Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Crystallinity”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,711 records · Page 95
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Unveiling the mechanism of phase and morphology selections during the devitrification of Al-Sm amorphous ribbon

The complex interplay between energetic and kinetic factors that governs the phase and morphology selections can originate at the earliest stage of crystallization in the amorphous parent phases. Because of the extreme difficulties in capturing the microscopic nucleation process, a detailed picture of how initial disordered structures affect the transformation pathway remains unclear. Here, we report the experimental observation of widely varying phase selection and grain size evolution during the devitrification of a homogeneous melt-spun glassy ribbon. Two different crystalline phases, θ-Al 5 Sm and ε-Al 60 Sm 11 , are found to form in the different regions of the same metallic glass ribbon during the devitrification. The grain size of ε-Al 60 Sm 11 phase shows a strong spatial heterogeneity. Coarse-grained ε-Al 60 Sm 11 phase coupled with the small volume fraction of θ-Al 5 Sm phase is preferably formed close to wheel side of the melt-spun ribbon. Combining experimental characterization and computational simulations, we show that phase selection and microstructure evolution can be traced back to different types and populations of atomic clusters that serve as precursors for the nucleation of different crystalline phases. Inhomogeneous cooling rates cause different structure orders across the glass sample during the quenching process. Our findings provide direct insight into the effect of structural order on the crystallization pathways during the devitrification of metallic glass. It also opens an avenue to study the detailed nucleation process at the atomic level using the metallic glass as a platform and suggests the opportunity of microstructure and property design via controlling the cooling process.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Charge-spin interconversion in epitaxial Pt probed by spin-orbit torques in a magnetic insulator

We measure spin-orbit torques (SOTs) in a model system of all-epitaxial ferrite/Pt bilayers to gain insights into charge-spin interconversion in Pt. With negligible electronic conduction in the insulating ferrite, the crystalline Pt film acts as the sole source of charge-to-spin conversion. A small fieldlike SOT independent of Pt thickness suggests a weak Rashba-Edelstein effect at the ferrite/Pt interface. By contrast, we observe a sizable dampinglike SOT that depends on the Pt thickness, from which we deduce the dominance of an extrinsic spin-Hall effect (skew scattering) and Dyakonov-Perel spin relaxation in the crystalline Pt film. Furthermore, our results point to a large internal spin-Hall ratio of ≈ 0.8 in epitaxial Pt. Furthermore, our experimental work takes an essential step towards understanding the mechanisms of charge-spin interconversion and SOTs in Pt-based heterostructures, which are crucial for power-efficient spintronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Cation and anion topotactic transformations in cobaltite thin films leading to Ruddlesden-Popper phases.

Topotactic transformations involve structural changes between related crystal structures due to a loss or gain of material while retaining a crystallographic relationship. The perovskite oxide La0.7Sr0.3CoO3 (LSCO) is an ideal system for investigating phase transformations due to its high oxygen vacancy conductivity, relatively low oxygen vacancy formation energy, and strong coupling of the magnetic and electronic properties to the oxygen stoichiometry. While the transition between cobaltite perovskite and brownmillerite (BM) phases has been widely reported, further reduction beyond the BM phase lacks systematic studies. In this paper, we study the evolution of the physical properties of LSCO thin films upon exposure to highly reducing environments. We observe the rarely reported crystalline Ruddlesden-Popper phase, which involves the loss of both oxygen anions and cobalt cations upon annealing where the cobalt is found as isolated Co ions or Co nanoparticles. First-principles calculations confirm that the concurrent loss of oxygen and cobalt ions is thermodynamically possible through an intermediary BM phase. The strong correlation of the magnetic and electronic properties to the crystal structure highlights the potential of utilizing ion migration as a basis for emerging applications such as neuromorphic computing.

Chiu, I-Ting↗
DOE OSTI2025

Metallic and ferromagnetic carbon allotrope discovered using molecular precursors

Although carbon materials are known for their versatile structures and properties, a crystalline phase of carbon being both metallic and ferromagnetic is yet to be found. Here, using an organic molecular precursor 3,3-dimethyl-1-butene ( C 6 H 12 ) and a comprehensive theoretical study, we have discovered a metastable crystalline carbon phase that is both metallic and ferromagnetic under ambient conditions. The new carbon structures, produced by stacking puckered layers of 4,6-membered rings, are found to exhibit exotic electronic, magnetic, and mechanical properties originating from a special s p 2 − s p 3 bonding topology. These findings open the prospect of realizing the metallic and ferromagnetic carbon allotrope in practice. Published by the American Physical Society 2025

Fang, Hong (ORCID:0000000209688687)↗
DOE OSTI2024

Symmetry Breaking and Ascending in the Magnetic Kagome Metal FeGe

Spontaneous symmetry breaking—the phenomenon in which an infinitesimal perturbation can cause the system to break the underlying symmetry—is a cornerstone concept in the understanding of interacting solid-state systems. In a typical series of temperature-driven phase transitions, higher-temperature phases are more symmetric due to the stabilizing effect of entropy that becomes dominant as the temperature is increased. However, the opposite is rare but possible when there are multiple degrees of freedom in the system. Here, we present such an example of a symmetry-ascending phenomenon upon cooling in a magnetic kagome metal FeGe by utilizing neutron Larmor diffraction and Raman spectroscopy. FeGe has a kagome lattice structure with simple A-type antiferromagnetic order below Néel temperature T N ≈ 400 K and a charge density wave (CDW) transition at T CDW ≈ 110 K , followed by a spin-canting transition at around 60 K. In the paramagnetic state at 460 K, we confirm that the crystal structure is indeed a hexagonal kagome lattice. On cooling to around T N , the crystal structure changes from hexagonal to monoclinic with in-plane lattice distortions on the order of 10 − 4 and the associated splitting of the double-degenerate phonon mode of the pristine kagome lattice. Upon further cooling to T CDW , the kagome lattice shows a small negative thermal expansion, and the crystal structure gradually becomes more symmetric upon further cooling. A tendency of increasing the crystalline symmetry upon cooling is unusual; it originates from an extremely weak structural instability that coexists and competes with the CDW and magnetic orders. These observations are against the expectations for a simple model with a single order parameter and hence can only be explained by a Landau free energy expansion that takes into account multiple lattice, charge, and spin degrees of freedom. Thus, the determination of the crystalline lattice symmetry as well as the unusual spin-lattice coupling is a first step towards understanding the rich electronic and magnetic properties of the system, and it sheds new light on intertwined orders where the lattice degree of freedom is no longer dominant. Published by the American Physical Society 2024

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Designing Ta C Virtual Substrates for Vertical Al x Ga 1 − x N Power Electronics Devices

Power electronics are critical for a sustainable energy future, playing a key role in electrification and integration of renewable energy sources into the grid. Advances in ultrawide band gap materials are needed to handle higher powers in smaller form factors while reducing electrical and thermal losses. High Al content Al x Ga 1 − x N is theoretically capable of meeting these demands, but its impact in power electronics has been severely restricted by a lack of substrates that can satisfy conductivity, lattice matching, and/or thermal expansion requirements. We demonstrate that electrically conductive Ta C can be used as a virtual substrate for Al x Ga 1 − x N heteroepitaxy. Scaleably sputtered Ta C grown on Al 2 O 3 , followed by high-temperature face-to-face annealing, produces a thin film Ta C template with an effective hexagonal lattice constant matched to Al 0.70 Ga 0.30 N . Annealing of the Ta C promotes recrystallization, significantly improving crystallinity and reducing crystalline defects from as-deposited columnar grains to a step-and-terrace surface morphology, enabling the subsequent growth of high-quality Al 0.70 Ga 0.30 N by molecular beam epitaxy. X-ray diffraction and scanning transmission electron microscopy confirm that the Al x Ga 1 − x N layer is heteroepitaxially aligned, strain-free, and lattice-matched, transitioning abruptly from Ta C to Al x Ga 1 − x N without intermediate phases. These results demonstrate Ta C virtual substrates as electrically conductive, lattice-matched, and thermally compatible templates for vertical Al x Ga 1 − x N devices that can meet the growing power needs of a sustainable energy future. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mutations in the Pectin Methyltransferase QUASIMODO2 Influence Cellulose Biosynthesis and Wall Integrity in Arabidopsis

Abstract Pectins are abundant in the cell walls of dicotyledonous plants, but how they interact with other wall polymers and influence wall integrity and cell growth has remained mysterious. Here, we verified that QUASIMODO2 (QUA2) is a pectin methyltransferase and determined that QUA2 is required for normal pectin biosynthesis. To gain further insight into how pectin affects wall assembly and integrity maintenance, we investigated cellulose biosynthesis, cellulose organization, cortical microtubules, and wall integrity signaling in two mutant alleles of Arabidopsis (Arabidopsis thaliana) QUA2, qua2 and tsd2. In both mutants, crystalline cellulose content is reduced, cellulose synthase particles move more slowly, and cellulose organization is aberrant. NMR analysis shows higher mobility of cellulose and matrix polysaccharides in the mutants. Microtubules in mutant hypocotyls have aberrant organization and depolymerize more readily upon treatment with oryzalin or external force. The expression of genes related to wall integrity, wall biosynthesis, and microtubule stability is dysregulated in both mutants. These data provide insights into how homogalacturonan is methylesterified upon its synthesis, the mechanisms by which pectin functionally interacts with cellulose, and how these interactions are translated into intracellular regulation to maintain the structural integrity of the cell wall during plant growth and development.

Biochemistry & Molecular Biology↗
DOE OSTI2024

Tracking copper nanofiller evolution in polysiloxane during processing into SiOC ceramic

Polymer-derived ceramics (PDCs) remain at the forefront of research for a variety of applications including ultra-high-temperature ceramics, energy storage and functional coatings. Despite their wide use, questions remain about the complex structural transition from polymer to ceramic and how local structure influences the final microstructure and resulting properties. This is further complicated when nanofillers are introduced to tailor structural and functional properties, as nanoparticle surfaces can interact with the matrix and influence the resulting structure. The inclusion of crystalline nanofiller produces a mixed crystalline–amorphous composite, which poses characterization challenges. With this study, we aim to address these challenges with a local-scale structural study that probes changes in a polysiloxane matrix with incorporated copper nanofiller. Composites were processed at three unique temperatures to capture mixing, pyrolysis and initial crystallization stages for the pre-ceramic polymer. We observed the evolution of the nanofiller with electron microscopy and applied synchrotron X-ray diffraction with differential pair distribution function (d-PDF) analysis to monitor changes in the matrix's local structure and interactions with the nanofiller. The application of the d-PDF to PDC materials is novel and informs future studies to understand interfacial interactions between nanofiller and matrix throughout PDC processing.

Chemistry↗
DOE OSTI2020

Making sense of vacancy correlations with single-crystal diffuse scattering data

Local ordering of atoms within a crystalline structure is increasingly recognized as essential to understanding the properties of a variety of interesting materials. This is shown by the success of pair distribution function (PDF) analysis of scattering data from powder samples to investigate departures from perfectly crystalline order (Billinge & Kanatzidis, 2004; Egami & Billinge, 2012). Diffuse scattering from single crystals can also be a powerful probe of local order, potentially providing key information that would be difficult to obtain from PDF methods; however, difficulties in both measurement and interpretation of data have too often restricted their use by a larger community. In this issue of IUCrJ, Rothet al.(2020) demonstrate how simple concepts can be applied to better understand single-crystal diffuse scattering from half-Heusler systems.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Psilocybin: crystal structure solutions enable phase analysis of prior art and recently patented examples

Psilocybin {systematic name: 3-[2-(dimethylamino)ethyl]-1 H -indol-4-yl dihydrogen phosphate} is a zwitterionic tryptamine natural product found in numerous species of fungi known for their psychoactive properties. Following its structural elucidation and chemical synthesis in 1959, purified synthetic psilocybin has been evaluated in clinical trials and has shown promise in the treatment of various mental health disorders. In a recent process-scale crystallization investigation, three crystalline forms of psilocybin were repeatedly observed: Hydrate A, Polymorph A, and Polymorph B. The crystal structure for Hydrate A was solved previously by single-crystal X-ray diffraction. This article presents new crystal structure solutions for the two anhydrates, Polymorphs A and B, based on Rietveld refinement using laboratory and synchrotron X-ray diffraction data, and density functional theory (DFT) calculations. Utilizing the three solved structures, an investigation was conducted via Rietveld method (RM) based quantitative phase analysis (QPA) to estimate the contribution of the three different forms in powder X-ray diffraction (PXRD) patterns provided by different sources of bulk psilocybin produced between 1963 and 2021. Over the last 57 years, each of these samples quantitatively reflect one or more of the hydrate and anhydrate polymorphs. In addition to quantitatively evaluating the composition of each sample, this article evaluates correlations between the crystal forms present, corresponding process methods, sample age, and storage conditions. Furthermore, revision is recommended on characterizations in recently granted patents that include descriptions of crystalline psilocybin inappropriately reported as a single-phase `isostructural variant.' Rietveld refinement demonstrated that the claimed material was composed of approximately 81% Polymorph A and 19% Polymorph B, both of which have been identified in historical samples. In this article, we show conclusively that all published data can be explained in terms of three well-defined forms of psilocybin and that no additional forms are needed to explain the diffraction patterns.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Autonomous Polycrystalline Material Decomposition For Hyperspectral Neutron Tomography

Hyperspectral neutron tomography is an effective method for analyzing crystalline material samples with complex compositions in a non-destructive manner. Since the counts in the hyperspectral neutron radiographs directly depend on the neutron cross-sections, materials may exhibit contrasting neutron responses across wavelengths. Therefore, it is possible to extract the unique signatures associated with each material and use them to separate the crystalline phases simultaneously.We introduce an autonomous material decomposition (AMD) algorithm to automatically characterize and localize polycrystalline structures using Bragg edges with contrasting neutron responses from hyperspectral data. The algorithm estimates the linear attenuation coefficient spectra from the measured radiographs and then uses these spectra to perform polycrystalline material decomposition and reconstructs 3D material volumes to localize materials in the spatial domain. Our results demonstrate that the method can accurately estimate both the linear attenuation coefficient spectra and associated reconstructions on both simulated and experimental neutron data.

Samin nur chowdhury, Mohammad↗
DOE OSTI2019

Field-Aged Glass/Backsheet and Glass/Glass PV Modules: Encapsulant Degradation Comparison

Ethylene vinyl acetate (EVA) is the predominant encapsulant in crystalline-silicon photovoltaic (PV) modules; however, its degradation is a subject of major concern, which causes significant power loss under field conditions. This article presents a comparison of EVA degradation in field-aged PV modules with glass/backsheet (G/B) and glass/glass (G/G) architectures. Modulelevel characterization included UV fluorescence imaging and I-V measurements. Material analytical techniques, including colorimetry, differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared spectroscopy, and Raman spectroscopy, were performed to correlate the module performance parameters with EVA material properties. An intense EVA discoloration in G/G modules was observed, which was corroborated by higher module Isc and Pmax degradation rates compared with its counterpart G/B modules. Higher power degradation was accompanied by a significant increase in EVA crosslinking, vinyl acetate content, yellowness index, and presence of functional groups containing unsaturated moieties that are linked to degradation products of photothermal reaction, and a higher decrease in the degree of crystallinity. The absence of a polymeric backsheet in hermetically sealed G/G modules, which restricts photobleaching and enhances the entrapment of volatile acetic acid and other degradation by-products, plays a major role in causing higher EVA degradation in G/G modules. This article concludes that EVA might have been a good choice of an encapsulant for the G/B modules over the decades, but it may prove to be an inappropriate choice for the G/G modules because of potential degassing, corrosion, and/or discoloration issues. Ionomers or polyester-based encapsulants like polyolefins could be best suited for G/G modules as it appears to be a current trend in the industry.

14 SOLAR ENERGY↗
DOE OSTI2020

Comparison of PID Shunting in Polycrystalline and Single-Crystal Silicon Modules via Multi-Scale, Multi-Technique Characterization

We used the methods we reported last year to investigate potential-induced degradation (PID). We have now applied these methods to single-crystalline silicon modules that have degraded during field deployment, as well as in minimodules stressed in the laboratory. We will compare these results to the polycrystalline results presented last year. Small cores have been removed from the modules and subjected to analysis. We use a combination of photoluminescence and dark lock-in thermography imaging, laser marking, electron-beam induced current measurements, and subsequent focused ion-beam marking to allow analysis of individual defects via time-of-flight secondary-ion mass spectrometry (TOF-SIMS) to investigate the root-cause mechanism for PID shunting. We see a direct correlation between recombination active shunts and sodium content. The sodium content in shunted areas peaks at the SiN/Si interface and is consistently observed at a concentration of 0.1%-1% in shunted areas. TOF-SIMS data taken on degraded and non-degraded single-crystalline sample areas show a similar trend as in the polycrystalline samples: more sodium is seen in the degraded areas.

14 SOLAR ENERGY↗
DOE OSTI2021

BACKFLIP: Identification of Materials and Changes Upon Aging of Emerging Fluoropolymer-Free and Industry-Benchmark PV Backsheets

Extending lifetimes of photovoltaic (PV) modules and decreasing manufacturing and decommissioning costs are motivating research of novel PV module backsheet materials. Backsheet integrity is critical to the safety and performance of a PV module, however, the polymeric materials are often vulnerable to environmental degradation. The long-term durability of emerging polyolefin (PO) materials is being examined to inform regarding the possible replacement of laminated backsheets containing polyethylene terephthalate (PET) cores and fluoropolymer protective inner/outer layers. This study compares traditional PET-based backsheets with novel, co-extruded, and recyclable PO-based backsheets after being subjected to hygrometric and UV photolytic accelerated weathering. A large set of characterization methods will compare physical, chemical, structural, mechanical, and insulating properties of these backsheets and the resulting mini-module (MiMo) PV performances. The study of chemical composition, glass- and phase-transition temperatures, degree of crystallinity, and crystalline structure are described here.

mini-module↗
DOE OSTI2021

Representative Modules for Accelerated Thermal Cycling and Static Load Testing

In this work, we explore the influence of module size on the rate of interconnect solder bond thermomechanical fatigue (TMF) damage and the probability of cell fracture. For the solder bond TMF damage evaluation, structural mechanics models of crystalline silicon PV models are created to solve with the Finite Element Method. For the probability of cell fracture evaluation, Weibull analysis and weakest link theory are employed to resolve the probability of crystalline silicon PV cell fracture when measured as bare cells and when stressed in reduced- and full-sized modules. Results conclusively demonstrate that the rate of solder bond TMF damage is independent of module size, interconnect location across the cell and cell location across the module and that smaller, representative, modules must be loaded to a much higher level than their parent full-sized modules to achieve an equivalent driving force for cell fracture.

accelerated testing↗
DOE OSTI2021

Spectral Effects in Albedo and Rearside Irradiance Measurement for Bifacial Performance Estimation

We investigate the impact of spectral dependence of ground surface reflectivity on albedo and rearside irradiance measurements necessary for bifacial photovoltaic (PV) module performance estimation and monitoring. Because PV modules are spectrally selective, albedo and irradiance measurements performed with common irradiance sensors may require spectral mismatch corrections when used for performance prediction. We investigate via simulation the differences in spectrally responsive albedo measured with thermopile pyranometers and crystalline silicon PV reference cells in comparison to a typical crystalline-silicon bifacial PV module. Simulations are performed for nine different representative ground surface materials using simulated solar spectra together with spectral reflectivity data distributed with the SMARTS simulation software. For the materials considered, the results show that albedo spectral mismatch relative to the bifacial module is distributed over a range of ±9.2% for thermopile pyranometers versus only ±3.7% for a typical PV reference cell. We consider the impact of this spectrally-responsive albedo mismatch on bifacial PV module rearside irradiance measurements. Using synthesized rearside spectral irradiance distributions, we find that for the nine different ground surface materials the predicted rearside irradiance measurement deviates from the effective irradiance observed by the PV module by on the order of 16.5 W/m 2 for the pyranometer and 3.6 W/m 2 for the PV reference cell. We discuss the implications for bifacial albedo and irradiance measurement.

41 EE - Solar Energy Technologies Office (EE-4S)↗
DOE OSTI2019

Utilizing TiO 2 amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics

Selective synthesis of metastable polymorphs requires a fundamental understanding of the complex energy landscapes in which these phases form. Recently, the development of in situ high temperature and controlled atmosphere transmission electron microscopy has enabled the direct observation of nucleation, growth, and phase transformations with near atomic resolution. In this work, we directly observe the crystallization behavior of amorphous TiO 2 thin films grown under different pulsed laser deposition conditions and quantify the mechanisms behind metastable crystalline polymorph stabilization. Films deposited at 10 mTorr chamber oxygen pressure crystallize into nanocrystalline Anatase at 325 degrees C, whereas films deposited at 2 mTorr crystallize into significantly larger needle-like grains of Brookite and Anatase at 270 degrees C. Increasing film deposition rate by a factor of 4 results in a 10x increase in the crystalline growth front velocity as well as a decrease in crystallization temperature from 270 degrees C to 225 degrees C. Engineering the amorphous precursor state through deposition conditions therefore provides routes to microstructure control and the accessibility of higher energy metastable phases.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Searching for correlations between vibrational spectral features and structural parameters of silicate glass network

Infrared (IR) and Raman spectroscopic features of silicate glasses are usually interpreted based on the analogy with those of smaller molecules, molecular clusters, or crystalline counterparts; this study tests the accuracy and validity of these widely cited peak assignment schemes by comparing vibrational spectral features with bond parameters of the glass network created by molecular dynamics (MD) simulations. A series of sodium silicate glasses with compositions of [Na 2 O] x [Al 2 O 3 ] 2 [SiO 2 ] 98- x with x = 7, 12, 17, and 22 were synthesized and analyzed with IR and Raman. A silica glass substrate and a crystalline quartz were also analyzed for comparison. Glass structures with the same compositions were generated with MD simulations using three types of potentials: fixed partial charge pairwise (Teter), partial diffuse charge potential (MGFF), and bond order-based charge transfer potential (ReaxFF). The comparison of simulated and experimental IR spectra showed that, among these three potentials tested, ReaxFF reproduces the concentration dependence of spectral features closest to the experimentally observed trend. Hence, the bond length and angle distributions as well as Si– Q n species and ring size distributions of silica and sodium silicate glasses were obtained from ReaxFF-MD simulations and further compared with the peak assignment or deconvolution schemes—which have been widely used since 1970s and 1980s—(a) correlation between the IR peak position in the Si–O stretch region (1050-1120 cm -1 ) and the Si–O–Si bond angle; (b) deconvolution of the Raman bands in the Si–O stretch region with the Q n speciation; and (c) assignment of the Raman bands in the 420-600 cm -1 region to the bending modes of (SiO) n rings with different sizes (typically, n = 3-6). The comparisons showed that none of these widely used methods is congruent with the bond parameters or structures of silicate glass networks produced via ReaxFF-MD simulations. This result invokes that the adequacy of these spectral interpretation methods must be questioned. Alternative interpretations are proposed, which are to be tested independently in future studies.

36 MATERIALS SCIENCE↗