Rutile solubility in NaF–NaCl–KCl-bearing aqueous fluids at 0.5–2.79GPa and 250–650°C
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The novel repetitive pulsed electric drill 250 (RePED 250) has the potential to greatly lower the costs and drilling times of geothermal projects. This tool discharges electric pulses through hard rock formations, shattering the rock in tension and allowing it to be quickly removed. One hurdle in bringing this technology to market is the RePED 250 downhole alternator. This component is essential for supplying power to the electronic drilling tool. There are currently no downhole tools on the market that meet the RePED 250 alternator's high temperature and power requirements. This report focuses on the path to commercialization for this novel alternator technology being developed as part of the RePED 250 project. One aim of this work is to identify the geothermal market size for the RePED 250 alternator, as well as other potential markets for this technology outside of geothermal. The geothermal market is very small, with only approximately 13 wells drilled in the United States each year. The worldwide market is several times this size and growing each year. The ability of the RePED 250 technology to drastically reduce the cost of geothermal projects may also lead to an increase in this market size. Technology developed for the high-temperature, high-power RePED 250 alternator can also be used to create high-temperature and high-power motors. These motors and alternators will have potential applications in oil and gas drilling, a $300 billion dollar industry in the United States alone, as well as in more distant industries such as aircraft, weapon systems, space exploration, and electric vehicles. Other aspects of the RePED 250 alternator's path to commercialization are also analyzed, including the supply chain for production materials and potential manufacturing methods. The supply chain and manufacturing practices for low-temperature motors and alternators are well established and require relatively minor changes for the high-temperature and high-power RePED 250 alternator. Sourcing for high-temperature materials has been identified, as well as potential supply chain risks. These most notably include electrical steel and high-temperature samarium cobalt (SmCo) magnets. Overall, these risks are not expected to be significant at the likely manufacturing scale required for the RePED 250.
The rare earth elements (REE) have important applications in green energy technologies. The formation of mineral deposits in geologic systems commonly involves hydrothermal fluids which can mobilize the REE. However, the REE speciation is not well known as a function of pH. The thermodynamic properties of REE hydroxyl complexes used in geochemical models are based on the Helgeson-Kirkham-Flowers (HKF) equation of state parameters which were derived by extrapolation of low temperature experimental and estimated data. In this study, Dy hydroxide solubility experiments are combined with available literature data to improve these models from 25 to 250 °C and optimize the thermodynamic properties of Dy 3+ and Dy hydroxyl complexes using GEMSFITS. Batch-type solubility experiments were conducted from 150 to 250 °C and at saturated water vapor pressure in perchloric acid solutions with initial pH values of 2 to 5 in 0.5 pH unit increments. The measured solubility of Dy hydroxide is retrograde with temperature and decreases with pH. The logarithm of total dissolved Dy molality ranges from –2.3 to –5.3 at 150 °C (pH 4.7–5.5), from –2.4 to –5.6 at 200 °C (pH 3.9–5.1), and from –3.7 to –6.9 at 250 °C (pH of 3.4 and 5.0). The optimized standard partial molal Gibbs energies of formation (Δ f G° T ) derived for Dy 3+ and DyOH 2+ display a close to linear relationship with temperature, fitting with previous optimizations based on DyPO 4 solubility data in the literature. A comparison of the optimized ΔfG°T values for aqueous Dy species with predictions from available HKF parameters indicates significant differences ranging from +11 to –26 kJ/mol between 25 and 250 °C. The experimental fits are used to derive the Dy hydroxide solubility products (K s0 ) and formation constants for the hydrolysis of Dy (β n with n = 1 to 3; Dy 3+ + nOH – = DyOH n 3-n ) as a function of temperature. The optimization method presented yields accurate thermodynamic properties for the Dy 3+ aqua ions and the DyOH 2+ species at the acidic to mildly acidic pH studied whereas more experimental work is needed at near-neutral and alkaline conditions to better constrain the other hydroxyl complexes. Furthermore, the optimized thermodynamic data have a significant impact on geochemical modeling of the mobility and solubility of REE minerals in acidic hydrothermal fluids.
The mobility of rare earth elements (REE) in natural hydrothermal systems can be assessed using geochemical modeling, which requires reliable thermodynamic data of relevant aqueous species. In this study, we evaluate the controls of pH and temperature on La speciation and the role of hydroxyl complexes in REE transport at hydrothermal conditions. Batch-type hydrothermal solubility experiments were conducted using synthetic La hydroxide powders equilibrated in perchloric acid-based aqueous solutions at temperatures between 150 and 250 °C and starting pH of 2 to 5. The La hydroxide solubility is retrograde with temperature and displays a strong pH dependence with a decrease in La concentrations from acidic to mildly acidic pH spanning between 3 and 5 orders of magnitude (e.g. log La molality of –2.5 to –7.2 at 250 °C). Thermodynamic optimizations using GEMSFITS allow to retrieve the standard partial molal Gibbs energies for the La 3+ aqua ion and the formation constants for the La hydroxyl species (i.e., LaOH 2+ , La(OH) 2 + , La(OH) 3 0 ) between 25 and 250 °C. A comparison between the experimentally derived thermodynamic properties with the calculated values from the Helgeson-Kirkham-Flowers equation of state parameters indicates an increased divergence with temperature. Discrepancies in standard partial molal Gibbs energies range between ~ 1 – 12 kJ/mol and result in a predicted La hydroxide solubility differing by up to 3 orders of magnitude at 250 °C. Speciation calculations indicate a higher stability of La 3+ and LaOH 2+ over the other La hydroxyl species in the studied pH range of 3.4 to 6. Here, the optimized thermodynamic properties for La aqueous species have important implications for modeling the solubility of REE minerals such as monazite and the mobility of REE in hydrothermal systems.
Maraging steels are known for their exceptional strength but suffer from limited work hardening and ductility. Here, in this study, we report an intermittent printing strategy to tailor the microstructure and mechanical properties of maraging 250 steel via tuning the thermal history during wire-arc directed energy deposition. By introducing a dwell time between adjacent layers, the maraging 250 steel is cooled below the martensite start temperature, triggering thermally-driven martensitic transformation during the printing process. Thermal cycling during subsequent layer deposition results in the formation of reverted austenite which shows a refined microstructure and induces elemental segregation between martensite and reverted austenite. The Ni enrichment in the austenite promotes stabilization of the reverted austenite upon cooling to room temperature. The reverted austenite is metastable during deformation, leading to strain-induced martensitic transformation under loading. Specifically, a 3 min interlayer dwell time produces a maraging 250 steel with approximately 8% reverted austenite, resulting in improved work hardening via martensitic transformation induced plasticity during deformation. Meanwhile, the higher cooling rate and refined prior austenite grains lead to substantially refined martensitic grains (by approximately fivefold) together with an increased dislocation density. With 3 min interlayer dwell time, the yield strength of the printed maraging 250 steel increases from 836 MPa to 990 MPa, and the uniform elongation is doubled from 3.2% to 6.5%. This intermittent deposition strategy demonstrates the potential to tune the microstructure of maraging steels for achieving strength-ductility synergy by engineering the thermal history during additive manufacturing.
Purpose: To develop an external beam surrogate of the Yb-169 brachytherapy source applying a filter-based spectrum modulation technique to 250 kVp x-rays. In-vitro/vivo studies performed with the modulated 250 kVp beam will help gauge the benefits of implementing gold nanoparticle-aided radiotherapy with the Yb-169 source. Methods: A previously validated MCNP5 model of the Phillips RT-250 orthovoltage unit was used to obtain the percentage depth dose (PDD) and filtered photon spectra for a variety of filtration and irradiation conditions. Photon spectra were obtained using the average flux F4 tally in air right after all collimation. A 30 x 30 x 30 cm{sup 3} water phantom was used to compute the PDD along the central axis (CAX) under the standards conditions of a 10 x 10 cm{sup 2} field size at 50 cm SSD. Cylindrical cells of 4 cm in diameter and the energy deposition F6 tally were used along the CAX to score the doses down to 20 cm depth. The number of particle history was set to 2 x 10{sup 8} in order to keep the relative uncertainty within each cell < 0.3%. The secondary electron spectrum within a gold-loaded tissue due to each photon spectrum was also calculated using EGSnrc and compared with that due to Yb-169 gamma rays. Results: Under the practical constraints for the spectrum modulation task, 250 kVp x-rays filtered by a 0.25 mm Erbium (Er) foil produced the best match with Yb-169 gamma rays, in terms of PDD and, more importantly, secondary electron spectrum. Conclusion: Modulation of 250kVp x-ray spectrum by an Er-filter was found effective in emulating the gamma ray spectrum of Yb-169. Possible benefits as predicted from the current MC model such as enhanced radiosensitization with the Er-filtered beam (as a surrogate of Yb-169) was confirmed with a separate in-vitro study. Supported by DOD/PCRP grant W81XWH-12-1-0198.
Results are presented for measurements of the IR spectral reflectance at near-normal incidence of aqueous solutions of sulfuric acid with acid concentrations of 75% and 95.6% by weight. Kramers-Kronig analyses of the reflectance data are employed to obtain values of the optical constants n(nu) and k(nu) in the spectral range from 400 to 6000 cm to the -1 power. The optical constants of these solutions at 250 K and 300 K are compared. It is found that in spectral regions remote from strong absorption bands, the values of the n(nu) indices obtained at 250 K agree with the values given by Lorentz-Lorenz correction of the same indices at 300 K. All absorption bands observed at 300 K are found to be present at 250 K with slight shifts in frequency and with significant differences in the k(nu) indices at the band maxima. Based on these results, it is concluded that the clouds of Venus probably consist of droplets of aqueous solutions of sulfuric acid with acid concentrations of about 75% by weight.
Thermal analyses were performed for two distinct configurations of a proposed space nuclear power system which combines General Purpose Heat Source (GPHS) modules with the state of the art Free-Piston Stirling Engines (FPSEs). The two configurations correspond to systems with power levels of 250 and 500 W(sub e). The 250 W(sub e) GPHS/FPSE power system utilizes four GPHS modules and one FPSE, and the 500 W(sub e) contains eight GPHS modules and two FPSEs. The configurations of the systems and the bases for selecting the configurations are described. Brief introductory sections are included to describe the GPHS modules and free piston Stirling engines. The primary focus of the thermal analyses is on the temperature of the iridium fuel clad within the GPHS modules. A design goal temperature of 1573 K was selected as the upper limit for the fuel clad during normal operating conditions. The basis for selecting this temperature limit is discussed in detail. Results obtained from thermal analysis of the 250 W(sub e) GPHS/FPSE power system indicate fuel clad temperatures which slightly exceed the design goal temperature of 1573 K. The results are considered favorable due to the numerous conservative assumptions used in developing the thermal model and performing the thermal analysis. To demonstrate the effects of the conservatism, a brief sensitivity analysis is performed in which a few of the key system parameters are varied to determine their effect on the fuel clad temperatures. It is concluded that thermal analysis of a more detailed thermal model would be expected to yield fuel clad temperatures below the design foal temperature limiy 1573 K.
This paper examines heat pump (HP) technologies to achieve heat supply temperatures above 250 °C, referred to as ultra-high-temperature heat pump (UHTHP). UHTHP, as a low-carbon heat delivery and heat augmentation technology, can offer an alternative to traditional combustion heating for decarbonizing high-temperature industrial processes. However, the heat supply temperature of over 250 °C surpasses the temperature range typically covered in the high-temperature HP literature and existing capabilities of commercial HP systems. This paper reviews HP technologies with the potential to evolve into UHTHP. Additionally, UHTHP studies in the literature are analyzed to compare the pros, cons, and technical potentials of various HPs using different thermodynamic cycles and fluids. Furthermore, we then pinpoint the technical gaps and challenges that have hindered widespread adoption of UHTHP in industry, explore potential improvements and solutions, and discuss the feasibility. Current efforts aim to lay the ground for future research, development, and commercial deployment for UHTHP.
The speciation of U in NaCl-bearing solutions at temperatures up to 250 °C and concentrations of NaCl up to 1.5 m has been investigated using an in situ spectroscopic technique. The recorded spectra permit us to identify the species present in the solutions as UO 2 2+ , UO 2 Cl + , and UO 2 Cl 2 °. UO 2 Cl 3 - is also likely present at high temperatures and NaCl concentrations, but concentrations of this species are insufficient for derivation of the formation constants. No evidence was found for species of higher ligand (Cl-) number. Thermodynamic stability constants derived for these species show fair agreement with published data for 25 °C, but differ significantly from those predicted by an earlier high-temperature study (Dargent et al., 2013), which suggested that UO 2 Cl 4 2- and UO 2 Cl 5 3- contribute significantly to the mass balance of uranyl chloride complexes, especially at high temperature. In contrast, our data suggest that the main uranyl-chloride complex present in aqueous solutions at T >150 °C and concentrations of NaCl relevant to natural hydrothermal systems is UO 2 Cl 2 °. The values of the logarithms of thermodynamic formation constants (β) for the reaction UO 2 2+ + Cl - = UO 2 Cl + are 0.02, 0.25, 0.55, 1.09, 1.59, and 2.28 derived at 25, 50, 100, 150, 200, and 250 °C, respectively. For the reaction UO 2 2+ + 2Cl - = UO 2 Cl 2 ° the values of log β derived at these temperatures are 0.4, 0.58, 0.74, 1.44, 2.18, and 3.42. Values of the formation constant estimated for uranyl-chloride species predict the high concentrations of U observed by Richard et al. (2011) in fluid inclusions of the giant McArthur River unconformity-type uranium deposit.
In this study, the solubility and speciation of Th in Cl-bearing solutions saturated in ThO2 was investigated experimentally at 150, 175, 200, 225 and 250°C, and saturated water vapor pressure. At these experimental conditions (pH 25°C < 3.8, mNaCl < 2.5), Th-chloride complexation is insignificant, and the solubility of Th is controlled by hydrolysis. The two main species in solution were identified as Th(OH) 2 2+ and Th(OH) 4 ° and formed via the reactions Th 4+ + 2OH - ↔ Th(OH)$2+\atop{2}$ and Th 4+ + 4OH - ↔ Th(OH)$0\atop{4}$. The logarithms of the formation constants determined for the first reaction are 23.91 ± 0.05, 24.79 ± 0.07, 25.78 ± 0.05, and 25.85 ± 0.05 for 175, 200, 225 and 250°C, respectively, and 42.18 ± 0.06, 43.50 ± 0.07, 43.17 ± 0.08, and 43.74 ± 0.11 for the second reaction at the same temperatures. Formation constants could not be determined reliably for 150 °C. Extrapolations of our formation constants to 25°C are in excellent agreement with the values determined at 25 °C by Neck and Kim (2001) and Ekberg et al. (2000). Finally, for natural systems buffered by thorianite (ThO 2 ), the solubility determined in our study likely reflects a minimum, as the presence of additional ligands would lead to higher solubility.
The speciation of uranyl in sulfate-bearing solutions at temperatures up to 250 ºC has been investigated using in situ UV-Visible spectrophotometry. Formation constants for the reactions UO$^{2+}_{2}$ + SO$^{2–}_{4}$ $\Longleftrightarrow$ UO 2 SO$^{0}_{4}$ (logβ 1 = 3.38, 4.40, 5.44, 6.33, 7.74) and UO$^{2+}_{2}$ + 2SO$^{2–}_{4}$ $\Longleftrightarrow$ UO 2 (SO 4 )$^{2–}_{2}$ (logβ 2 = 4.10, 5.26, 6.83, 8.00, 9.70) derived at 25, 100, 150, 200 and 250 ºC respectively. These formation constants were fitted to the modified Ryzhenko – Bryzgalin (MRB) model to derive pK(298), A(zz/a) and B(zz/a) values for both complexes: 3.262, 2.212, -197.96 (UO 2 SO$^{0}_{4}$) and 4.189, 3.21, -473.14 UO 2 (SO 4 )$^{2–}_{2}$ respectively. Compared with values extrapolated using previously available data for 25, 70 and 75 ºC, our new data suggest higher stability of UO 2 SO$^{0}_{4}$ at temperatures above 150 ºC and significantly lower stability of UO 2 (SO 4 )$^{2–}_{2}$ at all temperatures above 25Cº. Molar absorbances of both sulfate species were also derived. At 25 Cº we found our molar absorbance for UO 2 SO$^{0}_{4}$ agreed well with those reported previously in the literature, however we report lower peak amplitudes for UO 2 (SO 4 )$^{2–}_{2}$ . We also noted significant temperature-dependent red shifts in the molar absorbance of UO 2 SO$^{0}_{4}$. We imply that these shifts could be explained by changes in sulfate bonding behaviour around the uranyl O04 ion - namely shifts in the distribution of complexes with sulfate bound in either a monodentate or bidentate configuration. Simple models calculated with our new data suggest that sulfate complexes may readily predominate over chloride complexes even in solutions containing upwards of 20 wt% chloride and only 100 ppm sulfate. In addition, moderate concentrations of sulfate (~1 wt%) can increase the solubility of uranium by an order of magnitude. Therefore, we imply that sulfate could play a vital role in mobilising uranium in hydrothermal systems, and that the removal of sulfate via precipitation of sulfate minerals may act as a means of depositing uranium under oxidizing conditions. This in turn might explain the associations between sulfate minerals and uranium mineralisation occasionally seen in large uranium ore deposits such as Olympic Dam and MacArthur River.
Combined modeling and experimental studies are reported of the fueling of a large (28 kg capacity) 250-bar Type IV hydrogen tank of the type being deployed on early hydrogen ferries, such as the MV Sea Change. The primary goal was to determine how such tanks can be successfully fueled with hydrogen (state of charge greater than 97%) within 45 minutes without exceeding the 82 °C temperature limit for such tanks. The modeling studies show that a gas injector is needed to avoid thermal stratification during hydrogen fueling which can result in potential hot spots. Empirically, precooling of the hydrogen to 0 °C was found to be needed in some of the cases examined, as ambient conditions greatly affected the need for a precooling to achieve the 45-minute fill time desired by end users. The experimental results afforded a calibration of the engineering model SOFIL for these large 250-bar tanks, which now enables using SOFIL to predict volume-averaged hydrogen fueling temperatures to an accuracy of ±2.7°C for these tanks. The model can therefore be used to evaluate potential scenarios for development of a standardized fueling methodology for ferries utilizing large Type-IV tanks.
We report low doped n-type 4H-SiC epitaxial layers of thickness 50, 150, and 250 µm grown by hot wall chemical vapor deposition were used to fabricate Ni/4H-SiC Schottky radiation detectors. The epitaxial layers were grown on the (0001) face of highly conductive bulk 4H-SiC substrates 8° offcut towards the $\langle 11\bar{2}1\rangle$ direction. The 50, 150, and 250 µm thick epilayer detectors, under optimized settings, showed energy resolutions of 2.0%, 0.78%, and 0.63%, respectively for 5.48 MeV alpha particles. Deep level transient spectroscopy studies showed that the observed variation in the detector resolution is linked to the defect parameters in the devices. Least-squares fitting of the bias dependence of the charge collection efficiency according to a drift-diffusion model, revealed minority carrier diffusion lengths of 16, 10, and 9.2 µm, respectively, implying that the detectors are not limited by minority carrier trapping. The detector performance was observed to be primarily dependent on the concentration and capture cross-sections of the lifetime killing electron traps Z 1/2 and EH 6/7 .
The performance of metallic fuel alloys, U-10Mo and U-17Mo, was examined using the MiniFuel test system in the High Flux Isotope Reactor. Approximately 0.8 mm thick disks were irradiated at target temperatures of 250°C, 350°C, 450°C, and 500°C up to three different fission densities, culminating at a maximum fission density of 6.8 × 10 20 cm −3 . Fission rates decayed from 3 – 6 × 10 13 cm −3 s −1 to 2 – 4 × 10 13 cm −3 s −1 over the course of the longest, eight cycle, irradiation as the 235 U was consumed and the 239 Pu concentration accumulated. Actual irradiation temperature on the last day of irradiation was measured via dilatometry using the SiC passive thermometry recovered from the MiniFuel subcapsules and compared favorably with the thermal calculations using as-built geometry and test conditions. Furthermore, average simulated temperatures were within 50°C of the target temperatures, except for the 500°C irradiation, for which the temperature variation was 62°C, 32°C, and 90°C in the in two, four, and eight cycle irradiations, respectively. Fission gas release (FGR) measurements showed no release above recoil for any U-17Mo fuels or for the U-10Mo fuel irradiated at 250°C. Finally, significant (40%–80%) FGR was found for the medium- to highest-burnup U-10Mo samples irradiated at target temperatures 350°C–500°C. Significant FGR correlated with sample thickness swelling, which was as high as 13%–35% for high-release samples and below 7% for all other (low–gas release) samples.
The slip activity and slip interaction in tensile deformation of peak-aged cast and extruded Mg-10Gd-3Y-0.5Zr (wt.%) at 250 °C was investigated using in-situ scanning electron microscopy. Basal slip was the most likely system to be activated during the tensile deformation, while prismatic < a > and pyramidal < c + a > slip also contributed to the deformation. No twinning was observed. The number of non-basal slip systems accounted for ~ 36% of the total active slip systems for the cast alloy, while non-basal slip accounted for 12–17% of the total deformation observations in the extruded alloy. Multiple-slip was observed within grains, and the basal/prismatic pairing type dominated the multiple-slip observations. Slip transfer occurred across grain boundaries and most of the slip transfer observations showed basal-basal type. The involved slip systems of slip transfer pairs were always associated with the same < a > direction. The slip transfer occurred more easily at low angle boundaries (LABs) and boundaries with misorientations greater than 75°. - Highlights: • Slip deformation of a Mg-RE alloy at 250 °C was investigated using in-situ SEM. • The extruded-T5 GW103 alloy did not exhibit a high anisotropic behavior. • Multiple-slip was observed within grains, and basal/prismatic type dominated. • Slip transfer occurred and most of the observations showed basal-basal type. • Slip transfer occurred more easily at LABs and boundaries with misorientations > 75°.