freeze desalination technology is presented for purification of water produced from various industrial processes, including oil and gas extraction. The main innovative idea is introducing a water-immiscible intermediate-cold-liquid (ICL) medium which absorbs the cold from a refrigeration cycle and transfers it to a freezing chamber where it is mixed with brine. The cold ICL enters the freezing chamber at temperatures between -10°C to -30°C. Precooled brine in injected into the freezing chamber and pure water freezes out of the brine upon mixing with the ICL. The rate of freezing inside the chamber is controlled by adjusting the flow rate of the cold ICL relative to the inlet brine. Both eutectic freeze and non-eutectic freezing are possible by controlling the temperature of the freezing chamber. The solid-liquid slurry created in the freezing chamber flows to a filter separation unit after passing through a separation column. The ice crystals are separated from the liquid by a rotary filter device. The collected ice is rinsed by a centrifugal unit. The rinsed ice is melted to produce fresh water. The developed technology resolves the issues common to current freeze-desalination systems while offering superior heat transfer performance ascribed to direct-contact between the cooling medium and the brine in addition to producing solid salt and pure water. The system operates under atmospheric pressure. The low operation temperature minimizes the corrosion issues common in systems exposed to brine. Also, due to the low operating temperature, there are no concerns about evaporation of volatile organics from the produced water during the treatment. The developed technology effectively eliminates the use of chemicals for pretreatment of brine. The system can be constructed from commercially available components. Extensive testing using a lab-scale prototype by using synthetic brine and actual produced water with TDS values from 50,000 ppm to 300,000 ppm showed that freshwater could be achieved with relatively small dependency on the quality of the input brine. The quality of the treated water was found to be mainly a function of the duration of the centrifugal process. Treated water with TDS as low as 200 ppm could be achieved in the tests. Thermo-economic modeling coupled with system level thermochemical process model were developed for prediction of the LCOW. The LCOW was predicted to be $\$$0.50 to $\$$0.90 per barrel of produced water. The potential markets for deployment of the technology are the oil and gas, in-land thermoelectric powerplants, RO desalination plants, and mining industry.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

SPC-70734 Rev 1 MARVEL Primary Coolant System (PCS) Fill and Eutectic NaK Procurement

This specification contains the requirements for the filling the Microreactor Applications Research Validation and Evaluation (MARVEL) reactor Primary Coolant System (PCS) with eutectic sodium-potassium (NaK). The subcontractor will design and fabricate a NaK filling system (referred to herein as the PCS Fill System), the requisite volume of high purity NaK, and perform filling operations in conjunction with the Contractor Operations. The MARVEL reactor system will be operated by the Contractor, and the PCS fill system will be operated by Subcontractor personnel.

21 - SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLAN↗