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At least 1,549 records · Page 86

A microstructural signature of the coesite-quartz transformation: New insights from high-pressure experiments and EBSD

Ultra-high pressure (UHP) metamorphism is difficult to identify in continental crust as few petrological barometers are suitable for dominantly felsic lithologies. In such cases, burial to extreme depths is commonly identified through the preservation of coesite, a high-pressure polymorph of SiO 2 that typically forms at depths exceeding ∼ 100 km (i.e., > 2 GPa pressure). Unfortunately, coesite readily transforms to quartz upon exhumation, meaning that UHP terranes may often be overlooked. While some studies have suggested that quartz may inherit an orientation signature indicative of former coesite, both the specific nature of this signature and the conditions favouring its development remain uncertain. Here, to address this problem, we combine electron backscatter diffraction analysis of natural and experimental samples to explore microstructural evolution across the coesite-quartz phase transformation. We demonstrate that neighbouring domains of quartz commonly feature an 84 ± 4° rotation of [c] axes around the pole of a common {m} plane. This orientation relationship is a product of epitaxy, whereby the {$11\bar{2}2$} Japan twin plane in quartz nucleates on the (010) plane in coesite. In supercell simulations, the nucleation of Japan twins can be explained by the energetically favourable alignment of quartz tetrahedra on parental coesite tetrahedra. Through experiments, we demonstrate that this signature emerges over a broad range of conditions, regardless of the availability of nucleation sites (e.g., grain boundaries) or the density of crystal lattice defects (e.g., dislocations). Overall, our work provides a quantitative and unambiguous tool for identifying UHP terranes from quartz in isolation.

Coesite↗

Oscillating plasma bubble and its associated nonlinear studies in presence of low magnetic field

Oscillating plasma bubbles have been created around a cylindrical mesh grid of 75% optical transparency in a DC plasma system with a low magnetic field. Plasma bubbles are created by developing ion density gradient around a cylindrical grid of 20 cm in diameter and 25 cm in height, inserted into the plasma. Relaxation and contraction of the plasma bubbles in the presence of external conditions, such as magnetic field and pressure, have been studied. A Langmuir probe has been used to detect the plasma floating potential fluctuations at different imposed experimental conditions. Nonlinear behavior of the system has been characterized by adopting nonlinear techniques such as Fast Fourier Transform, Phase Space Plot, and Recurrence Plot. It shows that the system creates highly nonlinear phenomena associated with the plasma bubble under the imposed experimental conditions. A theoretical and numerical model has also been developed to satisfy the observed experimental analysis. Moreover, observations are extended further to study the growth of instability associated with the plasma bubbles. The intention of the present work is to correlate the findings about plasma bubbles and their related instability with the one existing in the equatorial F-region of the ionosphere.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Nucleation and growth of blue phase liquid crystals on chemically-patterned surfaces: a surface anchoring assisted blue phase correlation length

In condensed matter, the correlation length is an essential parameter which describes the distance over which a material maintains its structural properties. In liquid crystals, for the orientational order parameter this characteristic length is of the order of nanometers, while in solid crystals it can extend to macroscopic length scales. Here, we report the measurement of the correlation length, or persistence length, of the crystallographic orientation of blue phases (BPs)—chiral liquid crystals with long-range 3D-crystalline structures and submicron-sized lattice-parameters. These materials exhibit phase transformations that have been identified as the liquid analog of crystal-crystal martensitic transformations. In this work, we use liquid epitaxial growth to achieve spontaneous BP-crystal nucleation and subsequent growth. Specifically, we design patterned substrates made of a binary array of regions with different liquid crystal anchoring, which facilitate a uniform nucleation and growth of BP-crystals with (100)-lattice orientation and a simple cubic symmetry. Furthermore, our results indicate that this simple cubic BP, the so-called blue phase II (BPII), forms first on the patterned surface, thereby propagating the growth of domains in directions parallel or perpendicular to the patterned regions. These results are used to understand the emergence of a surface anchoring assisted BPII-correlation length, taken as the distance over which the BP preserves its lattice orientation, as a function of time and pattern characteristics. We found that BPII single crystals can be achieved on patterned regions whose lateral dimensions are equal to or larger than 10 μm, consistent with our measurements of the BPII-correlation length. This newly acquired understanding of the role of surfaces on the formation of BPs is then used to design processes that permit formation of macroscopically large mono-domain, single-crystal BPs by relying on significantly reduced patterned areas (only part of the area is patterned), a feature that could benefit the applications of this intriguing class of materials.

correlation length↗

Interplay between electron localization, magnetic order, and Jahn-Teller distortion dictates LiMnO2 phase stability

The development of manganese (Mn)-rich cathodes for Li-ion batteries promises to alleviate potential supply chain bottlenecks in battery manufacturing. Fundamental challenges in Mn-rich cathodes arise from phenomena such as structural changes due to cooperative Jahn-Teller (JT) distortions of in octahedral environments, Mn migration, and phase transformations to spinel-like order, all of which affect the electrochemical performance. These physically complex phenomena motivate an re-examination of the Li-Mn-O rock-salt space, with a focus on the thermodynamics of the prototypical, polymorphs. It is found that the generalized gradient approximation (GGA-PBEsol) and meta-GGA ( ) density functionals with empirically fitted on-site Hubbard corrections yield spurious stable phases for , such as predicting a phase with -like order ( ) to be the ground state instead of the orthorhombic (Pmmn) phase, which is the experimentally known ground state. Accounting for antiferromagnetic order in each structure is shown to have a substantial effect on the total energies and resulting phase stability. By using hybrid-GGA (HSE06) and GGA with self-consistent Hubbard parameters (on-site and inter-site ) calculated from linear response theory, the experimentally observed phase stability trends are recovered. The calculated on-site between Mn- states in the experimentally observed orthorhombic, layered, and spinel phases are significantly smaller than in and disordered layered structures, by within GGA. The smaller values of are shown to be correlated with a collinear ordering of JT distortions, in which all orbitals are oriented in the same direction. This cooperative JT effect can lead to greater electron delocalization from Mn along the states due to increased Mn-O covalency, which contributes to the greater electronic stability compared to the phases with noncollinear JT arrangements. The structures with collinear ordering of JT distortions also generate greater vibrational entropy, which helps stabilize these phases at high temperature. These phases are shown to be strongly insulating with large calculated band gaps , which are computed using HSE06 and .

Kam, Ronald L↗

Tethered balloon system and High-Resolution Mass Spectrometry Reveal Increased Organonitrates Aloft Compared to the Ground Level

Atmospheric particles play critical roles in climate. However, significant knowledge gaps remain regarding the vertically resolved organic molecular-level composition of atmospheric particles due to aloft sampling challenges. To address this, we use a tethered balloon system at the Southern Great Plains Observatory and high-resolution mass spectrometry to, respectively, collect and characterize organic molecular formulas (MF) in the ground level and aloft (up to 750 m) samples. We show that organic MF uniquely detected aloft were dominated by organonitrates (139 MF; 54% of all uniquely detected aloft MF). Organonitrates that were uniquely detected aloft featured elevated O/C ratios (0.73 ± 0.23) compared to aloft organonitrates that were commonly observed at the ground level (0.63 ± 0.22). Unique aloft organic molecular composition was positively associated with increased cloud coverage, increased aloft relative humidity (~40% increase compared to ground level), and decreased vertical wind variance. Furthermore, 29% of extremely low volatility organic compounds in the aloft sample were truly unique to the aloft sample compared to the ground level, emphasizing potential oligomer formation at higher altitudes. Overall, this study highlights the importance of considering vertically resolved organic molecular composition (particularly for organonitrates) and hypothesizes that aqueous phase transformations and vertical wind variance may be key variables affecting the molecular composition of aloft organic aerosol.

54 ENVIRONMENTAL SCIENCES↗

Activity and Stability of (Pr 1-x Nd x ) 2 NiO 4 as Cathodes for Solid Oxide Fuel Cells: Part V. In Situ Studies of Phase Evolution

This study is to complement an early report (the manuscript is attached for review purpose) on the role of interlayer on activity and performance stability in praseodymium nickelates. The aforementioned report showed a remarkable 48% increase in power density while switching from common GDC interlayer to a new interlayer chemistry (PGCO). Furthermore, a stable long-term performance was linked with suppressed reaction between the cathode and PGCO interlayer. In this article, we report in situ studies of the phase evolution. The high energy XRD studies at a synchrotron source showed fully suppressed phase transition in praseodymium nickelates with PGCO interlayer, while the electrodes on the GDC interlayer undergo substantial phase transformation. Furthermore, in operando and post-test XRD analyses shown fully suppressed structural changes in electrodes operated in full cells at 750°C and 0.80 V for 500 hours. SEM-EDS analysis showed that the formation of PrO x at the cathode-interlayer interface may play a role in a decrease of mechanical integrity of the interfaces, due to thermal expansion mismatch, leading to a local stress between the two phases. Furthermore, phase evolution at a narrow interface may propagate toward the electrode bulk, leading to structural changes Q1 and performance degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Making Every Microgram Count: Nanocalorimetry for Nuclear and Ultra-Rare Materials

The thermal analysis of nuclear and ultra-rare materials plays an important role in nuclear energy, planetary, environmental, and technological settings. Heat effects associated with the sample temperature, heat capacity, phase transformation, radiation damage and crystallographic defects are some of the thermochemistry measurements made with conventional differential scanning calorimeters. However, the measurement capabilities of the of traditional DSCs are often restricted when studying limited ultra-rare accessory minerals or materials submitted to extreme conditions, such as radiation in the nuclear fuel cycle and high pressure. We investigate the usage of nanocalorimetry for the energetic analysis of nuclear or ultra-rare materials, such as irradiated materials and high-pressure phases, with an emphasis on radiation damage and heat capacity measurements. Examples of how nanocalorimetry has been previously used for phase transitions, melting, and nucleation in ultra-fast heating and cooling rates are presented. Finally, an outlook of the field and future work, including beneficial safety and environmental outcomes from the potential usage of nanocalorimetry, are shown.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Reconfigurable self-assembly of porous anisotropic colloids in nematic liquid crystals

Dispersions of anisotropic nanoparticles in liquid crystalline hosts recently yielded new soft condensed matter states, like the thermally reconfigurable monoclinic and orthorhombic biaxial nematic liquid crystals, with a plethora of unusual phases and phase transformations. Our current study shows that the nanoscale porous nature of colloids with micrometer-range overall dimensions also enables highly reconfigurable orientations and assemblies of the microparticles, allowing for realization of condensed matter states with unusual combinations of low-symmetry nematic or smectic order and fluidity. Much like the anisotropic nanoparticles studied previously, these nanoporous anisotropic colloids exhibit thermally reconfigurable oriented alignment with respect to the far-field director, as well as diverse low-symmetry liquid crystalline phase behaviors. Furthermore, our findings open doors to fundamental and applied uses of low-symmetry molecular-colloidal orientationally ordered states of matter with uninhibited fluidity, as well as liquid crystals with partial positional ordering, like low-symmetry smectics, which could lead to applications in metamaterial designs, electro-optics, photonics, etc.

colloidal dispersion↗

Laser-driven ramp-compression experiments on the national ignition facility

This report details the analyses and related uncertainties in measuring longitudinal-stress–density paths in indirect laser-driven ramp equation-of-state (EOS) experiments. Experiments were conducted at the National Ignition Facility (NIF) located at the Lawrence Livermore National Laboratory. The NIF can deliver up to 2 MJ of laser energy over 30 ns and provide the necessary laser power and control to ramp compress materials to TPa pressures (1 TPa = 10 × 10 6 atmospheres). These data provide low-temperature solid-state EOS data relevant to the extreme conditions found in the deep interiors of giant planets. In these experiments, multi-stepped samples with thicknesses in the range of 40–120 µm experience an initial shock compression followed by a time-dependent ramp compression to peak pressure. Interface velocity measurements from each thickness combine to place a constraint on the Lagrangian sound speed as a function of particle velocity, which in turn allows for the determination of a continuous stress–density path to high levels of compressibility. In this report, we present a detailed description of the experimental techniques and measurement uncertainties and describe how these uncertainties combine to place a final uncertainty in both stress and density. Here, we address the effects of time-dependent deformation and the sensitivity of ramp EOS techniques to the onset of phase transformations.

47 OTHER INSTRUMENTATION↗

Time at Temperature Experiments on Neutron Irradiated Zircaloy-2 using Conventional & Flash DSC

Dryout events in Boiling Water Reactors (BWRs) are currently treated by NRC regulations as automatic disqualification for continued fuel rod operation, even though this criterion does not account for the rate or duration of power increases, associated changes in material behavior, or the possibility of rewetting. Operational history from Anticipated Operational Occurrences (AOOs) shows that short, transient power excursions often demand only modest heat removal, and industry experience suggests that fuel can briefly enter dryout yet return to safe, stable operation. The lack of detailed understanding of the material response during such events motivates the present series of experiments. This study uses unique and innovative methods to investigate microstructural evolution in irradiated Zircaloy-2 exposed to high temperatures in inert environments. Differential Scanning Calorimetry (DSC) and FlashDSC are combined to build a comprehensive experimental framework capable of identifying the a–ß phase transformation in zirconium and examining defect annealing under steep thermal gradients. FlashDSC enables rapid heating and cooling of Focused Ion Beam (FIB)–prepared large-area lift-outs (LALOs) of irradiated Zircaloy-2 at rates of 1,000 K/s to peak temperatures of 600°C, 750°C, and 900°C. The goal is to determine whether these conditions produce measurable microstructural changes that could influence cladding performance in typical BWR environments. Microstructural characterization includes quantifying dislocation density and assessing secondary phase particle (SPP) size and distribution using Transmission Electron Microscopy (TEM). Ongoing analysis, such as diffraction pattern indexing and 4D STEM processing, will further refine these observations.

36 - MATERIALS SCIENCE↗

Effect of carbonate and phosphate ratios on the transformation of calcium orthophosphates

Graphical abstract: Complexes among phosphate, carbonate and calcium have been prepared via a facile hydrothermal route. The synthesized product at the low (0.15) and the high (1.8) molar ratio of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} is calcium phosphate hydrate and hydroxylapatite (HAp), respectively. Molar ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} are effective on the reduction of carbonate activity during the crystallization of HAp. - Highlights: • Formation of different complexes from CO{sub 3}{sup 2−}, PO{sub 4}{sup 3−} and Ca{sup 2+} solutions at 60 °C. • Molar ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2} cause changes in phase and size of synthesized products. • Addition of PO{sub 4}{sup 3} inhibited the activity of CO{sub 3}{sup 2−} during bound with Ca{sup 2+}. • The phase transformation was completed, when CO{sub 3}{sup 2−} peaks disappeared in FTIR. • PO{sub 4}{sup 3−}, CO{sub 3}{sup 2−} and Ca{sup 2+} distributed heterogeneously on the surface of precipitation. - Abstract: Complexes among phosphate, carbonate and calcium have been synthesized by a designed hydrothermal method. Effects of carbonate and phosphate ratios on the transformation of calcium-orthophosphates were investigated. With X-ray diffraction measurement the synthesized product at the low (0.15) and the high (1.8) molar ratio of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} is calcium phosphate hydrate at pH 9.0, and hydroxylapatite (HAp) at pH 8.0, respectively. Fourier transform infrared spectroscopy of product at the high ratio (1.8) of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} shows that the CO{sub 3}{sup 2−} peaks disappear, and the strong peaks at 1412 and 1460 cm{sup −1} are assigned to the vibrations of PO{sub 4}{sup 3−} in HAp. {sup 31}P nuclear magnetic resonance spectra of products at the low (0.15–0.6) to the high (1.2–1.8) ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} are obtained at 2.9 and 2.7 ppm, respectively. Molar ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} are effective on the reduction of carbonate activity during the formation and infiltration events of calcium-phosphate surface precipitates, and are subsequently enclosed during HAp formation.

36 MATERIALS SCIENCE↗

Quench process modeling & simulation in the heat-treatment of critical aerospace components

To manufacture light-weight, advanced metal alloy components for gas turbine engines, quench heat-treatment processes are typically used. By quenching the component from elevated temperatures, the alloy sometimes undergoes a solid-state phase transformation which produces special microstructures with the required, enhanced mechanical properties. However, the quenching can also lead to cracks forming in the component. Addressing the quench cracking problems adds a significant burden to the cost, schedule, and energy demand of manufacture. Currently, optimizing the quench process to mitigate or avoid the cracking is performed largely by trial-and-error, relying heavily on costly experimental (thermocouple)trials to understand the local thermal gradients which cause the cracks to form. In this first part (Phase 1) of the work, high-performance computing is employed to establish the ability of modern CFD (computational fluid dynamics) to alleviate or wholly replace the experimental quenching trials by virtual testing. A Baseline CFD model is defined and its accuracy established to be comparable to(and which usually exceeds) the accuracy of existing HTC (heat-transfer coefficient) based simulation methods of quenching. As a first-principles based approach, “calibration” of the Baseline CFD model is independent of the quench process itself, but instead relies on the accuracy of the underlying (modeled),generic two-phase fluid processes which cannot be currently resolved by CFD for large, industrial-scale cases. A novel, high-fidelity DNS capability has been developed and verified to examine and further improve upon the mean-field closure submodels on which the Baseline CFD approach is based.1

99 GENERAL AND MISCELLANEOUS↗

Quench process modeling & simulation in the heat-treatment of critical aerospace components

To manufacture light-weight, advanced metal alloy components for gas turbine engines, quench heat-treatment processes are typically used. By quenching the component from elevated tempera-tures, the alloy sometimes undergoes a solid-state phase transformation which produces special microstructures with the required, enhanced mechanical properties. However, the quenching can also lead to cracks forming in the component. Addressing the quench cracking problems adds a significant burden to the cost, schedule, and energy demand of manufacture. Currently, optimizing the quench process to mitigate or avoid the cracking is performed largely by trial-and-error, relying heavily on costly experimental (thermocouple) trials to understand the local thermal gradients which cause the cracks to form. In this first part (Phase 1) of the work, high-performance computing is employed to establish the ability of modern CFD (computational fluid dynamics) to alleviate or wholly replace the experimental quenching trials by virtual testing. A baseline CFD model is defined and its accuracy established to be comparable to (and which usually exceeds) the accuracy of existing HTC (heat-transfer correlation) based simulation methods of quenching. As a first-principles based approach, “calibration” of the Baseline CFD model is independent of the quench process itself, but instead relies on the accuracy of the underlying (modeled), generic two-phase fluid processes which cannot be currently resolved by CFD for large, industrial-scale cases. A novel, high-fidelity DNS capability has been developed and verified to examine and further improve upon the mean-field closure submodels on which the Baseline CFD approach is based.

36 MATERIALS SCIENCE↗

In situ visualization of metallurgical reactions in nanoscale Cu/Sn diffusion couples

The Cu–Sn metallurgical soldering reaction in two-segmented Cu–Sn nanowires is visualized by in-situ transmission electron microscopy. By varying the relative lengths of Cu and Sn segments, we show that the metallurgical reaction starts at ~ 200 ° with the formation of a Cu–Sn solid solution for the Sn/Cu length ratio smaller than 1:5 while the formation of Cu–Sn intermetallic compounds (IMCs) for larger Sn/Cu length ratios. Upon heating the nanowires up to ~ 500 °C, two phase transformation pathways occur, η-Cu₆Sn₅ → ε-Cu₃Sn → δ-Cu₄₁Sn₁₁ for nanowires with a long Cu segment and η-Cu₆Sn₅ → ε-Cu₃Sn → γ-Cu₃Sn with a short Cu segment. The dynamic in situ TEM visualization of the evolution of Kirkendall voids demonstrates that Cu diffuses faster both in Sn and IMCs than that of Sn in Cu₃ and IMCs, which is the underlying cause of the dependence of the IMC formation and associated phase evolution on the relative lengths of the Cu and Sn segments.

36 MATERIALS SCIENCE↗

Optical transient grating pumped X-ray diffraction microscopy for studying mesoscale structural dynamics

Abstract A fundamental understanding of materials’ structural dynamics, with fine spatial and temporal control, underpins future developments in electronic and quantum materials. Here, we introduce an optical transient grating pump and focused X-ray diffraction probe technique (TGXD) to examine the structural evolution of materials excited by modulated light with a precisely controlled spatial profile. This method adds spatial resolution and direct structural sensitivity to the established utility of a sinusoidal transient-grating excitation. We demonstrate TGXD using two thin-film samples: epitaxial BiFeO 3 , which exhibits a photoinduced strain (structural grating) with an amplitude proportional to the optical fluence, and FeRh, which undergoes a magnetostructural phase transformation. In BiFeO 3 , structural relaxation is location independent, and the strain persists on the order of microseconds, consistent with the optical excitation of long-lived charge carriers. The strain profile of the structural grating in FeRh, in comparison, deviates from the sinusoidal excitation and exhibits both higher-order spatial frequencies and a location-dependent relaxation. The focused X-ray probe provides spatial resolution within the engineered optical excitation profile, resolving the spatiotemporal flow of heat through FeRh locally heated above the phase transition temperature. TGXD successfully characterizes mesoscopic energy transport in functional materials without relying on a specific transport model.

36 MATERIALS SCIENCE↗

Surface Structural and Chemical Evolution of Layered LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) under High Voltage and Elevated Temperature Conditions

This work reports new insights into structural and chemical evolution of surface phases of LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) held at constant high voltages (up to 4.75 V) as well as high temperatures (60 °C) by correlating crystal structure using high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) imaging with chemistry using electron energy loss spectroscopy (EELS). We also followed the Al distribution within individual NCA particles by X-ray energy dispersive spectroscopy (EDS). The progression of these phases as a function of distance from the edge shows simultaneous evolution of crystal structures and chemistry from rocksalt to layered, forming a complete solid solution. We have also observed an extended disordered phase with rocksalt (Fm3m) symmetry in which quantitative electron energy loss spectroscopy reveals it to be an oxygen deficient cation disordered phase with chemical characteristics, as determined by EELS, similar to spinel. The formation of these disordered phases with cation and oxygen vacancies has been driven by surface oxygen loss caused by reactions with the electrolyte followed by cation migration from the octahedral 3a M (M = Ni, Co, Al) layer to the octahedral 3b Li layer. These surface rocksalt phases are not fully dense as they contain Al and Li as well as a high concentration of cation and oxygen vacancies. After discharge, Li is detected within these phases indicative that Li transport has occurred through these rocksalt phases. At 60 °C and 4.75 V a very large impedance rise is observed leading to complete cell irreversibility which is caused by significant metal dissolution from the cathode and formation of surface porosity. In the near surface region of some particles, a phase transformation from R3m (O3) to P3m1 (O1) is also observed which has become thermodynamically stable from complete delithiation as well as from local Al surface depletion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗