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At least 199 records · Page 11

Stability and Phase Noise Tests of Two Cryo-Cooled Sapphire Oscillators

A cryocooled Compensated Sapphire Oscillator (CSO), developed for the Cassini Ka-band Radio Science experiment, and operating in the 8K - 10K temperature range was previously demonstrated to show ultra-high stability of sigma(sub y) = 2.5 x 10 (exp -15) for measuring times 200 seconds less than or equal to tau less than or equal to 600 seconds using a hydrogen maser as reference. We present here test results for a second unit which allows CSO short-term stability and phase noise to be measured for the first time. Also included are design details of a new RF receiver and an intercomparison with the first CSO unit. Cryogenic oscillators operating below about 10K offer the highest possible short term stability of any frequency sources. However, their use has so far been restricted to research environments due to the limited operating periods associated with liquid helium consumption. The cryocooled CSO is being built in support of the Cassini Ka-band Radio Science experiment and is designed to operate continuously for periods of a year or more. Performance targets are a stability of 3-4 x 10 (exp -15) (1 second less than or equal to tau less than or equal to 100 seconds) and phase noise of -73dB/Hz @ 1Hz measured at 34 GHz. Installation in 5 stations of NASA's deep space network (DSN) is planned in the years 2000 - 2002. In the previous tests, actual stability of the CSO for measuring times tau less than or equal to 200 seconds could not be directly measured, being masked by short-term fluctuations of the H-maser reference. Excellent short-term performance, however, could be inferred by the success of an application of the CSO as local oscillator (L.O.) to the JPL LITS passive atomic standard, where medium-term stability showed no degradation due to L.O. instabilities at a level of (sigma)y = 3 x 10 (exp -14)/square root of tau. A second CSO has now been constructed, and all cryogenic aspects have been verified, including a resonator turn-over temperature of 7.907 K, and Q of 7.4 x 10 (exp 8). These values compare to a turn-over of 8.821 K and Q of 1.0 x 10 (exp 9) for the first resonator. Operation of this second unit provides a capability to directly verify for the first time the short-term (1 second less than or equal to tau less than or equal to 200 seconds) stability and the phase noise of the CSO units. The RF receiver used in earlier tests was sufficient to meet Cassini requirements for tau greater than or equal to 10 seconds but had short-term stability limited to 2-4 x 10 (exp -14) at tau = 1 second, a value 10 times too high to meet our requirements. A new low-noise receiver has been designed to provide approximately equal to 10-15 performance at 1 second, and one receiver is now operational, demonstrating again short-term CSO performance with H maser-limited stability. Short-term performance was degraded in the old receiver due to insufficient tuning bandwidth in a 100MHZ quartz VCO that was frequency-locked to the cryogenic sapphire resonator. The new receivers are designed for sufficient bandwidth, loop gain and low noise to achieve the required performance.

Dick, G. John↗

Simultaneous Ka-Band Site Characterization: Goldstone, CA, White Sands, NM, and Guam, USA

To statistically characterize atmospheric effects on Ka-band links at NASA operational sites, NASA has constructed site test interferometers (STI s) which directly measure the tropospheric phase stability and rain attenuation. These instruments observe an unmodulated beacon signal broadcast from a geostationary satellite (e.g., Anik F2) and measure the phase difference between the signals received by the two antennas and its signal attenuation. Three STI s have been deployed so far: the first one at the NASA Deep Space Network Tracking Complex in Goldstone, California (May 2007); the second at the NASA White Sands Complex, in Las Cruses, New Mexico (February 2009); and the third at the NASA Tracking and Data Relay Satellite (TDRS) Remote Ground Terminal (GRGT) complex in Guam (May 2010). Two station-years of simultaneous atmospheric phase fluctuation data have been collected at Goldstone and White Sands, while one year of data has been collected in Guam. With identical instruments operating simultaneously, we can directly compare the phase stability and rain attenuation at the three sites. Phase stability is analyzed statistically in terms of the root-mean-square (rms) of the tropospheric induced time delay fluctuations over 10 minute blocks. For two years, the time delay fluctuations at the DSN site in Goldstone, CA, have been better than 2.5 picoseconds (ps) for 90% of the time (with reference to zenith), meanwhile at the White Sands, New Mexico site, the time delay fluctuations have been better than 2.2 ps with reference to zenith) for 90% of time. For Guam, the time delay fluctuations have been better than 12 ps (reference to zenith) at 90% of the time, the higher fluctuations are as expected from a high humidity tropical rain zone. This type of data analysis, as well as many other site quality characteristics (e.g., rain attenuation, infrastructure, etc.) will be used to determine the suitability of all the sites for NASA s future communication services at Ka-band.

Acosta, Roberto↗

An explanation for the plateau phenomenon in isoelectric focusing

Isoelectric focusing of mixtures of simple ampholytes occurs in two phases, an initial rapid separation phase and a second relatively slow stabilizing phase. Transient and steady-state computer simulation data are shown to predict the development of pH plateaus around neutrality during the stabilizing phase of the focusing of such mixtures. This occurs because a nonzero electrophoretic flux is present in a pure zone of focused ampholyte, which is a function of both its isolectric point (pI) and its Delta-pK value. For an ampholyte with a pI greater than 9 or less than 5, this flux causes the development of a significant concentration gradient within its focused zone which is accompanied by a contraction of this zone along the focusing axis. Acidic and basic ampholytes are thereby displayed toward the anode and cathode respectively, creating a pH plateau in the neutral region. Thus, there will be regions of the focusing column, closer to the electrodes and containing more acidic or basic pH values, within which the resolution of samples will reach a maximum and then decrease.

Mosher, Richard A.↗

High strain rate deformation of aged TRIP Ti-10V-2Fe-3Al (wt.%) examined by in-situ synchrotron X-ray diffraction

Transformation Induced Plasticity (TRIP) is a promising avenue for tailoring the work hardening response of metastable $β$ titanium (Ti) alloys. Here we show that aged TRIP Ti-10V-2Fe-3Al (wt.%) maintains higher elongations and flow stresses as strain rate increases, if phase stability and microstructural characteristics are tuned. Low temperature aging influences the matrix $β$ phase stability by $ω$ phase precipitation, which affords a promising way to impact the TRIP effect and obtain desirable mechanical properties, ranging from high damping capacity to good strength/ductility combinations. Although TRIP is active during quasi-static and dynamic testing up to 2000 s –1 , increasing aging time and/or strain rate reduces the overall propensity for the TRIP effect and extent of transformation, which occurs rapidly just at the onset of yielding. Importantly, TRIP with $ω$ phase precipitation provides interesting alloying, microstructure, and property design strategies for engineering applications like lightweight protective structures, where high strains and the need for energy absorption are encountered.

36 MATERIALS SCIENCE↗

Nonequilibrium defect-phase nanostructures stabilized by irradiation in undersaturated Ni-Si nanocrystalline alloy

Nanocrystalline thin films of the undersaturated alloy Ni-8.5 at% Si were subjected to 2 MeV Ti irradiation at temperatures ranging from 450˚C to 550˚C. Correlative microscopy combining transmission electron microscopy (TEM), scanning-TEM and atom probe tomography (APT revealed that large dose irradiation at 450˚C of samples with initial grain sizes below 100 nm stabilized a novel nanostructure which surprisingly contained three co-existing phases, the γ face-centered-cubic (FCC) matrix, γ' L12 ordered precipitates on intragranular dislocation loops and Ni 31 Si 12 precipitates at triple junctions (TJs). In contrast, irradiation at 550˚C and irradiation of larger grain-size samples at 450˚C only produced a γ-γ' two-phase coexistence. Analysis of the three-phase nanostructure and phase field simulations indicates that radiation-induced segregation is most pronounced at TJs, thus triggering the formation of Ni 31 Si 12 precipitates. These incoherent precipitates, in turn, are expected to stabilize the grain size under irradiation. The results are generalized using the concept of driven defect-phases. It is suggested that the stabilization of driven defect-phases may impart radiation resilience by providing localized relaxation modes to the microstructure evolution during and after temporary perturbations in irradiation conditions.

36 MATERIALS SCIENCE↗

On the Stability and Phase Behavior of Titan's Subsurface Liquid Columns

On Titan, liquid hydrocarbon may stay in the subsurface porous permeable crust known as the alkanofer, analogous to water in Earth’s aquifer. In addition to pressure gradient, the subsurface liquid in alkanofers is subject to vertical compositional grading due to the gravity and temperature gradient. The common wisdom is that the liquid would normally stay underground in a stability established by the pressure that increases with depth as observed in aquifers on Earth. However, Titan’s liquids consist of nitrogen and hydrocarbons, mainly methane and ethane, the behavior of which is very sensitive to temperature and pressure. Consequently, the liquid density does not always increase with depth, thus may introduce a reverse density profile that leads to vertical convective instability of the liquid column. If reverse density profiles are present, capillary pressures arising from liquid trapped within small pores in the crust can help with the column stability. The liquid held in the capillaries can seal the space below it thus helping with the stability, unless the overpressure built from underneath becomes larger than the capillary pressure, which causes leakage to allow the liquids to seep upward from the deep. This situation is analogous to hydrocarbon seeps on Earth, where oil and natural gas escape the reservoir and flow slowly through network of cracks to the surface. An algorithm based on an extended Gibbs equation commonly used in petroleum reservoir engineering is employed in this work to produce pressure, density, and compositional profiles for evaluating the stability and phase behavior of Titan’s subsurface fluids.

Sugata Tan↗

Complexions at the iron-magnetite interface

Synthesizing distinct phases and controlling crystalline defects are key concepts in materials design. These approaches are often decoupled, with the former grounded in equilibrium thermodynamics and the latter in nonequilibrium kinetics. By unifying them through defect phase diagrams, we can apply phase equilibrium models to thermodynamically evaluate defects—including dislocations, grain boundaries, and phase boundaries—establishing a theoretical framework linking material imperfections to properties. Using scanning transmission electron microscopy (STEM) with differential phase contrast (DPC) imaging, we achieve the simultaneous imaging of heavy Fe and light O atoms, precisely mapping the atomic structure and chemical composition at the iron-magnetite (Fe/Fe 3 O 4 ) interface. We identify a well-ordered two-layer interface-stabilized phase state (referred to as complexion) at the Fe[001]/Fe 3 O 4 [001] interface. Using density-functional theory (DFT), we explain the observed complexion and map out various interface-stabilized phases as a function of the O chemical potential. The formation of complexions increases interface adhesion by 20% and alters charge transfer between adjacent materials, impacting transport properties. Our findings highlight the potential of tunable defect-stabilized phase states as a degree of freedom in materials design, enabling optimized corrosion protection, catalysis, and redox-driven phase transitions, with applications in materials sustainability, efficient energy conversion, and green steel production.

36 MATERIALS SCIENCE↗

Computational discovery of ultra-strong, stable, and lightweight refractory multi-principal element alloys. Part II: comprehensive ternary design and validation

Abstract Here the discovery of refractory multi-principal element alloys (MPEAs) with high-temperature strength and stability is pursued within a constrained and application-relevant design space. A comprehensive approach is developed and applied to explore all 165 ternary systems in the Al-Ce-Fe-Hf-Mo-Nb-Ta-Ti-V-W-Zr family. A subset of ternary systems that contain large areas in composition–temperature space with high strength and robust BCC phase stability is found. Twelve sets of high-performing alloys are identified, each set optimized for one combination of phase constraint, optimization target, and temperature range. Preliminary mechanical tests support the viability of the method. This work highlights the importance of considering phase stability, exploring non-equiatomic regions of composition space, and applying application-relevant constraints. Parts I and II provide three down-selection techniques for identifying high-performing BCC refractory MPEAs, design guidelines, and many candidates predicted to have BCC phase stability and strengths 2–3 times higher than any reported to date.

36 MATERIALS SCIENCE↗

The CALPHAD approach for HEAs: Challenges and opportunities

Phases are key microstructural features that determine material properties. The most intuitive way of representing phase stability in a material is by its phase diagram. The vastness of the composition space is the most compelling reason for investigating high-entropy alloys (HEAs), but it also creates major challenges in controlling phases and microstructures of HEAs due to lack of experimental phase diagrams in highly concentrated multicomponent space. The CALPHAD (Calculation of Phase Diagram) approach, although it needs improvements, is the only viable way to calculate multicomponent phase diagrams. The two major property databases in CALPHAD, Gibbs energy and mobility, when coupled, can provide not only the equilibrium phase information, but also information about diffusion and kinetics. In this article, we will review the use of the CALPHAD approach in understanding phase stability and diffusion in high-entropy alloys. Finally, we will discuss the notable trend of coupling the high-throughput CALPHAD approach with machine learning in HEA design.

36 MATERIALS SCIENCE↗

Development of Corrosion Resistant Coatings for Structural Materials for Liquid Fueled Molten Salts Reactors Applications (Final Report)

Current structural alloys, code certified for the MSRs temperature ranges, contain high levels of chromium, making them highly susceptible to molten halide salt corrosion. One potential solution to circumvent the need for code certification of novel alloys, which is expensive and time consuming, is to design claddings that will protect the underlying code certified materials from corrosion damage during operation. In this work, we examined the corrosion of Ni and Cu electroplated, Ni and CuNi weld overlay, Mo-laser clad, and carburized claddings on SS316H for use in molten salt reactor environments. After characterization of the cladded materials (Task 1), static corrosion tests were used to assess corrosion resistance of the claddings in typical molten fluoride salts (Task 2). The corrosion tests were performed in molten FLiNaK at 700°C up to 1000 hours. Pre- and post-corrosion Scanning Electron Microscopy (SEM), energy-dispersive-spectroscopy (EDS), Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD) and glow-discharge-optical-emission-spectroscopy (GDOES) were performed on cladding cross-sections and surfaces to evaluate degradation. The Cu and Ni electroplated samples, as well as the carburized samples, showed excellent corrosion resistance relative to the bare SS316H. To assess high temperature cladding stability, ageing experiments were performed at temperatures up to 900 C in inert atmosphere for the electroplated and carburized samples and a diffusion model was developed to predict long term cladding behavior (Task 3). It was found that the Cu cladding was basically insensitive to the high temperature ageing, except for small secondary phases forming at the interface. On the other hand, the Ni electroplated cladding experienced significant interdiffusion. Nevertheless, the gain in corrosion resistance for a 100μm Ni electroplated cladding is phenomenal, with more than 50% reduction in chromium dissolution from the substrate material for the first 15 years of salt exposure at 700°C. To assess radiation resistance and phase stability, high-temperature 4MeV Ni heavy ion irradiation was performed across the cladding/substrate interface up to 50 displacement-per-atom (DPA) at 500°C and 700°C to assess the phase stability and irradiation behaviors of the electroplated systems (Task 4). The Ni and Cu electroplated systems did not experience void swelling at the contrary to the SS316H substrate due to their nanocrystalline nature. Some level of recrystallization was observed in the cladding, as well as radiation induced segregation and enhanced diffusion. The interface acted as a potent sink for point defects with the presence of a void denuded zone. The mechanical properties of the claddings were assessed using thermal shock, micro-indentation, nano-indentation, and four-point bend testing experiments (Task 5). These experiments were performed on the claddings in as-received, corroded, irradiated, and thermally aged states to determine the effects of typical molten salt reactor environments on cladding integrity. No significant mass loss was observed after repeated thermal shocks. While the electroplated samples softened after high-temperature ageing, irradiation hardening compensate this effect, such that there is little different with the as-received materials. The results of these experiments suggest that the electroplated (copper/nickel) show the greatest promise for application in molten salt reactor development. These claddings prevented any chromium dissolution from occurring during the static corrosion experiments. Additionally, they demonstrated favorable properties for high temperature diffusion, phase stability, interfacial mechanical properties, and irradiation resistance. Weld-overlay cladding are also of great interest and could reach properties similar to the electroplated samples upon optimization (especially with multiple weld passes). The carburized SS316H showed excellent behavior as well, but more work needs to be done to assess their long-term stability. Finally, the Mo-laser clad system was not pursued further due to the manufacturing challenges. It is also worth noting that the Ni cladding systems should behave relatively well in terms of weldability since the Ni-weld overlay microstructure and associated corrosion rate are sound. While the NiCu weld-overlay has even lower corrosion rates than the Ni-weld overlay, more studies on welding of Cu-electroplated systems are necessary since Cu clusters are known to embrittle steels.

36 MATERIALS SCIENCE↗

Manganese-based A-site high-entropy perovskite oxide for solar thermochemical hydrogen production

Non-stoichiometric perovskite oxides have been studied as a new family of redox oxides for solar thermochemical hydrogen (STCH) production owing to their favourable thermodynamic properties. However, conventional perovskite oxides suffer from limited phase stability and kinetic properties, and poor cyclability. Here, we report a strategy of introducing A-site multi-principal-component mixing to develop a high-entropy perovskite oxide, (La 1/6 Pr 1/6 Nd 1/6 Gd 1/6 Sr 1/6 Ba 1/6 )MnO 3 (LPNGSB_Mn), which shows desirable thermodynamic and kinetics properties as well as excellent phase stability and cycling durability. LPNGSB_Mn exhibits enhanced hydrogen production (~77.5 mmol mol oxide -1 ) compared to (La 2/3 Sr 1/3 )MnO 3 (~53.5 mmol mol oxide -1 ) in a short 1 hour redox duration and high STCH and phase stability for 50 cycles. LPNGSB_Mn possesses a moderate enthalpy of reduction (252.51–296.32 kJ (mol O) -1 ), a high entropy of reduction (126.95–168.85 J (mol O) -1 K -1 ), and fast surface oxygen exchange kinetics. All A-site cations do not show observable valence changes during the reduction and oxidation processes. In conclusion, this research preliminarily explores the use of one A-site high-entropy perovskite oxide for STCH.

08 HYDROGEN↗

Fermi Surface Structure and Isotropic Stability of Fulde-Ferrell-Larkin-Ovchinnikov Phase in Layered Organic Superconductor β''-(BEDT-TTF) 2 SF 5 CH 2 CF 2 SO 3

The Fermi surface structure of a layered organic superconductor β''-(BEDT-TTF) 2 SF 5 CH 2 CF 2 SO 3 was determined by angular-dependent magnetoresistance oscillations measurements and band-structure calculations. This salt was found to have two small pockets with the same area: a deformed square hole pocket and an elliptic electron pocket. Characteristic corrugations in the field dependence of the interlayer resistance in the superconducting phase were observed at any in-plane field directions. The features were ascribed to the commensurability (CM) effect between the Josephson vortex lattice and the periodic nodal structure of the superconducting gap in the Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) phase. The CM effect was observed in a similar field region for various in-plane field directions, in spite of the anisotropic nature of the Fermi surface. The results clearly showed that the FFLO phase stability is insensitive to the in-plane field directions.

36 MATERIALS SCIENCE↗

Effect of Mn on eutectic phase equilibria in Al-rich Al-Ce-Ni alloys

Microstructural analysis of additively manufactured (AM) Al-Ce-Ni-Mn alloys has identified phases not predicted from existing ternary liquidus projections in the Al-Ce-Ni system. Because the rapid cooling rate of AM is orders of magnitude above that of traditional casting, it is unclear if these additional phases arose from the non-equilibrium processing conditions of AM, a drastic shift in phase stability in the system due to the addition of 1 wt% Mn, or some combination of these two influences. The phases and microstructure of cast samples of Al-Ce-Ni and Al-Ce-Ni-Mn alloys were characterized for several annealing conditions which revealed the equilibrium phases at different temperatures. Phase analysis confirmed that minute levels of Mn substituted for Ni in the system drastically shifts the liquidus projection in the Al-rich corner of the ternary phase diagram such that the eutectic Al 3 Ni phase is suppressed in favor of the Al 23 Ni 6 (Ce,Mn) 4 phase. Further addition of Mn promotes the formation of Al 20 Mn 2 Ce and Al 10 Mn 2 Ce phases. The phase analysis data was then used to improve the CALPHAD modeling of the liquidus projection and isothermal sections for the Al-rich Al-Ce-Ni-Mn quaternary system. Thermodynamic modeling and experimental analysis on phases in the AM sample of Al-Ce-Ni with Mn confirmed that the phases present are consistent with Mn-containing Al-Ce-Ni cast samples. Here, this investigation demonstrates the potential for using secondary alloying elements to drastically alter phase stability and microstructure in alloy systems.

36 MATERIALS SCIENCE↗

Chain Redistribution Stabilizes Coexistence Phases in Block Copolymer Blends

The nanoscale morphologies of block copolymer (BCP) thin films are determined by chain architecture. Experimental studies of thin film blends of different BCP chain types have demonstrated that blending can stabilize new motifs, such as coexistence phases. Here, we deploy coarsegrained molecular dynamics (MD) simulations in order to better understand the self-assembly behavior of BCP blend thin films. Here, we consider blends of lamella- and cylinder-forming BCP chains, studying their morphological makeup, the chain distribution within the morphology, and the underlying polymer chain conformations. Our simulations show that there are local concentration deviations at the scale of the morphological objects that dictate the local structure, and that BCP chains redistribute within the morphology so as to stabilize the structure. Underlying these effects are measurable distortions in the BCP chain conformations. The conformational freedom afforded by BCP blending stabilizes defects and allows coexistence phases to appear, while also leading to kinetic trapping effects. These results highlight the power of blending in designing the morphology that forms.

36 MATERIALS SCIENCE↗

Irradiation-induced shift in the thermodynamic stability of phases and the self-healing effect in transformative high entropy alloys

Here, this work investigated Fe 40 Mn 20 Cr 15 Co 20 Si 5 high entropy alloy (CS-HEA), which exhibits transformation induced plasticity (TRIP) from γ-fcc → ε-hcp, as a probable candidate for nuclear applications. CS-HEA is an extensively-explored, low stacking fault energy alloy with superior strength, ductility, fatigue resistance, and corrosion resistance. This study delved into the effect of irradiation on the shift in thermodynamic stability of the phases and thus radiation tolerance. The evolution of phases, lattice parameters, and transformation volume, V γ→ε , were evaluated from X-ray diffraction experiments along with the mechanical response from nanoindentation. The alloy exhibited a recently-proposed novel self-healing mechanism possible due to the TRIP effect to minimize irradiation damage by restraining the γ-fcc → ε-hcp transformation via thermal aid; this self-healing mechanism was confirmed by transmission electron microscopy. The results were corroborated by a negative change in V γ→ε and a low |V γ→ε |, which is an important criterion for recovery of parent γ-fcc phase. Thus, this alloy was deemed a good radiation-tolerant candidate for nuclear application.

36 MATERIALS SCIENCE↗

Processing and characterization of the homologous Zr x Ta 2 O 2x+5 series

In this study, Zr x Ta 2 O 2x+5 (ZTOx) was systematically studied to determine ideal solid-state synthesis and pressureless sintering conditions. For Zr 6 Ta 2 O 17 (ZTO6) and other compositions with values of x in ZTOx the optimal synthesis temperature of 1100 °C with 1 h dwell time was optimal. XRD phase analysis of the homologous series indicated that for ZTOx, x = 5, 6, 7, and 8 were within the phase stability field while x = 4 and x = 9 were outside the phase stability field. Unit cell lattice parameters changed anisotropically with Zr:Ta ratio with an overall <0.1% change in unit cell volume across the solid solution. Some Raman modes red shifted while others blue shifted, indicating competing tensile and compressive strains. Sintering of ZTOx required a progressively higher temperature as Zr-content increased despite the same starting powder grain sizes and synthesis temperature. Higher Vickers hardness for Zr-rich (12.7–12.8 GPa) than Ta-rich Zr x Ta 2 O 2x+5 (11.6–11.7 GPa) disappeared when accounting for different sintering temperatures. Indentation toughness was similar for all compositions (1.2–1.4 MPa m 1/2 ). Properties of Zr x Ta 2 O 2x+5 series indicate tunability of Zr:Ta composition ratio while maintaining the structure and room temperature mechanical properties comparable to Hf 6 Ta 2 O 17 and 8 mol% yttria stabilized zirconia ceramics.

36 MATERIALS SCIENCE↗