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At least 289 records · Page 16

Effects of HCP/BCC element ratios on the room-temperature tensile properties of Ti-Zr-Hf-Nb-Ta refractory high-entropy alloys

Equiatomic and non-equiatomic Ti-Zr-Hf-Nb-Ta refractory high-entropy alloys (RHEAs) were arc melted, homogenized, cold rolled, and recrystallized to produce single-phase, body-centered cubic (BCC), microstructures with weak texture and equiaxed grains 76–199 μm in size. Here, the non-equiatomic alloys had either a 60:40 or 80:20 atomic ratio of hexagonal close-packed (HCP) elements (Ti + Zr + Hf) to BCC elements (Nb + Ta). Alloy compositions were measured after thermomechanical processing to determine the concentrations of the major (substitutional) and minor (interstitial) elements. We investigated how elastic constants and uniaxial tensile properties were affected by changes in the relative concentrations of the constituent elements at fixed HCP:BCC ratios. Yield strengths ranged from 801 to 922 MPa and ultimate tensile strengths from 815 to 933 MPa. Good agreement is obtained between the experimental yield strengths and those predicted by a strength theory based on edge dislocations indicating that the observed compositional effects are due to their effects on shear modulus and volume misfit. Fracture occurred by dimpled rupture with fracture strains of 19.4%–25.7%, but uniform strains were an order of magnitude lower at 1.1%–3.2%, calling into question the useable ductility (prior to necking) of RHEAs considered to be ductile based on their fracture strain. Contrary to predictions in the literature that HCP elements promote ductility, our present results show that increasing the HCP:BCC ratio decreases both the total strain and the uniform strain. Similar trends were not evident in the yield or ultimate strengths; rather, strengths were affected mainly by shear modulus and volume misfit.

BCC high-entropy alloys↗

The role of Si in determining the stability of the θ; precipitate in Al-Cu-Mn-Zr alloys

Precipitate-strengthened Al-Cu-Mn-Zr (ACMZ) alloys demonstrate improved microstructural stability compared to conventional Al-Cu alloys. Si is typically considered an impurity in these alloys, but a systematic analysis of ACMZ alloys with a range of Si levels revealed that there is a Si content range (~0.05 wt. % < Si < ~0.10 wt. %) for achieving optimal high temperature microstructural stability. A combination of hardness testing, scanning electron microscopy, and atom probe tomography has been used to understand the relationship between Si content, aging response, and thermal stability in ACMZ alloys. It is shown that the optimum Si content range corresponds to a reduced as-aged hardness, but a greater hardness value retained by the alloy after thermal exposure to 350 °C for 200 hours. A mechanism is proposed in which optimum Si levels reduce the number density of nucleation sites for θ' precipitates, resulting in larger precipitates that, on average, provide a reduced as-aged strength but are more coarsening resistant. This inherent θ' coarsening resistance allows more time for slow-diffusing Mn and Zr to reach the θ' interface and further stabilize the precipitates. Designing the optimal as-aged microstructure for improved thermal stability of the alloy by controlling impurity levels is a concept that has implications beyond the investigated Al-Cu alloy system.

36 MATERIALS SCIENCE↗

Spark plasma sintered, MoNbTi-based multi-principal element alloys with Cr, V, and Zr

MoNbTi, MoNbTiZr, CrMoNbTiZr, and MoNbTiVZr multi-principal element alloys (MPEAs) were fabricated via spark plasma sintering (SPS) and investigated for use in high-strength applications. The fabrication method by SPS and powder metallurgy differs from those presented in the prior literature, where most MPEAs are fabricated using arc melting (AM) methods. Here cryogenic milling was used to maximize potential defect sinks (grain boundaries) for radiation resistance and to increase ultimate tensile strength through the Hall-Petch effect. SPS was chosen for consolidation in order to maintain a fine-grained structure during densification. Each alloy was characterized using x-ray diffraction and scanning electron microscopy for phase identification and compositional homogeneity. The base ternary alloy MoNbTi presented a predominantly single BCC system with minor cubic phases. The introduction of additional alloying elements—Zr, V, and Cr—heightened the phase complexity and increased the fractions of a secondary BCC phase and an HCP phase from Zr. The addition of Cr induced a larger fraction of the Laves phase to form. The addition of V caused the precipitation of small Mo inclusions. Thermodynamic analysis was performed to understand the separation of phases in each alloy. Discrepancies among the phase predictions generated by thermodynamic models, phases previously presented in the literature, and the characterization results suggest that MPEA fabrication methods, especially solid-state methods, require significant investigation to ensure that alloys can remain stable throughout their anticipated service lifetimes.

36 MATERIALS SCIENCE↗

Structural evolution and magnetic hardness of (Sm,Zr)(Fe,Co,Ti) 12 alloy particles via reduction-diffusion

The quest for achieving high coercivity in Sm(Fe,Co,Ti) 12 alloys, despite their inherent strong magnetocrystalline anisotropy, has posed significant challenges. Recently, (Sm,Zr)(Fe,Co,Ti) 12 monocrystalline particles have exhibited coercivity μ 0 H c > 1.2 T, showcasing promising prospects and significant potential for both manufacturing and research endeavors. This study delves into the structural evolution of (Sm,Zr)(Fe,Co,Ti) 12 (1:12) alloy particles made via the calciothermic reduction-diffusion synthesis process as influenced by the molar ratios of Ca atoms to O 2- ions (Ca/O), annealing time and annealing temperature. Critical insight that informs conditions to optimize the magnetic response is gained via systematic experimentation and advanced electron microscopy. Complex structural features, including core-shell morphologies and intricate multiphase compositions within individual particles, are unveiled. An optimal Ca/O ratio of 1.30 produces particles with a coercivity up to μ 0 H c = 1.63 T, while higher Ca/O ratios induce the formation of a Sm-rich TbCu 7 -type (1: 7 ) phase, which only partially transforms into the desired 1:12 phase during annealing. Persistent remnants of the 1:7 phase locally impact atomic structure, particle morphology, and coercivity. Furthermore, these findings underscore the complex interplay between synthesis parameters, resulting structures, and magnetic properties, informing the design and optimization of high-performance permanent magnets comprised of the (1:12) compound.

36 MATERIALS SCIENCE↗

Intermetallic phase formation in Al-Si-Zr alloys during hot isostatic pressing revealed by experiments and molecular dynamics

Understanding phase transformations at alloy interfaces is critical for the design of advanced structural materials. Here, in this study, we investigate the formation mechanisms of the Al 2 SiZr intermetallic phase in the Al-Si-Zr system under hot isostatic pressing (HIP) using molecular dynamics (MD) simulations and thermodynamic analysis. A unique aspect of our approach in MD involves the replacement of a disordered Al 2 SiZr stoichiometry with an ordered phase at the Al-Zr interface once HIP results in the desired Al 2 SiZr stoichiometry, allowing us to compute the total energetic cost of transformation by accounting for both formation energies and diffusion barriers. Diffusion coefficients and activation energies, extracted across a range of temperatures, reveal that HIP substantially enhances atomic mobility, creating favorable stoichiometry for phase evolution. Our results show that Al 2 SiZr phase formation is kinetically unfavorable at lower temperatures but becomes feasible when the thermodynamic driving energy surpass a critical energy threshold.

Roy, Ankit [Pacific Northwest National Laboratory ↗

Phase evolution during reactive flash sintering of Li 6.25 Al 0.25 La 3 Zr 2 O 12 starting from a chemically prepared powder

Here, reactive flash sintering (RFS) of a chemically prepared multiphase precursor powder was performed to fabricate Li 6.25 Al 0.25 La 3 Zr 2 O 12 (Al-LLZO) ceramics. This approach allowed for obtaining single-phase dense samples in a remarkably short processing time of 30 s, at a furnace temperature of 600 °C, with an electric field of 50 V cm -1 and a current limit of 150 mA mm -2 . The ceramics display high bulk conductivity of 0.18 mS cm -1 at room temperature. Furthermore, phase evolution is studied by in-situ X-ray diffraction during: i) conventional heating and ii) RFS under current rate mode. As expected, the intermediate phases progressively dissolved into the Al-LLZO matrix by conventional heating. On the other hand, RFS promoted the growth of the intermediate La 2 Zr 2 O 7 , an effect that was overcome by the thermally driven formation of Al-LLZO at higher temperatures. The observed different reaction pathway suggests that RFS can be used for stabilizing phases that are not thermodynamically favored upon conventional heating.

36 MATERIALS SCIENCE↗

Isotropic nanocrystalline Sm(Fe,Co) 11.3 Ti 0.7 magnets modified with B and Zr

Rare-earth-lean Sm(Fe,Co,Ti) 12 alloys with the ThMn 12 crystal structure and less than one Ti atom per formula unit have the potential of exceptionally powerful permanent magnets, but all prior attempts to develop high coercivity in bulk alloys, especially coercivity combined with crystallographic texture, have fallen short of the expectations. This study was aimed at improvement of the currently best Sm(Fe,Co,Ti) 12 magnets prepared through melt-spinning which are inherently isotropic. Modifications of the alloys with B and Zr, already demonstrated in earlier studies to be effective separately, have been implemented simultaneously. Here, a systematic study of Sm 1.1-x (Fe,Co) 11.3-y Ti 0.7 B y alloys melt-spun at a tangential speed of 50 m/s and annealed at 600–950 °C allowed for monitoring the continuous evolution of the two consecutive crystal structures, those of the TbCu 7 and ThMn 12 types. Zirconium was found to facilitate the formation of the 1:12 structure at the expense of the 1:7, whereas boron has the opposite effect, at certain concentrations completely suppressing the 1:12. When the two alloying elements are introduced simultaneously, they inhibit growth of the 1:12 crystallites at annealing temperatures higher than 800 °C, thus allowing for the development of a higher coercivity. Because of instrumental limitations, bulk magnets were prepared through a two-step process – compaction of the melt-spun ribbons at 650 °C and additional treatment at a higher temperature – and they were characterized by a reduced, 90–93%, density. Nevertheless, an isotropic Sm 0.9 Zr 0.2 (Fe,Co) 10.8 Ti 0.7 B 0.5 magnet exhibited fair values of the remanence (7.4 kG), maximum energy product (8.5 MGOe) and coercivity (5.4 kOe), as well as high Curie temperature of 525 °C and remarkably small temperature coefficient of the coercivity, -0.25%/°C.

36 MATERIALS SCIENCE↗

Glassy correlated state induced by disorder in the frustrated antiferromagnet Tb 2 Zr 2 O 7

Here, we study the low-temperature thermomagnetic properties of the polycrystalline material Tb 2 Zr 2 O 7 through ac susceptibility and specific heat measurements. This zirconate displays a defect-fluorite structure in which the magnetic Tb 3+ and nonmagnetic Zr 4+ cations sit randomly on the same metal sublattice. No long-range magnetic order is found down to 100 mK, although dominant antiferromagnetic interactions are observed and the spins remain dynamic down to the lowest temperatures investigated. We observed a frequency-dependent peak around 2.5 K which is well described by many models of a canonical spin-glass transition. In-field specific heat measurements and the recovered entropy of the system R ln(4) suggest a two doublets ground state separated by 7 K. Comparisons to the pyrochlores Tb 2 Ti 2 O 7 and Tb 2 Hf 2 O 7 reinforce the collective spin-glass-type behavior and the opening for discussions of an exotic Coulomb phase in this material.

36 MATERIALS SCIENCE↗

Intrinsic and hard magnetic properties of (Sm 1-x R x )-Fe-Co-V alloys (R = Gd, Zr, and Y)

SmFe 12 -based compounds with the ThMn 12 -type structure have a great potential as future rare-earth-lean permanent magnets. However, their reliance on stabilizing non-magnetic elements has impeded practical applications. Therefore, elements such as Gd, Y, and Zr have gained popularity as candidates to minimize the need for stabilizing elements by reducing the formation energy of the ThMn 12 (1:12) phase. Here, this study examines the effect of Gd, Y, and Zr on the intrinsic and hard magnetic properties in (Sm 1-x R x ) 1.2 Fe 8.4 Co 2.1 V 1.5 (or with nominal composition of (Sm 1-x R x ) 9.1 Fe 63.6 Co 15.9 V 11.4 ) with a single 1:12 phase for 0 ≤ x ≤ 0.3. Notably, samples substituted with Gd exhibit an enhanced temperature dependence of the magnetic properties.

36 MATERIALS SCIENCE↗

Cluster dynamics modeling of irradiation growth in single crystal Zr

Irradiation growth of single-crystal Zr is modeled with a reduced set of cluster dynamics equations. Nucleation and growth of basal and prismatic dislocation loops are both accounted for in the model. Equations are developed for the time evolution of single point defects, a limited number of point defect clusters, interstitial and vacancy loop nucleation rates, as well as for the growth of vacancy loops on basal planes and interstitial loops on prismatic planes. Reduction of the usual infinite hierarchy of cluster dynamics equations to the simple set studied here is justified on the physical basis of the stability of small loops once nucleated. This simplified cluster dynamics model with a small number of adjustable parameters avoids the complexity of explicit representation of higher order point defect clusters. The model shows consistency with experimental observations of the following aspects: (1) the growth rates of Zr crystals along the a- and c-axes; (2) the onset dose for breakaway irradiation growth; (3) the saturation dislocation loop densities of vacancy and interstitial loops; (4) the effects of cold work and temperature on irradiation growth.

36 MATERIALS SCIENCE↗

The complex structural and chemical nature of monolithic U-10Mo fuel and Zr barrier layer

Nanoscale microstructural characterization by advanced transmission electron microscopy techniques on a U-10Mo/Zr barrier layer monolithic fuel plate was performed to evaluate the microstructural evaluation after high burn-up. Gas bubble superlattice evolution, grain restructuring, and evolution of the Zr interaction layer is investigated through detailed electron microscopy characterization. The use of automated crystallographic orientation mapping to irradiated U-10Mo fuel highlights that the restructured ultra-fine grains are separated by high angle grain boundaries at a burn up of 4.42 × 10 21 fissions/cm 3 . Additionally, advanced chemical analysis and multi-variable statistical analysis shows spatial clustering of solid fission product precipitates. Finally, characterization of a newly observed porous nanocrystalline Zr region in the barrier layer is studied. Finally, this work provides insights into the grain subdivision and restructuring process while using advanced microscopy techniques to analyze fission products in neutron-irradiated U-10Mo fuel.

36 MATERIALS SCIENCE↗

Plutonium migration and phase evolution in irradiated U-Pu-Zr metallic fuels: An integrated EPMA-SEM-TEM study

Constituent redistribution is a defining feature of irradiated U-Pu-Zr metallic fuels, yet its mechanisms and effects on fuel performance are not sufficiently resolved to guide model development. Although decades of irradiation testing have established broad trends, a true mechanistic understanding of constituent redistribution has not been achieved. Here, in this study, we use electron probe microanalysis (EPMA), scanning electron microscopy (SEM), and transmission electron microscopy-based (TEM) selective area electron diffraction (SAED) on a EBR-II irradiated U-19 wt.% Pu-6 wt.% Zr fuel pin cross-section to correlate the composition, porosity, and crystallographic phases formed after irradiation. Constituent redistribution is thought to consist of three distinct zones, in which uranium and zirconium migrate while plutonium remains relatively unchanged. Our EPMA results resolve eight distinct compositional regions, and more importantly, show that plutonium redistributes alongside zirconium, contrary to historical assumptions. The distribution of fission products was highly asymmetric with a few large lanthanide precipitates observed at isolated sites on the pin periphery instead of a uniform distribution of smaller precipitates around the periphery. Using thermodynamic data from TAF-ID and the measured EPMA compositions, matrix phase fractions were predicted across the fuel radius. Phase predictions based on composition did not match TEM/SAED results, which revealed a much higher fraction of α−U phase than would be expected if phases were retained from reactor temperatures. These findings highlight the need for expanded SAED phase identification to capture post-irradiation and storage effects, as well as rigorous uncertainty quantification in fuel performance and phase diagram modeling to better constrain predictions from compositional data.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multimodal and multiscale strengthening mechanisms in Al-Ni-Zr-Ti-Mn alloy processed by laser powder bed fusion additive manufacturing

The unique thermokinetics of laser-powder bed fusion additive manufacturing (L-PBFAM) has been exploited for development of a novel high-strength Al-Ni-Ti-Zr-Mn alloy. The addition of 0.5 wt% Mn leads to extraordinary improvement in ultimate tensile strength (502 MPa) and work hardening due to the activation of two Mn-induced strengthening mechanisms. First, by a bimodal particle strengthening effect due to Al 31 Mn 6 Ni 12 nano-quasi-crystal particles rejected in inter-dendritic spaces and fibrous Al 3 Ni eutectic dendritic channels, which predominately contributes to the strength improvement, and second by solid solution strengthening from remaining Mn entrapped in Al. These mechanisms supplement the particle strengthening effect imparted by coherent and incoherent Al 3 (Ti,Zr) co-precipitates present at melt pool boundaries, dislocation strengthening due to solidification induced strain, and Hall-Petch and backstress strengthening effect due to heterogenous grain size distribution occurring at various length scales. In conclusion, the solidification dynamics and hierarchical heat distribution that are associated with L-PBFAM resulted in complex spatial variations in these strengthening phenomena and were investigated via a high-throughput multiscale structure–property correlation that involved thermokinetic simulation, X-ray diffraction, high-resolution nanoindentation mapping, and site-specific transmission electron microscopy of the alloy.

36 MATERIALS SCIENCE↗

Laser powder bed fusion of ODS Fe–Cr–Al (0.3Zr, 0.3Y 2 O 3 ): Unveiling processing-microstructure- mechanical property relationships

Here, this study investigates the fabrication of oxide dispersion strengthened (ODS) Fe-Cr-Al alloys via laser powder bed fusion (LPBF) with strategic additions of 0.3 wt% Zr and 0.3 wt% Y 2 O 3 for enhanced mechanical performance in nuclear applications. Systematic processing parameter optimization yielded three distinct conditions: one low-density product with significant defects and two near-full-density materials with improved consolidation. Comprehensive characterization confirmed single-phase α-ferrite matrix formation with successful incorporation of Y-, Zr-, O-, and C-rich precipitates characteristic of ODS alloys. However, precipitate density remained low (∼10 7 cm −3 ), resulting in sink strength values substantially below optimal levels for radiation resistance. Microhardness values (mid-200s HV) correlated inversely with grain size following the Hall-Petch relationship, indicating grain boundary strengthening as the dominant mechanism rather than precipitation strengthening. The optimized processing conditions achieved excellent mechanical properties with room temperature yield strength of approximately 500 MPa and 30 % elongation, demonstrating superior strength-ductility synergy compared to other additively manufactured ODS materials and performance consistent with literature values for LPBF-processed ODS-FeCrAl alloys. This investigation reveals both the potential and limitations of LPBF processing for ODS Fe-Cr-Al alloys. While successful defect-free fabrication was achieved, results highlight the critical need for systematic optimization of processing parameters and post-processing heat treatments to enhance precipitate density for effective dispersion strengthening and radiation resistance while maintaining additive manufacturing advantages.

Additive manufacturing↗

A combined experimental and machine learning exploration of Ti 2-x Zr x MnCrFeNi high entropy Laves hydrides

A series of high entropy AB 2 -type Ti 2-x Zr x MnCrFeNi alloys (x = 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 and 1.2) were synthesized to investigate their potential for hydrogen storage and chemical compression. The influence of the Ti/Zr ratio was explored in terms of structural, microstructural and thermodynamic properties. The storage capacity together with the reaction enthalpy and entropy changes of the synthesized high entropy alloys were compared to predictions from Machine Learning (ML) to investigate changes in these properties across the explored composition space. The results revealed that a decreasing Zr content consistently lowered the hydride formation enthalpy and increased the plateau pressure from 8 to >90 bar H 2 at 25 °C, in good agreement with ML predictions. Selected compositions (x = 1.0 and 1.2) demonstrated reversible hydrogen storage capability over 150 cycles, with capacities of 1.34–1.40 wt % H 2 and remarkable reaction kinetics (<4 min) at ambient temperature. These experimental and computational findings highlight the potential of this Laves-HEA system as tuneable, stable, and cost-effective materials suitable for long-term operations in stationary hydrogen storage and compression applications.

36 MATERIALS SCIENCE↗

Fracture toughness evaluation for Zr-4 clad tubing structure with pellet inserts

Applying fracture mechanics approach to spent nuclear fuel (SNF) system reliability investigation is warranted due to the inherent flaws and hydride structures existed in a SNF system after nuclear reactor operation. However, none of the existing fracture toughness data deal with fuel cladding specific geometry or spent fuel material conditions, such as cladding structure with the pellet-inserts and the associated pellet clad mechanical interactions induced mixed-mode damage mechanisms. Thus, the development of an intrinsic fracture mechanics approach that is suitable for SNF materials is needed. Due to thin wall and small dimension of clad tubing structure, the spiral notch torsion test (SNTT) method of small specimen approach was used to estimate the clad tubing structure fracture toughness. The estimated fracture toughness for Zr-4 cladding with alumina-pellet inserts are presented in this report. For SNTT samples with a short or medium crack length, between 5.4-mm and 8-mm, the estimate JIQ upon fracture initiation for the baseline Zr-4 cladding is at 50 kJ/m2 with 2-sigma uncertainty of 3.26 kJ/m2, and the associated KIQ is at 67.46 MPa√m. For SNTT samples with a long crack length, around 13-mm, the crack initialization is deviated from that of the Mode-I tensile fracture and appears to be a mixed-mode fracture of Mode I – tensile stress and Mode III – out of plane shear stress; the estimated JMQ is at 18.9 kJ/m2, the associated KMQ is at 41.4 MPa√m.

36 MATERIALS SCIENCE↗

Domain-Matching Epitaxy of Ferroelectric Hf 0.5 Zr 0.5 O 2 (111) on La 2/3 Sr 1/3 MnO 3 (001)

Epitaxial ferroelectric HfO2 films are the most suitable to investigate intrinsic properties of the material and for prototyping emerging devices. Ferroelectric Hf 0.5 Zr 0.5 O 2 (111) films were epitaxially stabilized on La 2/3 Sr 1/3 MnO 3 (001) electrodes. This epitaxy, considering the symmetry dissimilarity and the huge lattice mismatch, is not compatible with conventional mechanisms of epitaxy. In this work, to gain insight into the epitaxy mechanism, scanning transmission electron microscopy characterization of the interface was performed, revealing arrays of dislocations with short periodicities. Additionally, these observed periodicities agree with those expected for domain matching epitaxy, indicating that this unconventional mechanism could be the prevailing factor in the stabilization of ferroelectric Hf0.5Zr0.5O2 with (111) orientation in the epitaxial Hf 0.5 Zr 0.5 O 2 (111)/La 2/3 Sr 1/3 MnO 3 (001)heterostructure.

36 MATERIALS SCIENCE↗

Thermally Driven Interfacial Degradation between Li 7 La 3 Zr 2 O 12 Electrolyte and LiNi 0.6 Mn 0.2 Co 0.2 O 2 Cathode

Solid-state batteries offer higher energy density and enhanced safety compared to the present lithium-ion batteries using liquid electrolytes. A challenge to implement them is the high resistances, especially at the solid electrolyte interface with the cathode. Sintering at elevated temperature is needed in order to get good contact between the ceramic solid electrolyte and oxide cathodes and thus to reduce contact resistances. Many solid electrolyte and cathode materials react to form secondary phases. It is necessary to find out which phases arise as a result of interface sintering and evaluate their effect on electrochemical properties. Herein, we assessed the interfacial reactions between LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and Li 7 La 3 Zr 2 O 12 (LLZO) as a function of temperature in air. We prepared model systems by depositing thin-film NMC622 cathode layers on LLZO pellets. The thin-film cathode approach enabled us to use interface-sensitive techniques such as X-ray absorption spectroscopy in the near-edge as well as the extended regimes and identify the onset of detrimental reactions. We found that the Ni and Co chemical environments change already at moderate temperatures, on-setting from 500 °C and becoming especially prominent at 700 °C. By analyzing spectroscopy results along with X-ray diffraction, we identified Li 2 CO 3 , La 2 Zr 2 O 7 , and La(Ni,Co)O 3 as the secondary phases that formed at 700 °C. The interfacial resistance for Li transfer, measured by electrochemical impedance spectroscopy, increases significantly upon the onset and evolution of the detected interface chemistry. Our findings suggest that limiting the bonding temperature and avoiding CO 2 in the sintering environment can help to remedy the interfacial degradation.

36 MATERIALS SCIENCE↗