Search NASA⌕ Search

Engineering topics

Zhang, Xin

Publications and source records attributed to Zhang, Xin.

At least 73 records · Page 4

Interplay between Facets and Defects during the Dissociative and Molecular Adsorption of Water on Metal Oxide Surfaces

Both surface terminations and defects play a central role in determining how water interacts with metal oxides, thereby setting important properties of the interface that govern reactivity such as the type and distribution of hydroxyl groups. However, the interconnections between facets and defects remain poorly understood, limiting the usefulness of conventional notions such as that hydroxylation is controlled by metal cation exposure at the surface. Here, using hematite (α-Fe 2 O 3 ) as a model system, we show how oxygen vacancies overwhelm surface cation-dependent hydroxylation behavior. Synchrotron-based ambient-pressure X-ray photoelectron spectroscopy was used to monitor the adsorption of molecular water and its dissociation to form hydroxyl groups in situ on (001), (012), or (104) facet-engineered hematite nanoparticles. Supported by density functional theory calculations of the respective surface energies and oxygen vacancy formation energies, the findings show how oxygen vacancies are more prone to form on higher energy facets and induce surface hydroxylation at extremely low relative humidity values of 5 x10 - 5 %. Further, when these vacancies are eliminated, the extent of surface hydroxylation across the facets is as expected from the areal density of exposed iron cations at the surface. These findings help answer fundamental questions about the nature of reducible metal oxide-water interfaces in natural and technological settings and lay the groundwork for rational design of improved oxide-based catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Growth of Mesoscale Ordered Two-Dimensional Hydrogen-Bond Organic Framework with the Observation of Flat Band

Flat bands (FBs), presenting a strongly interacting quantum system, have drawn increasing interest recently. However, experimental growth and synthesis of FB materials have been challenging and have remained elusive for the ideal form of monolayer materials where the FB arises from destructive quantum interference as predicted in 2D lattice models. Here, we report surface growth of a self-assembled monolayer of 2D hydrogen-bond (H-bond) organic frameworks (HOFs) of 1,3,5-tris(4-hydroxyphenyl)benzene (THPB) on Au(111) substrate and the observation of FB. High-resolution scanning tunneling microscopy or spectroscopy shows mesoscale, highly ordered, and uniform THPB HOF domains, while angle-resolved photoemission spectroscopy highlights a FB over the whole Brillouin zone. Density-functional-theory calculations and analyses reveal that the observed topological FB arises from a hidden electronic breathing-kagome lattice without atomically breathing bonds. In conclusion, our findings demonstrate that self-assembly of HOFs provides a viable approach for synthesis of 2D organic topological materials, paving the way to explore many-body quantum states of topological FBs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Pulsed Thermal Tomography Nondestructive Examination of Additively Manufactured Reactor Materials and Components (Final Technical Report)

Metal Additive Manufacturing (AM) is a promising method for cost-efficient fabrication of complex shape structures for applications in harsh environment, such as in a nuclear reactor. However, internal defects (pores) occur in high-strength AM alloys, which are manufactured with Laser Powder Bed Fusion (LPBF) AM method. Pulsed Infrared Thermography (PIT) is an efficient nondestructive evaluation (NDE) method to examine actual structures, because this method offers one-sided non-contact measurements, and fast processing of large sample areas. However, imaging of material defects, particularly defects with sizes at microscopic level, is challenging. In this report, we benchmark the performance of several Unsupervised Learning (UL) algorithms designed to enhance imaging of microscopic defects in metals with PIT. UL aims to learn the latent principal patterns (dictionaries) in PIT data to detect defects with minimal human supervision. Performance of Independent Component Analysis (ICA), Sparse Coding (SC), Principal Component Analysis (PCA) and Exploratory Factor Analysis (EFA) was compared using F-score, UL model training time and defects reconstruction time. We obtained the average F-score of 0.75, and a highest F-score of 0.89 for the EFA algorithm. Overall, EFA outperforms other UL algorithms considered in this study. In another approach, we investigate Thermal Tomography (TT), which is a computational method for reconstruction of depth profile of internal material defects from PIT nondestructive evaluation (NDE). TT algorithm obtains depth reconstructions of thermal effusivity, which has been shown to provide visualization of subsurface internals defects in metals. In many applications, one needs to determine the defect shape and orientation from reconstructed effusivity images. Interpretation of TT images is non-trivial because of blurring, which increases with depth due to heat diffusion-based nature of image formation. We have developed a deep learning convolutional neural network (CNN) to classify size and orientation of subsurface material defects in TT images. CNN was trained with TT images produced with computer simulations of 2D metallic structures (thin plates) containing elliptical subsurface voids. Performance of CNN was investigated using test TT images developed with computer simulations of plates containing elliptical defects, and defects with shape imported from scanning electron microscopy (SEM) images. CNN demonstrated the ability to classify radii and angular orientation of elliptical defects in previously unseen test TT images. We have also demonstrated that CNN trained on TT images of elliptical defects is capable of classifying shape and orientation of irregular defects. Training the CNN on irregular defect shapes instead of on elliptical shapes would make the resulting classifications more descriptive of actual defect shapes. However, this requires a much higher volume of SEM images of material defects, which are difficult to obtain because of random occurrence of defects in LPBF. To address this challenge, we developed a generative adversarial network (GAN) to augment the existing dataset of SEM defect images. The GAN model is demonstrated to create novel yet realistic defect shapes that can be used as input for simulated PTT images to train CNN. We also investigate several approaches based on Gaussian Random Circle and Bezier Curves for constructing parametric models of irregular-shape defects.

36 MATERIALS SCIENCE↗

Magnetic cores with high reluctance differences in flux paths

Embodiment of the present invention includes a magnetic structure and a magnetic structure used in a direct current (DC) to DC energy converter. The magnetic structure has an E-core and a plate, with the plate positioned in contact or in near contact with the post surfaces of the E-core. The E-core has a base, a no-winding leg, a transformer leg, and an inductor leg. The no-winding leg, the transformer leg, and the inductor leg are perpendicular and magnetically in contact with the base. The plate is a flat slab with lateral dimensions generally larger than its thickness. The plate has a plate nose that overlaps a top no-winding leg surface of the no-winding leg with a no-winding gap area to form a no-winding gap with a no-winding gap reluctance. The plate also has a plate end that overlaps a top inductor leg surface of the inductor leg with an inductor gap area to form an inductor gap with an inductor gap reluctance. In some embodiments, e.g., where the duty cycle is less than 50 percent, the inductor gap reluctance will be designed to be less than the no-winding gap reluctance. In these cases, the majority of the magnetic flux that passes through the transformer leg will return through the inductor leg, instead of through the no-winding leg. The inductor and no-winding gap reluctances can he adjusted, so that the electromotive force applied to a charge passing through the inductor will partially cancel the electromotive force applied by the transformer secondary. The gap reluctance ratio can be defined, so that the difference in secondary and inductor electromotive forces is equal to the output voltage defined by an optimal no-ripple duty cycle. In this way no changing current is required through the inductor to create a dI/dt inductive voltage drop across the output inductor. Zero output current ripple is achieved.Various embodiments of the plate, plate shape, and no-winding leg are disclosed. These embodiments allow achieving a high ratio of no-winding gap reluctance to inductor gap reluctance, for practical, affordable magnetic material structures and aspect ratios. A high gap reluctance ratio enables zero output current ripple for the high transformer turns ratios that are needed to achieve high input to output voltage ratios. The embodiments therefore allow achieving low output current ripple for 48 V or higher input voltages, 1 V or lower output voltages, and high output currents.

Yao, Yuan↗

A cellulose-derived supramolecule for fast ion transport

Supramolecular frameworks have been widely synthesized for ion transport applications. However, conventional approaches of constructing ion transport pathways in supramolecular frameworks typically require complex processes and display poor scalability, high cost, and limited sustainability. Here, we report the scalable and cost-effective synthesis of an ion-conducting (e.g., Na + ) cellulose-derived supramolecule (Na-CS) that features a three-dimensional, hierarchical, and crystalline structure composed of massively aligned, one-dimensional, and ångström-scale open channels. Using wood-based Na-CS as a model material, we achieve high ionic conductivities (e.g., 0.23 S/cm in 20 wt% NaOH at 25 °C) even with a highly dense microstructure, in stark contrast to conventional membranes that typically rely on large pores (e.g., submicrometers to a few micrometers) to obtain comparable ionic conductivities. This synthesis approach can be universally applied to a variety of cellulose materials beyond wood, including cotton textiles, fibers, paper, and ink, which suggests excellent potential for a number of applications such as ion-conductive membranes, ionic cables, and ionotronic devices.

36 MATERIALS SCIENCE↗

The role of amorphous ZIF in ZIF-8 crystallization kinetics and morphology

Understanding the composition and structure of amorphous precursor phases is fundamental for elucidating two-step crystallization mechanisms and designing shape- and size-controlled nanomaterials. However, that understanding is largely lacking for metal–organic framework compounds despite their growing significance as functional materials. Here, in this study, we report the crystallization of zeolite imidazolate frameworks-8 (ZIF-8, Zn(C 4 H 5 N 2 ) 2 ) via an amorphous ZIF (am-ZIF) solid precursor phase with a rough stoichiometric composition of Zn(C 4 H 5 N 2 ) 1.78 (C 4 H 6 N 2 ) 0.17 (CH 3 COO) 0.22 . The formation of am-ZIF is attributed to the incomplete deprotonation of 2-Methylimidazole (HmIm) and the involvement of the hydrogen bond between CH 3 COO– and –HN, which can further transform into the dense Dia(Zn) structure with a diamondoid crystal topology in pure water. Taking am-ZIF as a precursor, the tunable dissolution and recrystallization kinetics of am-ZIF into ZIF-8, due to the addition of EtOH and CTAB, allows the selective fabrication of dodecahedral, cubic, and hollow ZIF-8. Overall, an in-depth understanding of the differences in composition and structure of am-ZIF from ZIF-8 and the resulting crystallization kinetics suggests a novel approach to designing metal–organic frameworks with controlled crystal morphology.

36 MATERIALS SCIENCE↗

Coal-derived graphene foam and micron-sized silicon composite anodes for lithium-ion batteries

Silicon-based materials demonstrate significant potential as lithium-ion batteries (LIBs) anode, but their expansion and degradation present engineering design challenges for commercial application. In this study, a porous three-dimensional (3D) graphene and micron-sized silicon composite anode (Si@G foam) was synthesized using humic acid (HA) derived from coal as a graphene precursor. In-situ formation of graphene structure through reducing HA was confirmed by Raman spectra. The reduced HA (rHA) shows similar electrical conductivity compared to the commercial conductive carbon. SEM images depict a 3D skeleton of coal-derived graphene, with silicon particles distributed on the 3D graphene foam's internal surface. The Si@G composite-anode displays a good reversible capacity of ~656 mAh/g at a current density of 50 mA/g, as well as a high-rate capability of ~433 mAh/g at a current density of 800 mA/g, and outstanding cycling stability –89.8% capacity retention after 300 cycles, which is significantly higher than that of other foam structures. During lithiation and de-lithiation, the graphene foam serves as a matrix of electrical conductors and a volume expansion support for silicon. This 3D graphene network will be beneficial for developing advanced silicon-based anodes for high-performance LIBs.

25 ENERGY STORAGE↗

Predicting the structural basis of targeted protein degradation by integrating molecular dynamics simulations with structural mass spectrometry

Targeted protein degradation (TPD) is a promising approach in drug discovery for degrading proteins implicated in diseases. A key step in this process is the formation of a ternary complex where a heterobifunctional molecule induces proximity of an E3 ligase to a protein of interest (POI), thus facilitating ubiquitin transfer to the POI. In this work, we characterize 3 steps in the TPD process. (1) We simulate the ternary complex formation of SMARCA2 bromodomain and VHL E3 ligase by combining hydrogen-deuterium exchange mass spectrometry with weighted ensemble molecular dynamics (MD). (2) We characterize the conformational heterogeneity of the ternary complex using Hamiltonian replica exchange simulations and small-angle X-ray scattering. (3) We assess the ubiquitination of the POI in the context of the full Cullin-RING Ligase, confirming experimental ubiquitinomics results. Differences in degradation efficiency can be explained by the proximity of lysine residues on the POI relative to ubiquitin.

59 BASIC BIOLOGICAL SCIENCES↗

Using ammonia as a shipping fuel could disturb the nitrogen cycle

Ammonia has been proposed as a shipping fuel, yet potential adverse side-effects are poorly understood. Here we argue that if nitrogen releases from ammonia are not tightly controlled, the scale of the demands of maritime transport are such that the global nitrogen cycle could be substantially altered.

54 ENVIRONMENTAL SCIENCES↗

Phosphate adsorption kinetics and equilibria on natural iron and manganese oxide composites

We report that it is well known that phosphate retention in soils and sediments is strongly influenced by binding to secondary iron oxides, there have been relatively few studies examining its adsorption/desorption behavior on multicomponent particles of realistic natural complexity. In this study, natural Mn-rich limonite (LM), was used to prepare naturally complex Fe- and Mn-oxide composite materials to examine phosphate adsorption/desorption. To clarify the role of the Mn-oxides, results for the LM sample were compared to those for an acid treated version (LAT), in which the acid-extractable Mn-oxide fraction has been selectively eliminated while leaving the Fe-oxide fraction intact. The saturated adsorption capacity on LAT was almost double that on LM, suggesting that phosphate adsorption to the iron oxides is strongly occluded by the Mn-oxide fraction. This result is reinforced by the comparing the pH dependence and fits to adsorption isotherms, and by desorption experiments and STEM-EDS mapping showing that phosphate loading on Mn-oxides was limited. Hence, although the collective results confirm that phosphate uptake and strong binding is selectively controlled by the Fe-oxide fraction, our study reveals that the Mn-oxide fraction strongly interferes with this process. Therefore, phosphate uptake behavior on metal oxides cannot be predicted solely on the basis of the Fe-oxide fraction present, but instead must take into account the deleterious impacts of other intimately associated phases. For co-diagenetic Fe/Mn-oxide composites in particular, Mn-oxides appear to severely limit phosphate uptake on the Fe-oxide fraction, either by hindering access to binding sites on the Fe-oxide or by lowering their affinity for P.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The histone code of the fungal genus Aspergillus uncovered by evolutionary and proteomic analyses

Chemical modifications of DNA and histone proteins impact the organization of chromatin within the nucleus. Changes in these modifications, catalysed by different chromatin-modifying enzymes, influence chromatin organization, which in turn is thought to impact the spatial and temporal regulation of gene expression. While combinations of different histone modifications, the histone code, have been studied in several model species, we know very little about histone modifications in the fungal genus Aspergillus, whose members are generally well studied due to their importance as models in cell and molecular biology as well as their medical and biotechnological relevance. Here, we used phylogenetic analyses in 94 Aspergilli as well as other fungi to uncover the occurrence and evolutionary trajectories of enzymes and protein complexes with roles in chromatin modifications or regulation. We found that these enzymes and complexes are highly conserved in Aspergilli, pointing towards a complex repertoire of chromatin modifications. Nevertheless, we also observed few recent gene duplications or losses, highlighting Aspergillus species to further study the roles of specific chromatin modifications. SET7 (KMT6) and other components of PRC2 (Polycomb Repressive Complex 2), which is responsible for methylation on histone H3 at lysine 27 in many eukaryotes including fungi, are absent in Aspergilli as well as in closely related Penicillium species, suggesting that these lost the capacity for this histone modification. We corroborated our computational predictions by performing untargeted MS analysis of histone post-translational modifications in Aspergillus nidulans. This systematic analysis will pave the way for future research into the complexity of the histone code and its functional implications on genome architecture and gene regulation in fungi.

59 BASIC BIOLOGICAL SCIENCES↗

Determination of the Structures of Lignin Subunits and Nanoparticles in Solution by Small‐Angle Neutron Scattering: Towards Improving Lignin Valorization

Abstract Lignin nanoparticles (LNPs) are usually produced from lignin solution through supersaturation. The structure of the lignin in solution is still poorly understood due to structural variability of isolated lignins. Here, lignins were extracted from different plants to establish a general pattern of their structure in several lignin solvents. Lignin molecules (lignin subunits) and larger aggregates were observed in dimethyl sulfoxide (DMSO), ethylene glycol (EG) and 0.1 N NaOD solutions by small‐angle neutron scattering (SANS). It was proposed that the aggregates were composed of lignin subunits with a higher molecular weight and a higher ratio of the aliphatic to phenolic hydroxyl groups. The size, shape, and compactness are important factors that affect the uses of the LNPs, which were obtained from the SANS data for the first time. A discrepancy in the radius between SANS and DLS was discovered, pointing to a large hydration shell around the LNPs in aqueous solutions. The cytotoxicity of the corncob lignin, kraft lignin, and their LNPs were measured and compared.

Zhang, Xin↗

Preservation of high-pressure volatiles in nanostructured diamond capsules

High pressure induces dramatic changes and novel phenomena in condensed volatiles(1,2) that are usually not preserved after recovery from pressure vessels. In this study we report a process that pressurizes volatiles into nanopores of type 1 glassy carbon precursors, converts glassy carbon into nanocrystalline diamond by heating and synthesizes free-standing nanostructured diamond capsules (NDCs) capable of permanently preserving volatiles at high pressures, even after release back to ambient conditions for various vacuum-based diagnostic probes including electron microscopy. As a demonstration, we perform a comprehensive study of a high-pressure argon sample preserved in NDCs. Synchrotron X-ray diffraction and high-resolution transmission electron microscopy show nanometre-sized argon crystals at around 22.0 gigapascals embedded in nanocrystalline diamond, energy-dispersive X-ray spectroscopy provides quantitative compositional analysis and electron energy-loss spectroscopy details the chemical bonding nature of high-pressure argon. The preserved pressure of the argon sample inside NDCs can be tuned by controlling NDC synthesis pressure. To test the general applicability of the NDC process, we show that high-pressure neon can also be trapped in NDCs and that type 2 glassy carbon can be used as the precursor container material. Additional experiments on other volatiles and carbon allotropes open the possibility of bringing high-pressure explorations on a par with mainstream condensed-matter investigations and applications.

36 MATERIALS SCIENCE↗

Power Converter Circuit Design Automation using Parallel Monte Carlo Tree Search

The tidal waves of modern electronic/electrical devices have led to increasing demands for ubiquitous application-specific power converters. A conventional manual design procedure of such power converters is computation- and labor-intensive, which involves selecting and connecting component devices, tuning component-wise parameters and control schemes, and iteratively evaluating and optimizing the design. To automate and speed up this design process, we propose an automatic framework that designs custom power converters from design specifications using Monte Carlo Tree Search. Specifically, the framework embraces the upper-confidence-bound-tree (UCT), a variant of Monte Carlo Tree Search, to automate topology space exploration with circuit design specification-encoded reward signals. Moreover, our UCT-based approach can exploit small offline data via the specially designed default policy and can run in parallel to accelerate topology space exploration. Further, it utilizes a hybrid circuit evaluation strategy to substantially reduce design evaluation costs. Empirically, we demonstrated that our framework could generate energy-efficient circuit topologies for various target voltage conversion ratios. Compared to existing automatic topology optimization strategies, the proposed method is much more computationally efficient --- the sequential version can generate topologies with the same quality while being up to 67% faster. Here, the parallelization schemes can further achieve high speedups compared to the sequential version.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Persistent exchange splitting in the chiral helimagnet $\mathrm{Cr}_{1/3}\mathrm{NbS}_2$

Here, using high-resolution angle-resolved photoemission spectroscopy and ab initio calculation, we systematically investigate the electronic structure of the chiral helimagnet Cr 1/3 NbS 2 and its temperature evolution. The comparison with NbS 2 suggests that the electronic structure of Cr 1/3 NbS 2 is strongly modified by the intercalation of Cr atoms. Our ab initio calculation, consistent with experimental results, suggests strong hybridization between Nb- and Cr-derived states near the Fermi level. In the chiral helimagnetic state (below the Curie temperature, T c ), we observe exchange splitting of the energy bands crossing the Fermi level, which follows the temperature evolution of the magnetic moment, suggesting a strong interaction between the conduction electrons and Cr spin moments. Interestingly, the exchange splitting persists far above T c with weak temperature dependence, in drastic contrast to the itinerant ferromagnetism described by the Stoner model, indicating the existence of short-range magnetic order. Our results provide important insights into the interplay between the electronic structure and magnetism in Cr 1/3 NbS 2 , which is helpful for understanding the microscopic mechanism of chiral helimagnetic ordering.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Report on PTT Imaging of Defects in AM Metallic Materials-Part 2

Metal Additive Manufacturing (AM) is a promising method for cost-efficient fabrication of complex shape structures for applications in harsh environment, such as in a nuclear reactor. However, internal defects (pores) occur in high-strength AM alloys, which are manufactured with Laser Powder Bed Fusion (LPBF) AM method. Pulsed Infrared Thermography (PIT) is an efficient nondestructive evaluation (NDE) method to examine actual structures, because this method offers one-sided non-contact measurements, and fast processing of large sample areas. However, imaging of material defects, particularly defects with sizes at microscopic level, is challenging. In this report, we benchmark the performance of several Unsupervised Learning (UL) algorithms designed to enhance imaging of microscopic defects in metals with PIT. UL aims to learn the latent principal patterns (dictionaries) in PIT data to detect defects with minimal human supervision. Performance of Independent Component Analysis (ICA), Sparse Coding (SC), Principal Component Analysis (PCA) and Exploratory Factor Analysis (EFA) was compared using F-score, UL model training time and defects reconstruction time. We obtained the average F-score of 0.75, and a highest F-score of 0.89 for the EFA algorithm. Overall, EFA outperforms other UL algorithms considered in this study.

36 MATERIALS SCIENCE↗