Structural Chemistry of Akdalaite, Al[subscript 10]O[subscript 14](OH)[subscript 2], the Isostructural Aluminum Analogue of Ferrihydrite
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A regeneratively-cooled nozzle is a critical component for expansion of the hot gases to enable high temperature and performance liquid rocket engines systems. Channel wall nozzles are a design solution used across the propulsion industry as a simplified method to fabricate the nozzle structure with internal coolant passages. The scale and complexity of the channel wall nozzle (CWN) design is challenging to fabricate leading to extended lead times and higher costs. Some of these challenges include: 1) unique and high temperature materials, 2) Tight tolerances during manufacturing and assembly to contain high pressure propellants, 3) thin-walled features to maintain adequate wall temperatures, and 4) Unique manufacturing process operations and tooling. The United States (U.S.) National Aeronautics and Space Administration (NASA) along with U.S. specialty manufacturing vendors are maturing modern fabrication techniques to reduce complexity and decrease costs associated with channel wall nozzle manufacturing technology. Additive Manufacturing (AM) is one of the key technology advancements being evaluated for channel wall nozzles. Much of additive manufacturing for propulsion components has focused on powder bed fusion, but the scale is not yet feasible for application to large scale nozzles. NASA is evolving directed energy deposition (DED) techniques for nozzles including arc-based deposition, blown powder deposition, and Laser Wire Direct Closeout (LWDC). There are different approaches being considered for fabrication of the nozzle and each of these DED processes offer unique process steps for rapid fabrication. The arc-based and blown powder deposition techniques are being used for the forming of the CWN liner. A variety of materials are being demonstrated including Inconel 625, Haynes 230, JBK-75, and NASA HR-1. The blown powder DED process is also being demonstrated for forming an integral channel nozzle in a single operation in similar materials. The LWDC process is a method for closing out the channels within the liner and forming the structural jacket using a localized laser wire deposition technique. Identical materials mentioned above have been used for this process in addition to bimetallic closeout (C-18150–SS347, and C-18150–Inconel 625). NASA has completed process development, material characterization, and hot-fire testing on a variety of these channel wall nozzle fabrication techniques. This paper will present an overview of the various processes and materials being evaluated and the results from the hot-fire testing. Future development and technology focus areas will also be discussed relative to channel wall nozzle manufacturing.
A regeneratively-cooled or dump-cooled nozzle is a critical component for expansion of hot gases to enable high temperature and performance in liquid rocket engines systems. Regeneratively-cooled channel wall nozzles are a design solution used across the propulsion industry as a simplified method to fabricate the nozzle structure with internal coolant passages. The scale and complexity of the channel wall nozzle (CWN) design can be challenging to fabricate which results in extended lead times and higher costs. Some of these challenges include: 1) Unique and high temperature materials, 2) Tight tolerances on large parts during manufacturing and assembly to contain high pressure propellants, 3) Thin-walled features to maintain adequate wall temperatures, and 4) Unique manufacturing process operations and complex tooling. The United States (U.S.) National Aeronautics and Space Administration (NASA) and U.S. specialty manufacturing vendors are maturing modern fabrication techniques to reduce complexity and decrease costs associated with channel wall nozzle manufacturing technology. Additive Manufacturing (AM) is one of the key technology advancements under evaluation for channel wall nozzles. Much of additive manufacturing for propulsion components has focused on laser powder bed fusion (L-PBF), but the scale is not yet feasible for application to large scale nozzles. NASA is evolving directed energy deposition (DED) techniques for nozzles including arc-based deposition, blown powder deposition, and Laser Wire Direct Closeout (LWDC). There are different approaches being considered for fabrication of the nozzle, and each of these DED processes offer unique process steps for rapid fabrication. The arc-based and blown powder deposition techniques are used for the forming of the CWN liner. A variety of materials are being demonstrated including Inconel 625, Haynes 230, JBK-75, and NASA HR-1. The blown powder DED process is also being demonstrated for forming an integral channel nozzle in a single operation in similar materials. The LWDC process is a method for closing out the channels within the liner and forming the structural jacket using a localized laser wire deposition technique. Identical materials mentioned above have been used for this process in addition to bimetallic closeout (C-18150–SS347, and C-18150–Inconel 625). NASA has completed process development, material characterization, and hot-fire testing on a variety of these channel wall nozzle fabrication technique. This publication presents an overview of the various channel wall nozzle manufacturing processes and materials under evaluation including results from the hot-fire testing. Future development and technology focus areas is also discussed relative to channel wall nozzle manufacturing.
Nonstoichiometric lead oxides play a key role in the formation and cycling of the positive electrodes in a lead acid battery. These phases have been linked to the underutilization of the positive active material but also play a key role in the battery’s cycle life, providing inter-particle adhesion and the connection to the underlying lead grid. Similar phases have previously been identified by mass loss or color change during thermal annealing of PbO2 to PbO, suggesting that at least two intermediate PbOx phases exist. Using multiple in situ analysis techniques (powder diffraction, x-ray absorption, x-ray photoelectron spectroscopy) and ex situ nuclear magnetic resonance measurements, the structural conversion and changes in the lead oxidation states were identified during this process. Isolation of the PbOx phases enabled confirmation of Pb3O5 and Pb2O3 by diffraction and the first 207Pb NMR measurement of these intermediates.
Abstract Methionine side chains are flexible entities which play important roles in defining hydrophobic interfaces. We utilize deuterium static solid‐state NMR to assess rotameric inter‐conversions and other dynamic modes of the methionine in the context of a nine‐residue random‐coil peptide (RC9) with the low‐complexity sequence GGKGMGFGL. The measurements in the temperature range of 313 to 161 K demonstrate that the rotameric interconversions in the hydrated solid powder state persist to temperatures below 200 K. Removal of solvation significantly reduces the rate of the rotameric motions. We employed 2 H NMR line shape analysis, longitudinal and rotation frame relaxation, and chemical exchange saturation transfer methods and found that the combination of multiple techniques creates a significantly more refined model in comparison with a single technique. Further, we compare the most essential features of the dynamics in RC9 to two different methionine‐containing systems, characterized previously. Namely, the M35 of hydrated amyloid‐β 1–40 in the three‐fold symmetric polymorph as well as Fluorenylmethyloxycarbonyl (FMOC)‐methionine amino acid with the bulky hydrophobic group. The comparison suggests that the driving force for the enhanced methionine side chain mobility in RC9 is the thermodynamic factor stemming from distributions of rotameric populations, rather than the increase in the rate constant.
Here, advanced microstructural characterization techniques, such as scanning electron microscopy (SEM) and scanning transmission electron microscopy - energy dispersive x-ray spectroscopy (STEM-EDS), were used to interpret the fuel microstructure evolution and fission products behavior in U-Mo dispersion fuel irradiated in the Advanced Test Reactor (ATR) as part of the European Mini-Plate Irradiation Experiment (EMPIrE) test. The larger as-fabricated fuel grain size achieved by heat-treating the U-Mo powder resulted in slower high burnup structure (HBS) development and reduced fission gas porosity. Slower HBS kinetics was observed at the fuel kernels’ periphery, which contained smaller and less fission gas bubbles at all fission densities (FDs) investigated and was attributed to a locally reduced damage density and fission products concentration, as corroborated with Monte Carlo simulations. The non-refined grains at the fuel kernel periphery hosted a perfectly ordered fission Gas Bubble Superlattice (GBS) up to 6.3 × 10 21 fissions/cm 3 . Nano-scale STEM-EDS analysis presented in this study provided useful information on the GBS characteristic morphology and evolution in U-Mo fuel. The concentration of fission gas in the GBS progressively increased with FD, pointing to an evolution of the nanobubble pressure status with irradiation. A possible connection between the GBS collapse and HBS onset is proposed for which there exists a threshold in the misorientation of the refined sub-grains above which the GBS stability during irradiation is no longer preserved, resulting in the GBS collapse.
Here, we present neutron diffraction, electronic structure calculations, and optical vibrational spectroscopic characterization of hydronium uranyl phosphate (HUP), the synthetic analog of chernikovite ((H 3 O)(UO 2 )(PO 4 )·3H 2 O) to gain insight into structural features of the hydronium cation in the solid state. HUP crystallizes in P2 1 /c instead of previously reported P4/ncc 1 at room temperature and Pccn below 302 K. Lower symmetry was required due to hydronium and interstitial water positions within the structure. Crystallographic positions of hydronium cations determined from powder neutron diffraction data are bolstered by Raman and attenuated total reflectance infrared spectroscopic measurements and are further informed by density functional theory with phonon eigenvector analysis for spectral assignments. Finally, HUP and its arsenate analog (trogerite, (H 3 O)(UO 2 )(AsO 4 )·3H 2 O), (HUAs) were studied using He 2+ irradiation as an analog for α radiolysis to investigate the irradiation stability of these phases and the stability of hydronium cations in the solid state. Dose studies were employed wherein each sample was irradiated to 5, 10, 15, 25, and 50 MGy. Structural insight regarding irradiated materials is gained using optical vibrational spectroscopy and powder X-ray diffraction. Surprising irradiation stability of HUAs was found up to 50 MGy of dose, which may have important implications for understanding and modeling the geologic stability of legacy U.
A linear thermoplastic polyimide, LARC-TPI, has been characterized and developed for a variety of high-temperature applications. In its fully imidized form, this new material can be used as an adhesive for bonding metals such as titanium, aluminum, copper, brass, and stainless steel. LARC-TPI is being evaluated as a thermoplastic for bonding large pieces of polyimide film to produce flexible, 100% void-free laminates for flexible circuit applications. The further development of LARC-TPI as a potential molding powder, composite matrix resin, high-temperature film and fiber will also be discussed.
A linear thermoplastic polyimide, LARC-TPI, has been characterized and developed for a variety of high-temperature applications. In its fully imidized form, this new material can be used as an adhesive for bonding metals such as titanium, aluminum, copper, brass, and stainless steel. LARC-TPI is being evaluated as a thermoplastic for bonding large pieces of polyimide film to produce flexible, 100% void-free laminates for flexible circuit applications. The further development of LARC-TPI as a potential molding powder, composite matrix resin, high-temperature film and fiber is also discussed.
The National Aeronautics and Space Administration (NASA) has actively pursued metal additive manufacturing (AM) technologies for spaceflight applications since the late 2000s. AM offers transformative advantages in cost, schedule, part consolidation, and design flexibility. Among the various AM techniques, laser powder directed energy deposition (LP-DED) is particularly well suited for fabricating complex geometries with fine feature resolution. In propulsion systems that utilize high-pressure gaseous hydrogen—such as liquid hydrogen rocket engines—hydrogen environment embrittlement (HEE) presents a serious threat to material performance 1,2 . Mechanical property degradation under these conditions can compromise component reliability, especially under cyclic loading. To address this challenge, NASA developed NASA HR-1 (Hydrogen Resistant-1) as a solution for liquid rocket engine components operating in hydrogen-rich environments, using the LP-DED technique 3-9 . A key component in a liquid rocket engine is the exhaust nozzle, which is typically regeneratively cooled (regen) due to the high heat flux. NASA HR-1 was specifically developed for regen nozzle applications using hydrogen as a propellant, providing resistance to HEE, a critical issue for many materials. The AM version of NASA HR-1 was also formulated to achieve high ultimate tensile strength, along with high yield strength and ductility in this environment 5,6 . Low-cycle fatigue (LCF) is another important consideration in nozzle design, as components are expected to endure multiple starts and missions. Additionally, the LP-DED version of the alloy exhibits improved thermal conductivity compared to its wrought counterpart, which benefits nozzle cooling. Overall, NASA HR-1 offers an excellent balance of high strength, HEE resistance, LCF performance, thermal conductivity, and ductility to meet the demanding requirements of channel-cooled nozzles and other components used with hydrogen and other propellants. The LP-DED–processed NASA HR-1 requires several post-processing heat treatment steps to achieve the material properties desirable for its intended application 6 . These steps include stress relief, homogenization, solution annealing, and aging for precipitation hardening. The stress relief treatment mitigates residual stresses accumulated during the LP-DED process and minimizes the potential for distortion. Homogenization, a common step for AM materials, reduces elemental segregation and promotes recrystallization to develop a more equiaxed grain structure. The subsequent solution annealing treatment heats the part to a solid solution temperature to dissolve the undesirable η-phase that forms during cooling from homogenization, followed by rapid cooling to retain an η-phase–free microstructure. Finally, aging promotes precipitation of the strengthening γ′ phase in the alloy. The integration of compositional design and optimized thermal processing enables high-quality LP-DED NASA HR-1 components with excellent microstructural and mechanical stability. Improved chemical and microstructure homogeneity enhances ductility and fatigue resistance—both critical for safe and reliable operation in high-pressure hydrogen environments. NASA has successfully fabricated and hot-fire tested multiple subscale and full-scale channel wall nozzles using LP-DED NASA HR-1 5,6, 9-14 . These efforts included process refinements to support thin-wall construction and various channel geometries. Throughout development, several key observations emerged. After homogenization, the as-built columnar grain structure transforms into a fully equiaxed microstructure. However, subsequent treatments—such as solution annealing and aging—result in changes that are more difficult to track. The grain structure remains largely unchanged, and the γ′ precipitates, typically 5–10 nm in diameter, are beyond the resolution of scanning electron microscopy (SEM). While transmission electron microscopy (TEM) can resolve these fine precipitates, TEM sample preparation is time-consuming and difficult for LP-DED material. As an alternative, differential scanning calorimetry (DSC) offers a useful, qualitative approach to monitor precipitate evolution throughout different stages of heat treatment. The overall goal is to improve the understanding of how heat treatment affects the microstructure and mechanical performance of LP-DED NASA HR-1. This paper presents heat treatment design considerations, microstructural characterization, mechanical testing – including tensile and LCF testing in both air and hydrogen environments.
There is an increasing need for functional materials to support high heat flux applications and optimize weight by using bimetallic additive manufacturing (AM). While one promising fabrication technology is the use of blown powder directed energy deposition (DED) AM, challenges remain with bi-metallic combinations. Prominent among these challenges is the need to understand mixing of materials at the bimetallic interface for forming stronger, more durable and reliable joints to extend the versatility of AM into critical applications. One application is the manufacturing of combustion chambers with copper-alloy liners and Superalloy structural jackets. In this application, material combinations are selected for effective heat dissipation, using copper, and retention of strength at high temperatures using Inconel 625. Currently, the dominant problem with this configuration is the highly variable strength of the interface and its correlation with deposition parameters. In this study, samples were fabricated at several vendors with Inconel 625 deposited onto wrought C-18150 (Cu-Cr-Zr) to form a bimetallic interface. Characterization of the interfaces were achieved through optical and electron microscopy, mechanical testing of mini tensile specimens, and electron dispersion spectroscopy to understand diffusion and bulk mixing behaviors at the joint. A theoretical framework was constructed in the context of solidification and mixing mechanisms to explain the resulting differences in the interface. This qualitative approach utilized a fluid dynamics perspective to sum the order of magnitudes of the various acting forces on the weld pool during deposition to predict convection trends based off known parameters. The predicted trends for each vendor are compared to obtain a better understanding of how mixing in the molten pool varied based on deposition parameters.
In the electron beam powder bed fusion (EB-PBF) process, a substantial number of high-gamma prime Ni-based superalloys are considered as non-printable due to a high propensity to form cracks. In this research, we focused on computational modeling framework to predict solidification-related cracking phenomena in EB-PBF processes. The cracking analysis was performed on cylindrical overhang structures where the cracks are observed only on one side of the part. Comprehensive microstructural characterization correlated the cracking tendency to low-melting point liquid-film formation along columnar grain boundaries with high misorientation angles due to partitioning of alloying elements. Uncoupled numerical thermal and mechanical models were used to rationalize the relationship between process parameters, build geometry, and cracking. The simulations showed asymmetric temperature distributions and associated asymmetric tensile thermal stresses over a cross section due to differences in section modulus and periodic changes in beam scanning directions. Here, the results provide a potential pathway based on spatially varying beam scanning strategies to reduce the cracking tendency during additive manufacturing of complex geometries on the overhang structure in high-gamma prime nickel-based superalloys.
A compositionally graded material comprised IN718 (718, γ'/γ" strengthened superalloy) and René41 (R41, a medium γ' strengthened superalloy) was fabricated using laser blown-powder directed energy deposition (DED/LB-M). Hot gas path components that require high and low temperature capabilities at different locations may benefit from such graded superalloy, potentially eliminating the use of welded or mechanically joined components and reducing cost. In the present work, microstructure and 650°C tensile behavior of 718-R41 graded superalloy in as-built and heat-treated states are investigated by Digital Image Correlation (DIC), in-situ neutron diffraction, coupled with conventional characterization techniques. The applied heat treatment generates static recrystallization and equiaxed grains in 718 rich compositions, while R41 rich compositions remain partially or un-recrystallized. Yield strengths of 718 and R41 sections in heat-treated state are comparable to wrought forms but the graded compositions show weakness. From neutron experiment, diffraction elastic constants and single crystal elastic constants are calculated, which show small difference between the as-built and heat-treated states and between the γ and γ' phases. Grain-level load transfer from the (220) grains to (200) grains is found to be composition dependent, and qualitatively agrees with DIC measured macroscopic yield strength. Within the (200) grains, the γ/γ' phases deform elastically until the γ phase yields and afterwards the γ' phase takes load from γ phase.
To investigate the dynamical properties of the novel hybrid compound, lithium benzimidazolate-borohydride Li 2 (bIm)BH 4 (where bIm denotes a benzimidazolate anion, C 7 N 2 H 5 - ), we have used a set of complementary techniques: neutron powder diffraction, ab initio density functional theory calculations, neutron vibrational spectroscopy, nuclear magnetic resonance, neutron spin echo, and quasi-elastic neutron scattering. Our measurements performed over the temperature range from 1.5 to 385 K have revealed the exceptionally fast low-temperature reorientational motion of BH 4 - anions. This motion is facilitated by the unusual coordination of tetrahedral BH 4 - anions in Li2(bIm)BH4: each anion has one of its H atoms anchored within a nearly square hollow formed by four coplanar Li+ cations, while the remaining -BH 3 fragment extends into a relatively open space, being only loosely coordinated to other atoms. As a result, the energy barriers for reorientations of this fragment around the anchored B-H bond axis are very small, and at low temperatures, this motion can be described as rotational tunneling. The tunnel splitting derived from the neutron spin echo measurements at 3.6 K is 0.43(2) ueV. With increasing temperature, we have observed a gradual transition from the regime of low-temperature quantum dynamics to the regime of classical thermally activated jump reorientations. The jump rate of the uniaxial 3-fold reorientations reaches 5 x 10 11 s -1 at 80 K. Nearer room temperature and above, both nuclear magnetic resonance and quasi-elastic neutron scattering measurements have revealed the second process of BH4- reorientations characterized by the activation energy of 261 meV. This process is several orders of magnitude slower than the uniaxial 3-fold reorientations; the corresponding jump rate reaches ~7 x 10 8 s -1 at 300 K.
Atomization and spraying are well-established methods for the production of submicrometer- and micrometer- sized powders. In addition, they could be of interest to the immobilization of photocatalytic nanoparticles onto supports because they enable the formation of microporous films with photocatalytic activity. Here, we provide a comparison of aerosol-assisted immobilization methods, such as spray-drying (SD), spray atomization (SA), and spray gun (SG), which were used for the deposition of TiO 2 dispersions onto fibrous filter media. The morphology, microstructure, and electronic properties of the structures with deposited TiO 2 were characterized by SEM and TEM, BET and USAXS, and UV-Vis spectrometry, respectively. The photocatalytic performances of the functionalized filters were evaluated and compared to the benchmark dip-coating method. Our results showed that the SG and SA immobilization methods led to the best photocatalytic and operational performance for the degradation of toluene, whereas the SD method showed the lowest degradation efficiency and poor stability of coating. We demonstrated that TiO2 sprays using the SG and SA methods with direct deposition onto filter media involving dispersed colloidal droplets revealed to be promising alternatives to the dip-coating method owing to the ability to uniformly cover the filter fibers. In addition, the SA method allowed for fast and simple control of the coating thickness as the dispersed particles were continuously directed onto the filter media without the need for repetitive coatings, which is common for the SG and dip-coating methods. Our study highlighted the importance of the proper immobilization method for the efficient photocatalytic degradation of VOCs.
Additive manufacturing (AM) offers opportunities to produce complex part geometries not possible with conventional processing and in some cases even improve part performance. However, adoption has been slowed by difficulties assessing microstructure variability and there is no straightforward approach to relate processing to grain structure characteristics. In this study, datasets from AdditiveFOAM heat transport simulations of laser powder bed fusion (LPBF) are used to drive ExaCA simulations of grain structure. The GPU utilization of ExaCA and an algorithmic update for modeling melt pool overlap region solidification enabled rapid and parallel simulation across a wider range of process conditions than previously explored with cellular automata-based solidification models. A texture selection angle $θ_s$ is defined based on melt pool overlap geometry, and the range of $θ_s$ over which a commonly observed texture transition occurs in characterized AM builds was well-reproduced by ExaCA simulations over a wide range of melt pool shape, hatch spacing, and layer height. ExaCA simulations with 90 degree rotation of the scan direction on every other layer reproduced a number of trends from the AM literature including grain refinement, the dominance of layers with larger melt pools on the final grain structure, and the weakening or strengthening of texture depending on odd and even layer melt pool overlap geometry. EBSD data from a benchmark AM part is used to validate the simulated mechanism of a layer rotation-induced texture strengthening effect. Importantly, these results expand the understanding of the mechanisms for texture selection in alloys with cubic crystal symmetry and offer an approach to easily evaluate processing conditions. With this new understanding, these modeling tools will enable anticipation of previously unexpected variations in grain structure and target specific microstructures and properties.
This study investigates a novel environmentally friendly coating technique using yeast fermentation to obtain super porous Zeolite 13X adsorbent layers through freeze-drying technique for CO 2 capture applications. Several mass ratios of sugar to yeast were used to control the porosity and pore sizes in the adsorbent layer. A unique peeling process was integrated to obtain foamy, hollow structures to have deeper layer accessibility of adsorbent for adsorption applications. These coated adsorbent layers were experimentally characterized as a function of the mass ratio of sugar to yeast and adsorbent solid fraction. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and Fourier-transform infrared spectroscopy (FT-IR) are used to analyze the coated layers. Here, the void fraction for coated samples is found to vary between 0.48 and 0.56, making the samples applicable for adsorption applications. Adsorption performance experiments are performed to test the coated samples' performance compared to 13X powder. Due to their simplistic fabrication, cost-effectiveness, rapid pore formation, and high adsorption capacity, these porous 13X layers hold potential for large-scale fabrication and CO 2 capture applications.
In this work, the microstructures of Ti-6Al-4V manufactured by different additive manufacturing (AM) processes have been characterized and compared. The microstructural features that were characterized are the α lath thickness, grain boundary α (GB-α) thickness, prior β grain size and α colony size. In addition, the microhardnesses were also measured and compared. The microstructure of shaped metal deposited (SMD) Ti-6Al-4V material showed the smallest variations in α lath size, whereas the material manufactured with laser metal wire deposition-0 (LMwD-0) showed the largest variation. The prior β grain size was found to be smaller in material manufactured with powder bed fusion (PBF) as compared with corresponding material manufactured with the directed energy deposition (DED) processes. Parallel bands were only observed in materials manufactured with DED processes while being non-present in material manufactured with PBF processes.