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At least 37 records · Page 2

In-situ synchrotron X-ray investigation of phase evolution in gas atomized powder enabling manufacturing of nanoscale oxide-dispersion strengthened ferritic steels

Here, we present an investigation of Fe-14Cr-3W-0.4Y-0.4Zr-0.18Ti (wt.%) as a reduced-activation oxide-dispersion strengthened (ODS) ferritic steel, an alternative to the “14YWT” structural alloys designed for nuclear energy applications. Gas atomization reaction synthesis (GARS) was used to produce these Zr-modified powders with a non-equilibrium (metastable) phase that enable a heat treatment (delayed) route for producing nanoscale oxide-dispersion strengthening. In situ synchrotron X-ray diffraction and transmission electron microscopy were used to analyze phase evolution as a function of temperature and time, revealing formation of highly dispersed oxide nanoprecipitate phases at temperatures above those needed for powder consolidation and shaping of components. This would allow fabrication of net-shape parts using conventional powder-processing methods prior to thermal activation of a reaction producing nanocrystalline Y-(Ti, Zr)-O particles, with a size of 20 ± 7 nm. These results can inform processing of tubes, cladding, sheets, and plates for use in advanced fission and fusion reactors.

In-situ synchrotron X-ray diffraction

Ternary molecular switching in a single-crystal optical actuator with correlated crystal strain

A growing portfolio of single-crystal optical actuators is forging a new class of photonic materials that hold prospects for quantum technologies. Ruthenium-based complexes that exhibit this phenomenon via SO 2 -linkage photoisomerisation are of particular interest since they display multiple metastable states, once induced by green light; yet, complete photoconversion into each SO 2 -isomeric state is rarely achieved. We discover a new complex, trans-[Ru(SO 2 )(NH 3 ) 4 (4-bromopyridine)]tosylate 2 , that produces 100% photoconverted η 1 -OSO isomeric crystal structures at 90 K, which fully transition into η 2 -(OS)O photoisomers upon warming to 100 K, while the dark-state η 1 -SO 2 structure is wholly recovered by heating the crystal to room temperature. Crystal structures and optical-absorption profiles of each state are captured via in-situ light-induced single-crystal X-ray diffraction and optical-absorption spectroscopy. Results show that both photoisomeric species behave as optical switches, but with distinct optical properties. The photoisomerisation process causes thermally-reversible micro- and nanoscopic crystal strain, as characterised by optical microscopy and in-situ light-induced atomic-force microscopy.

actuators

Quantification of grain rotation in bulk nanostructured copper via in situ heating white beam synchrotron X-ray diffraction

Grain rotation during microstructural relaxation under heating is conventionally studied extensively through transmission electron microscopy and simulations. However, there is a shortage in examining grain rotations at larger length and volume scales in bulk materials. It is critical to understand the thermal stability of bulk nanostructured metals, since those enhanced mechanical properties have been well recognized. Here, this study aimed to employ a white beam microdiffraction X-ray technique under in situ heating from 300 K to 1073 K at 12 K/min on a nanostructured copper processed by high-pressure torsion, yielding an initial grain size of ∼260 nm before the heating. Evaluation across a wide range of temperatures reveals transition temperatures associated with microstructural relaxation processes. By tracking separate Laue diffraction peaks stemming from individual grains, changes in their orientations can be estimated and quantified. This approach becomes particularly effective when the number of grains within the probed volume is reasonably small. At temperatures above 940 K, about 7.5 % of Cu grains are rotating at speeds of ∼2 × 10 –3 °/s. The radial direction of the disk specimen is found to be the preferred direction of grain rotation, with the rotation axis along the shear direction. Further analysis found no correlation between peak intensity and peak size, related to grain sizes and deviatoric strain, respectively, with rotation conditions or speed. These findings demonstrate that the diffraction technique utilizing white beam X-rays is a complementary and novel characterization tool for understanding microstructural evolution, especially in grain rotations, of bulk crystalline materials.

Grain orientation

Probing the high-pressure densification of amorphous silica nanomaterials using SBA-15: An investigation into the paradoxical nature of the first sharp diffraction peak

The densification and X-ray scattering of mesoporous silica (SBA-15) were measured simultaneously under gigapascal (GPa) pressures. The results are compared to previous work on amorphous silica (aSiO 2 ) and demonstrate the feasibility of measuring the densification of aSiO 2 nanomaterials with small angle X-ray scattering (SAXS) in-situ in a diamond anvil cell. Compared to fused silica, the position of the SBA-15 first sharp diffraction peak (FSDP) is 7 times more sensitive to pressure and has a transition in its pressure dependance at a lower pressure (~2 GPa vs.~13 GPa). SBA-15 has two densification regimes, low-density amorphous and highdensity amorphous, which have equations of state comparable to low-density amorphous and high-density amorphous fused silica. Further, the transition between these two regimes occurs at a lower pressure than for fused silica (~1.5 GPa vs.~13 GPa). The results suggest that there is no direct relationship between the FSDP position and the aSiO 2 density during compression.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

In-situ synchrotron X-ray study on microstructure and stress evolutions of electroplated copper upon self-annealing

Background: The self-annealing behavior of electroplated copper (Cu) at room temperature is gaining attention in the microelectronics industry due to its significant impact on reliability issues such as substrate warpage and electrical resistivity. Methods: In this study, in-situ analysis of the microstructure transition and stress relaxation of the electroplated copper upon self-annealing was conducted via synchrotron white X-ray nanodiffraction (beamline 21A, Taiwan Photon Source) and grazing-incidence X-ray diffraction (beamline 17B1, Taiwan Light Source). Significant Findings: Remarkable relaxations of deviatoric stress and absolute strain component along the [002] direction were closely related to the Cu grain growth and crystallographic reorientation at the early stage of selfannealing, and a complete stress/strain relaxation can be achieved with the cessation of microstructure transition. In conclusion, the in-situ synchrotron X-ray studies provided an insight into Cu self-annealing mechanism, offering valuable information for improving Cu interconnect reliability.

Cu Self-annealing

High-resolution in-situ characterization of laser powder bed fusion via transmission X-ray microscopy at X-ray free electron lasers

In this work, we describe the instrumentation used to perform the first operando transmission X-ray microscopy (TXM) and simultaneous X-ray diffraction of laser melting simulating laser powder bed fusion on the XCS instrument at the Linac Coherent Light Source (LCLS) X-ray free-electron laser (XFEL). Our TXM with 40× magnification in the X-ray regime at 11 keV gave spatial resolutions down to 940 nm per line pair, with effective pixel sizes down to 206 nm, image integration times of <100 fs, and frame rates tunable between 2.1 and 119 ns for two probe frames (0.48 GHz to 8.4 MHz). Images were recorded on Zyla and Icarus (UXI) detectors to trade off between spatial resolution and time dynamics. A 1 kW CW IR laser was coupled into the interaction point to conduct pump–probe studies of laser melting and solidification dynamics. Our temporal and spatial resolution with attenuation-based contrast exceeds that currently possible with synchrotron-based high-speed radiography. This system was sensitive to feature velocities of 10–12000 m s −1 but we did not observe any motion in this range in the laser melting of Al6061 alloy. Shockwaves were not observed and hot cracking proceeded at velocities below the detection limits. Pore accumulation was observed between successive shots, indicating that bubble escape mechanisms were not active. With proper experimental design, the spatial resolution, contrast and field of view could be further improved or modified. The increased brightness and narrower bandwidth of the XFEL allowed for this imaging technique and it lays the groundwork for a wide range of operando techniques to study additive manufacturing.

47 OTHER INSTRUMENTATION

High hardness and oxidation-resistant Cr-containing medium entropy ZrTaW diboride

This study reports the successful synthesis of a Cr-containing (Zr 0.30 Ta 0.34 Cr 0.06 W 0.30 )B 2 medium-entropy boride (MEB) via an in-situ reactive borothermal reduction route from oxide precursors. High-energy ball milling was employed to homogenize the precursor mixture prior to reactive densification. X-ray diffraction confirmed the formation of a predominantly AlB₂-type hexagonal diboride structure together with a secondary (W X , M 1-X )B monoboride phase. Microstructural characterization revealed compositional heterogeneity and localized W-rich regions associated with the secondary phase. The synthesized medium-entropy boride exhibited enhanced mechanical properties, which are attributed to lattice distortion and solid-solution strengthening effects. Thermogravimetric analysis revealed complex multistage oxidation behavior, and the oxidation resistance was compared with conventional ultra-high-temperature diborides. The results demonstrate the strong relationship between oxide-derived processing, compositional complexity, phase evolution, and oxidation behavior, highlighting the potential of medium-entropy borides for high-temperature structural applications

36 MATERIALS SCIENCE

Direct observation of strain-enhanced hydrogen segregation and failure at high-angle grain boundaries in nickel

Understanding the mechanisms underlying hydrogen embrittlement remains difficult, even in single-element metals. Both microstructure and stress state influence hydrogen distribution in metals and alloys, which impacts deformation and failure. Here, in this work, we use in-situ Kelvin probe force microscopy (KPFM) to monitor the hydrogen distribution in pure nickel over time at 1.1 % and 3.5 % strain. The sample strained to 3.5 % results in preferential hydrogen segregation to high-angle grain boundaries whereas the sample strained to 1.1 % does not exhibit preferential hydrogen segregation. Optical digital image correlation (DIC) shows that hydrogen charging results in both localized and reduced strains during tensile testing of a notched sample. Later stages of deformation and failure (e.g. microcracking) are studied by using in-situ transmission X-ray microscopy (TXM). TXM reveals nanoscale structural changes to a propagating crack in a hydrogen environment. Localized void growth and secondary cracking occur at grain boundaries near the primary crack front. Correlative electron backscattering diffraction (EBSD) is used to relate the cracking at grain boundaries to the hydrogen segregation observed in KPFM. These findings are unified in a proposed hydrogen embrittlement mechanism that describes the interaction of hydrogen with grain boundaries, and the role of grain boundaries in hydrogen embrittlement.

Grain boundary fracture

Coupled Chemical and Mechanical Control of Phase Stability in Lanthanide-Substituted BiVO 4

Doping is widely used to enhance the photoelectrochemical performance of BiVO 4 , yet solubility limits and polymorphic stability constrain compositional tuning. Here, in this study, the role of trivalent cation substitution (Ln = La, Nd, Dy, Ho, Y) on pressure-induced phase transformations in Bi 1–x Ln x VO 4 (x ≤ 0.5) is described. Powder X-ray and neutron diffraction reveal that increasing Ln content stabilizes the tetragonal zircon-type polymorph under ambient conditions, while applied pressures of up to ∼5 GPa promote conversion to the monoclinic fergusonite-type polymorph. In-situ neutron diffraction on Bi 0.8 La 0.2 VO 4 shows a reversible monoclinic to tetragonal transition near 2–3 GPa with a bulk modulus of 147 GPa. The extent of conversion depends strongly on dopant identity, concentration, and synthetic route, with mixed-phase solid-state samples converting more efficiently than phase-pure coprecipitated materials. These results demonstrate pressure as a viable pathway to access metastable, doped BiVO 4 compositions beyond conventional solubility limits.

Sypkes, Kathryn I. [University of Sydney, NSW (Aus

Storage-Induced Collapse of Lignin Macromolecular Structure and Its Impacts on the Biorefinery

Lignin plays a vital role in the economics of biorefineries, serving as a source of process energy and a feedstock for sustainable fuels and chemical production. While understanding lignin’s chemical composition is crucial, emerging evidence suggests that a more comprehensive understanding of its macromolecular structure is critical to explaining its complex behavior in the biorefinery. This study investigated the partial collapse of the lignin network in corn stover feedstock after harvest and storage as a result of the microbial digestion of hemicellulose. Fluorescence microscopy was used to detect the collapse of lignin in terms of lignin’s inter-molecular interaction and the re-orientation of lignin’s chromophores, by the changes in lignin’s fluorescence lifetime, anisotropy, and the number of effective emitters. With minimal sample perturbation, our in-situ microscopic results revealed lignin's coil-globule transition phenomena, which was only previously predicted by molecular dynamics modeling extracted lignin in solvent. This collapse of lignin macromolecular structure was confirmed by results from NMR, IR, Raman, and powder X-ray diffraction. We also investigated the impact of this storage-induced collapse on the downstream biorefinery processes. Our study revealed that the two major approaches for lignin valorization in the lignin-first biorefinery model, namely monomer extraction and milled wood lignin extraction, were negatively impacted by the lignin collapse. As changes during storage are a source of feedstock variability, our study highlights the importance of understanding the effect of feedstock handling on biorefinery operations and economics.

09 BIOMASS FUELS

Evolution of dislocations during the rapid solidification in additive manufacturing

Materials processed by fusion-based additive manufacturing (AM) typically exhibit relatively high dislocation densities, along with cellular structures and elemental segregation. This representative structural feature significantly influences material performance; however, post-mortem microstructure characterizations of AM materials cannot capture the dynamic evolution of dislocations during the manufacturing process, thereby offering limited mechanism-based guidance for further advancing AM techniques and facilitating the qualification and certification of AM products. In this study, we conduct operando high-energy synchrotron X-ray diffraction experiments on wire-laser directed energy deposition of 316 L stainless steel. Through a unique configuration, our operando synchrotron experiments semi-quantitatively probe the dislocation density in solid phases and their dynamic changes during solidification and subsequent cooling. By integrating this advanced synchrotron technique with multi-physics simulation, in-situ neutron diffraction, and multi-scale electron microscopy characterization, our mechanistic study aims to elucidate the effects of rapid cooling and subsequent thermal cycling on the dislocation generation and evolution.

36 MATERIALS SCIENCE

Solid-state transformations during laser directed energy deposition of Ti-6Al-4V powder hydride-dehydrided from scrap metals

During laser directed energy deposition (DED-LB), thermal cycling and powder chemical composition produce distinct thermal histories, which vary mechanical properties. Using real-time X-ray diffraction, this study investigates solid-state transformations during DED-LB to understand process-structure-property relationships for angular Ti-6Al-4V powder hydride–dehydrided from scrap metals. Results showed that regions near the molten pool experienced high cooling rates, leading to martensitic transformation from the β phase and increased hardness. Regions farther from the molten pool underwent tempering without solid-state transformation and decreased hardness. These findings support alternative feedstocks for metal additive manufacturing for a circular economy and resilient supply chains.

Additive manufacturing (AM)

Quantifying precursors to void nucleation and coalescence in aluminum

Ductile rupture is a common failure mode for engineering alloys. It is generally comprised of three mechanisms: void nucleation at secondary particles, void growth, and coalescence of voids. Conventional models for ductile rupture have limited precision for predicting macroscopic failure. This is partially because they have been corroborated using ex-situ observations of these three mechanisms and calibrated by macroscopic strain or stress metrics. In this study, in-situ high-energy X-ray characterization was conducted to correlate sites of void nucleation via particle cracking and sites of void growth with grain-scale metrics. Here it is shown that particle cracking is not predicated by elevated stress metrics, which disagrees with classical models. Instead, particle cracking tended to occur for the largest, least spherical particles. This trend persisted on the aggregate-scale and within individual neighborhoods around particles. Furthermore, an Eshelby analysis illuminated a statistically significant increase in maximum principal stress within a cracked particle, compared to an uncracked particle. In-situ observations also revealed two separate examples of intragranular void growth comprised of flat, crack-like features that grew showing alignment with slip systems of the highest resolved shear stress. Post-mortem fractography revealed a secondary population of dimples on these crack-like features, implying that void sheeting may be occurring during this crack-like void growth. Furthermore, these in-situ observations imply that classical models for void growth, that assume a homogenous medium, should be extended to account for the anisotropic grain-level behavior to correctly capture distinct features of void nucleation and growth.

Al-2219

Defect-Driven Redox Interplay on Anatase TiO 2 : Surface-Structure Dependent Activation for CO 2 Hydrogenation Catalysis

Titanium dioxide (TiO 2 ) is one of the most extensively studied oxides as an active catalyst or catalyst support, particularly in energy and environmental applications, but the atomistic mechanisms governing its dynamic response to reactive environments and their correlation to reactivity remain largely elusive. Using in situ environmental transmission electron microscopy (ETEM), synchrotron X-ray diffraction (XRD), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), temperature-programmed reduction (TPR), reactivity measurements, and theoretical modeling, we reveal the dynamic interplay between oxygen loss and replenishment of anatase TiO 2 under varying reactive conditions. Under H 2 exposure, anatase TiO 2 undergoes surface reduction via lattice oxygen loss, forming Ti 3 O 5 . In contrast, CO 2 exposure induces oxygen replenishment, reversing stoichiometry. In mixed H2/CO 2 environments, the reverse water–gas shift (RWGS) reaction proceeds selectively on stepped and high-indexed TiO 2 surfaces, whereas the thermodynamically stable TiO 2 (101) surface remains inactive and intact. Critically, H 2 pretreatment generates oxygen vacancies on TiO 2 (101), transforming it into an active Ti 3 O 5 or defect-rich surface that catalyzes RWGS. By correlating surface structure, defect dynamics, and gas-phase interactions, this work deciphers the competition between H 2 -driven reduction and CO 2 -driven oxidation pathways at the atomic scale. Furthermore, these insights establish defect engineering as a strategic lever to activate inert TiO 2 facets, advancing the design of adaptive catalysts for sustainable fuel synthesis technologies.

36 MATERIALS SCIENCE

In-Situ Visualization of a Growing Brittle Crack in Aluminum Oxynitride Using Synchrotron X-Rays and the Double-Cleavage Drilled Compression Geometry

Brittle fracture is difficult to study in situ due to the speed of a growing crack and the often-catastrophic nature of failure in brittle materials. As a result, the influence of microstructural considerations, such as orientation, grain boundary locations, and strain field, on the crack path remains poorly understood. Presented in this study is a method addressing this knowledge gap, which utilizes the double-cleavage drilled compression geometry to achieve quasi-stable fracture in aluminum oxynitride (AlON). Synchrotron X-ray micro-computed tomography is used to characterize the crack shape and length, while high-energy diffraction microscopy provides information on the strains, orientations, and shapes of grains in the microstructure surrounding the crack tip. During testing, the crack grew in discrete and irregular jumps while the fracture toughness falls within reported ranges. The crack in AlON is found to have no greater tendency to crack intergranularly as compared to transgranularly, and grains which are cracked transgranularly do not display a trend in orientation or stress when compared to those around which the crack followed a grain boundary. The high resolution of the crack path and microstructural data provides a path forward for modeling and understanding 3D brittle fracture.

Gorske, Sara F.

Influence of thermal treatment on structure and catalytic performance of ceria-zirconia supported copper oxide (CuO x /Ce y Zr 1-y O 2 ) catalysts for CO oxidation

Copper oxide (CuO x ) supported on ceria-zirconia (Ce y Zr 1-y O 2 , y = 1.0, 0.5, 0.0) catalysts were investigated to elucidate the effects of thermal treatment on their physicochemical properties and catalytic performance in carbon monoxide (CO) oxidation. Here, the catalysts were synthesized via a one-pot chemical vapor deposition (OP-CVD) method at 700˚C and 900˚C with controlled Cu loading. Characterization techniques, including synchrotron X-ray diffraction (S-XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma spectroscopy (ICP), and N 2 adsorption-desorption, were implemented to probe the crystalline structure, molecular and electronic structure, oxygen vacancies, specific surface area (SSA) and metal loading. CO oxidation was chosen as a model reaction to explore the structure-catalytic performance relationship. A ∼100% CO conversion was achieved at < 150˚C, particularly with the CuO x /CeO 2 catalyst calcined at 700˚C. In contrast, calcination at 900˚C caused a ∼90% decrease in SSA and a ∼24% increase in T 50 . Activity tests revealed that increasing ZrO 2 content lowered CO oxidation activity despite generating more defect sites. In-situ measurement of the 700 °C calcined samples revealed the presence of stable and unstable defects in CuO x /Ce 0.5 Zr 0.5 O 2 and CeO 2 respectively, which play a key role in the activity of the catalysts. The results highlight that catalytic performance is closely related to the SSA. Furthermore, an optimum calcination temperature favor significant oxygen vacancy formation with required CuO x -support interactions, enhancing redox properties and catalytic performance.

36 MATERIALS SCIENCE

Experimental and theoretical investigation of the crystalline surface, film, and interface properties of antiperovskite Mn 3 GaN grown by molecular beam epitaxy on MgO(001)

Here, we present a study of the epitaxial growth, characterization, and theoretical modeling of thin film antiperovskite Mn 3 GaN, an antiferromagnetic material with kagome structure which is grown on MgO (001) substrates using N-plasma-assisted molecular beam epitaxy. Reflection high energy electron diffraction is used to assess the in-plane evolution of the film structure during growth, and the surface is investigated in-situ using scanning tunneling microscopy and Auger electron spectroscopy. These results are combined with precision measurements done ex-situ determining the film lattice constants using a combination of x-ray diffraction with reciprocal space mapping and scanning transmission electron microscopy. Overall, a uniform, homogeneous film with an atomically smooth vacuum surface and atomically sharp substrate interface is found having very small in-plane tensile strain and mild out-of-plane compressive strain. First-principles theoretical calculations are applied in order to ascertain the lowest energy models for both the Mn 3 GaN surface and the Mn 3 GaN/MgO film/substrate interface. Models including MnGa versus MnN surface layers and MnGa versus MnN interfacial layers are considered as functions of both the Mn and Ga chemical potentials. The predictions are discussed in comparison to the experimental results. The overall findings suggest that Mn 3 GaN on MgO(001) is a viable epitaxial film which can be further explored in connection with antiferromagnetic spintronics.

Density functional theory

Fe-single atom catalysts facilitate fast electron transfer with MoS 2 /SnS 2 cathodes in lithium–sulfur batteries

Lithium–sulfur batteries (LSBs) emerge as promising next-generation energy storage systems offering cost-effectiveness, environmental friendliness, and high theoretical energy density. The practical implementation of LSBs faces significant hindrances due to the shuttle effect and sluggish redox reactions. To address these challenges, single-atom catalyst (SAC) based combination materials from d-block elements can offer increased active catalytic sites, rapid charge transfer, accelerated electron migration, and fast sulfur redox conversion kinetics of lithium polysulfides (LiPSs). In this study, we fabricated three different LSB cathodes: pure S, S@MoS 2 /SnS 2 , and S@Fe–MoS 2 /SnS 2 . These cathodes were then used to explore the cycle life, capacity, rate capability, and redox kinetic reactions of LiPSs while assessing the influence of Fe-SACs on their performance. As a result, LSBs with S@Fe–MoS 2 /SnS 2 cathodes demonstrate an extended cycle life of 1000 cycles at a C-rate of 0.2C, maintaining a capacity close to 500 mA h g −1 , the highest initial discharge capacity of 1622 mA h g −1 and 1066 mA h g −1 at 0.05C and 0.2C, and excellent rate capabilities of 708 mA h g −1 and 558 mA h g −1 at 1C and 2C, respectively. The synergistic effect of the Fe-SAC-based combination cathode (S@Fe–MoS 2 /SnS 2 ) creates plentiful adsorptive and highly active catalytic sites, resulting in substantially enhanced capacity for adsorbing soluble long-chain LiPSs. This facilitates ultra-fast redox kinetics, surpassing the performance of the S@MoS 2 /SnS 2 and pure S cathodes. In the ex situ analysis, results from powder X-ray diffraction (XRD) to observe the new phase, soft X-ray absorption spectroscopy (XAS) to investigate the electronic structure, and hard X-ray photoelectron microscopy (HAXPES) with different energies (900 eV, 2000 eV, and 6000 eV) to track the chemical-state evolution of Fe-SACs in MoS 2 /SnS 2 cathodes displayed notable electrochemical reversibility involving S 8 ⇄ LiPSs ⇄ Li 2 S conversion even after 1000 cycles. Additionally, in situ, operando Raman analysis can unveil a novel catalytic mechanism of Fe-SACs in MoS 2 /SnS 2 “facilitating rapid electron transfer” during the discharge and charge processes of LSBs involving the conversion of S 8 ⇄ long-chain LiPSs ⇄ Li 2 S 2 /Li 2 S. This study elucidates the working mechanism of Fe-SAC cathodes, offering insights into overcoming the shuttle effect and facilitating sulfur redox kinetics to advance commercial LSBs.

36 MATERIALS SCIENCE