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At least 1,225 records · Page 68
All sourcesNASA NTRSDOE OSTI
NASA NTRS2017

Climate Limits Across Space and Time on European Forest Structure

The impact climate has on forests has been extensively studied. However, the large scale effect climate has on forest structures, such as average diameters, heights and basal area are understudied in a spatially explicit manner. The limits, tipping points and thresholds that climate places on forest structures dictate the services a forest may provide, the vulnerability of a forest to mortality and the potential value of the timber there within. The majority of current research either investigates climate impacts on forest pools and fluxes, on a tree physiological scale or on case studies that are used to extrapolate results and potential impacts. A spatially explicit study on how climate affects forest structure over a large region would give valuable information to stakeholders who are more concerned with ecosystem services that cannot be described by pools and fluxes but require spatially explicit information - such as biodiversity, habitat suitability, and market values. In this study, we quantified the limits that climate (maximum, minimum temperature and precipitation) places on 3 forest structures, diameter at breast height, height, and basal area throughout Europe. Our results show clear climatic zones of high and low upper limits for each forest structure variable studied. We also spatially analyzed how climate restricts the potential bio-physical upper limits and creates tipping points of each forest structure variable and which climate factors are most limiting. Further, we demonstrated how the climate change has affected 8 individual forests across Europe and then the continent as a whole. We find that diameter, height and basal area are limited by climate in different ways and that areas may have high upper limits in one structure and low upper limits in another limited by different climate variables. We also found that even though individual forests may have increased their potential upper limit forest structure values, European forests as a whole have lost, on average, 5.0%, 1.7% and 6.5% in potential mean forest diameter, height and basal area, respectively.

Moreno, Adam La Salle↗
NASA NTRSDate not supplied

Advanced Composite Structures and Materials Technologies for Launch Vehicles

The NASA's Advanced Composites Technologies (ACT) Project has the potential to develop composite materials and structures technologies for the largest composite aerospace structures ever made. The objective the ACT Project of is to develop mid-technology readiness level (TRL) composite materials and structures technologies to TRL 6 for specific heavy lift Ares V launch vehicle and Altair lunar lander applications. To accomplish this objective, the ACT Project has four major technical elements: materials and manufacturing; structural concepts development and assessment of lightweight components; testing and evaluation; and highly loaded composite struts. The Project uses capabilities from across NASA to form multi-disciplinary, cross-center teams to meet the milestones of these technical elements. This presentation will describe the activities and plans for the ACT Project. Studies from the first execution year of the project will be summarized including results from materials selection and structural concept evaluation studies. Plans for continuing activities include studies for nondestructive evaluation/structural health monitoring, damage tolerance, joints, and material and structural testing, and these studies will be described. A major emphasis this fiscal year is the start of work for a manufacturing demonstration barrel. This structure will be composed of six, 5-m-diameter, 3-m-long curved panels that when assembled, result in a 10-m-diameter barrel. Activities related to the development of this structure will also be described.

Mark J Shuart↗
NASA NTRS2022

Constraining Venus and Mars Internal Structures from the Gravity Response to Atmospheric Loading

The gravity fields of celestial bodies that possess an atmosphere are periodically perturbed by the redistribution of fluid mass associated with the atmospheric dynamics. A component of this perturbation is due to the gravitational response of the body to the deformation of its surface induced by the atmospheric pressure loading. The magnitude of this effect depends on the relation between the loading and the response in terms of geopotential variations measured by the load Love numbers. In this work, we simulate and analyze the gravity field generated by the atmospheres of Venus and Mars by accounting for different models of their internal structure. By precisely characterizing the phenomena that drive the mass transportation in the atmosphere through general circulation models, we determine the effect of the interior structure on the response to the atmospheric loading. An accurate estimation of the time-varying gravity field, which measures the atmospheric contribution, may provide significant constraints on the interior structure through the measurement of the load Love numbers. A combined determination of tidal and load Love numbers would enhance our knowledge of the interior of planetary bodies, providing further geophysical constraints in the inversion of internal structure models.The gravity fields of celestial bodies that possess an atmosphere are periodically perturbed by the redistribution of fluid mass associated with the atmospheric dynamics. A component of this perturbation is due to the gravitational response of the body to the deformation of its surface induced by the atmospheric pressure loading. The magnitude of this effect depends on the relation between the loading and the response in terms of geopotential variations measured by the load Love numbers. In this work, we simulate and analyze the gravity field generated by the atmospheres of Venus and Mars by accounting for different models of their internal structure. By precisely characterizing the phenomena that drive the mass transportation in the atmosphere through general circulation models, we determine the effect of the interior structure on the response to the atmospheric loading. An accurate estimation of the time-varying gravity field, which measures the atmospheric contribution, may provide significant constraints on the interior structure through the measurement of the load Love numbers. A combined determination of tidal and load Love numbers would enhance our knowledge of the interior of planetary bodies, providing further geophysical constraints in the inversion of internal structure models.

Mars↗
NASA NTRSDate not supplied

Effects of Defects Analysis and Sizing Framework for Efficient Design of Composite Structures

Design of large composite structures requires striking a balance between permitted flaw size,strength margins, weight, and production rate. Stringent requirements manufacturing flaws can result in a lightweight structure because the strength properties are assumed to be closer to pristine. However, these stringent requirements can lead to production delays due to increased inspection and rework needed during the layup and rejection of parts after cure. Conversely, permitting larger flaws can reduce production delays, but will likely result in a heavier structure due to increased conservatism needed to maintain acceptable structural margins. The tradeoff between these criteria can vary between different structures and material systems, so the balance between manufacturing and design requirements is always a moving target. Assessment of this tradeoff requires having the ability to quickly evaluate the impact of flaw size on strength margin across an entire structure for a large number of load cases. The approach taken in this work is to implement an effects of defects analysis and sizing framework within HyperX. HyperX performs optimization of composite structures; this capability has been enhanced to include structural flaw data in the margin of safety calculations performed during optimization. Both the flaw import process and analysis of flaws have been generalized such that any flaw type from any source can be considered. The resulting tool enables rapid assessment of the impact of defects both at a vehicle and part level.

Effects of defects↗
NASA NTRSDate not supplied

Structural Dynamics Observations in Space Launch System Green Run Hot Fire Testing

The Space Launch System (SLS) Core Stage (CS) Thrust Vector Control (TVC) system is comprised of eight mechanical feedback Shuttle heritage Type III TVC actuators and four RS-25 engines, each attached to a Shuttle heritage gimbal block/bearing. Two actuators are used to move each engine in two planes perpendicular to one another (i.e., pitch and yaw). The TVC system design leverages hardware from the Space Shuttle program as well as new hardware designed specifically for the Core Stage. The Green Run Hot Fire (GRHF) of the SLS Core Stage provided a flight-like ground test environment for verification of integrated vehicle TVC performance. A TVC model coupled to a vehicle structural dynamic model has been developed previously and incrementally validated in subsystem tests and simulations. Still, some aspects of TVC performance in GRHF were not anticipated. The ensuing investigation demonstrated the need for well-instrumented test environments, various levels of modeling fidelity, test-representative structural models, and caution in reuse of legacy components. This paper is the sixth installment in a seven-paper series surveying the design, engineering, test validation, and flight performance of the Core Stage Thrust Vector Control system. It introduces the salient structural dynamic phenomena uncovered in ambient and hot fire testing. During the Green Run test campaign, a comparison of ambient and hot fire step responses showed a significant change in apparent damping due to the presence of friction, challenging long standing assumptions that friction could be neglected. Additionally, the characteristic response of the engine and thrust structure during GRHF proved to be more complex than anticipated, as evidenced by the available actuator, thrust structure, and engine measurements. While the string-potentiometer based test instrumentation was intended to allow for reconstruction of the engine angles along the two control axes, the geometric placement, location uncertainty, and responses in overlapping frequency spectra revealed additional phenomena requiring further analysis and post-processing. The observations from both modal and frequency response testing during the Green Run ambient and hot fire configurations led to Engine and Core Stage FEM (finite element model) updates. When evidence of unexpected engine motion was found in engine section accelerometer data, the authors pursued additional structural analysis leading to FEM updates associated with the TVC gimbal and thrust structure. Through collaboration between structures, TVC, and flight control disciplines, the test-informed models and root-cause analysis led to confident flight rationale for the first flight of the SLS launch vehicle.

Richard K. Moore↗
NASA NTRSDate not supplied

Structural Dynamics Observations in Space Launch System Green Run Hot Fire Testing

The Space Launch System (SLS) Core Stage (CS) Thrust Vector Control (TVC) system is comprised of eight mechanical feedback Shuttle heritage Type III TVC actuators and four RS-25 engines, each attached to a Shuttle heritage gimbal block/bearing. Two actuators are used to move each engine in two planes perpendicular to one another (i.e., pitch and yaw). The TVC system design leverages hardware from the Space Shuttle program as well as new hardware designed specifically for the Core Stage. The Green Run Hot Fire (GRHF) of the SLS Core Stage provided a flight-like ground test environment for verification of integrated vehicle TVC performance. A TVC model coupled to a vehicle structural dynamic model has been developed previously and incrementally validated in subsystem tests and simulations. Still, some aspects of TVC performance in GRHF were not anticipated. The ensuing investigation demonstrated the need for well-instrumented test environments, various levels of modeling fidelity, test-representative structural models, and caution in reuse of legacy components. This paper is the sixth installment in a seven-paper series surveying the design, engineering, test validation, and flight performance of the Core Stage Thrust Vector Control system. It introduces the salient structural dynamic phenomena uncovered in ambient and hot fire testing. During the Green Run test campaign, a comparison of ambient and hot fire step responses showed a significant change in apparent damping due to the presence of friction, challenging long standing assumptions that friction could be neglected. Additionally, the characteristic response of the engine and thrust structure during GRHF proved to be more complex than anticipated, as evidenced by the available actuator, thrust structure, and engine measurements. While the string-potentiometer based test instrumentation was intended to allow for reconstruction of the engine angles along the two control axes, the geometric placement, location uncertainty, and responses in overlapping frequency spectra revealed additional phenomena requiring further analysis and post-processing. The observations from both modal and frequency response testing during the Green Run ambient and hot fire configurations led to Engine and Core Stage FEM (finite element model) updates. When evidence of unexpected engine motion was found in engine section accelerometer data, the authors pursued additional structural analysis leading to FEM updates associated with the TVC gimbal and thrust structure. Through collaboration between structures, TVC, and flight control disciplines, the test-informed models and root-cause analysis led to confident flight rationale for the first flight of the SLS launch vehicle.

Richard Moore↗
NASA NTRSDate not supplied

Effects of Defects Analysis and Sizing Framework for Efficient Design of Composite Structures

Design of large composite structures requires striking a balance between permitted flaw size,strength margins, weight, and production rate. Stringent requirements manufacturing flaws can result in a lightweight structure because the strength properties are assumed to be closer to pristine. However, these stringent requirements can lead to production delays due to increased inspection and rework needed during the layup and rejection of parts after cure. Conversely, permitting larger flaws can reduce production delays, but will likely result in a heavier structure due to increased conservatism needed to maintain acceptable structural margins. The tradeoff between these criteria can vary between different structures and material systems, so the balance between manufacturing and design requirements is always a moving target. Assessment of this tradeoff requires having the ability to quickly evaluate the impact of flaw size on strength margin across an entire structure for a large number of load cases. The approach taken in this work is to implement an effects of defects analysis and sizing framework within HyperX. HyperX performs optimization of composite structures; this capability has been enhanced to include structural flaw data in the margin of safety calculations performed during optimization. Both the flaw import process and analysis of flaws have been generalized such that any flaw type from any source can be considered. The resulting tool enables rapid assessment of the impact of defects both at a vehicle and part level.

Effects of defects↗
NASA NTRSDate not supplied

Flexible Data and Frame Synchronization Structure for the LunaNet PNT Signal

A LunaNet Lunar Augmented Navigation Service (LANS) is being developed to enable a position, navigation, and timing service for future Lunar operations [1]. The signal includes two components. An in-phase data channel signal is spread by a 1.023 MCPS ranging code that provides a high-rate data message at 250 bps and is encoded by a strong Low Density Parity Check (LDPC) code. A pilot channel with a 5.115 MCPS spreading code is also provided. The pilot code is configured with a secondary (overlay) code that does not currently provide absolute time or frame Synchronization as is the case for L1C [2] [3]. This work shows the advantage of implementing an overlay structure that provides absolute time for the LunaNet LANS signal structure known as the Augmented Forward Signal (AFS). The LunaNet AFS structure was developed to service two classes of user receivers. The first class is a low-complexity user receiver that only receives the 1.023 MCPS signal and does not use the 5.115 MCPS pilot channel. For this class of user, a data frame Sync word is needed. The second class of receiver is a high-end receiver that can processes both data and pilot channels to take advantage of the higher chip rate pilot channel for enhanced robustness and improved accuracy. In the current draft LunaNet LANS AFS design, these users must employ the frame Sync word in the data channel and obtain absolute time after decoding the AFS navigation message [2]. The signal structure would greatly benefit from the addition of a pilot overlay structure that provides absolute time and robust frame Sync for high-end users as done for L1C [3]. To provide a more robust and interoperable AFS structure, this work summarizes a study and recommends alternatives for a new overlay code on the pilot channel that provides absolute time and a Sync word approach on the data channel. The overlay code and Sync word are designed to allow for flexible and robust data synchronization for both low- complexity and high-end user receivers. The new overlay code structure permits frame synchronization performance that is as good as or better than the L1 C signal, while enabling a determination of absolute time upon frame Sync to aid high-end assisted LANS AFS user receivers at low signal to noise levels. We also present the design of rate-matched 5G new radio (5GNR) LDPC codes that fit within the current 6000-symbol frame size along with a time of interval (TOI) word, frame ID (FID) word, and the remaining LunaNet AFS data message blocks. The paper describes and demonstrates robust frame Synchronization performance of the overlay code and Synch word approaches. The results are described in terms of probability of missed detection and probability of false alarm for a correct frame Synchronization at low Eb/No levels expected for decoding the TOI word and LDPC encoded data. Advantages of the proposed data Synchronization structure will be described along with use cases for low-end and high-end receivers. Practical implementation considerations will also be described.

Philip Dafesh↗
NASA NTRSDate not supplied

Flexible Data and Frame Synchronization Structure for the LunaNet PNT Signal

A LunaNet Lunar Augmented Navigation Service (LANS) is being developed to enable a position, navigation, and timing service for future Lunar operations. The signal includes two components. An in-phase data channel signal is spread by a 1.023 MCPS ranging code that provides a high-rate data message at 250 bps and is encoded by a strong Low Density Parity Check (LDPC) code. A pilot channel with a 5.115 MCPS spreading code is also provided. The pilot code is configured with a secondary (overlay) code that does not currently provide absolute time or frame Synchronization as is the case for L1C. This work shows the advantage of implementing an overlay structure that provides absolute time for the LunaNet LANS signal structure known as the Augmented Forward Signal (AFS). The LunaNet AFS structure was developed to service two classes of user receivers. The first class is a low-complexity user receiver that only receives the 1.023 MCPS signal and does not use the 5.115 MCPS pilot channel. For this class of user, a data frame Sync word is needed. The second class of receiver is a high-end receiver that can processes both data and pilot channels to take advantage of the higher chip rate pilot channel for enhanced robustness and improved accuracy. In the current draft LunaNet LANS AFS design, these users must employ the frame Sync word in the data channel and obtain absolute time after decoding the AFS navigation message. The signal structure would greatly benefit from the addition of a pilot overlay structure that provides absolute time and robust frame Sync for high-end users as done for L1C. To provide a more robust and interoperable AFS structure, this work summarizes a study and recommends alternatives for a new overlay code on the pilot channel that provides absolute time and a Sync word approach on the data channel. The overlay code and Sync word are designed to allow for flexible and robust data synchronization for both low- complexity and high-end user receivers. The new overlay code structure permits frame synchronization performance that is as good as or better than the L1 C signal, while enabling a determination of absolute time upon frame Sync to aid high-end assisted LANS AFS user receivers at low signal to noise levels. We also present the design of rate-matched 5G new radio (5GNR) LDPC codes that fit within the current 6000-symbol frame size along with a time of interval (TOI) word, frame ID (FID) word, and the remaining LunaNet AFS data message blocks. The paper describes and demonstrates robust frame Synchronization performance of the overlay code and Synch word approaches. The results are described in terms of probability of missed detection and probability of false alarm for a correct frame Synchronization at low Eb/No levels expected for decoding the TOI word and LDPC encoded data. Advantages of the proposed data Synchronization structure will be described along with use cases for low-end and high-end receivers. Practical implementation considerations will also be described.

LunaNet↗
DOE OSTI2021

Three dimensional vertically structured electronic devices

In one embodiment, a method of forming a vertical transistor includes forming a layer comprising a semiconductor material above a substrate, defining three dimensional (3D) structures in the layer, forming a second region in at least one vertical sidewall of each 3D structure, and forming an isolation region between the 3D structures. In another embodiment, an apparatus includes at least one vertical transistor, where the at least one vertical transistor includes: a substrate comprising a semiconductor material, an array of 3D structures above the substrate, and an isolation region positioned between the 3D structures. Each 3D structure includes the semiconductor material. Each 3D structure also includes a first region having a first conductivity type and a second region having a second conductivity type, the second region including a portion of at least one vertical sidewall of the 3D structure.

Conway, Adam↗
DOE OSTI2023

Additively manufactured structure with reinforced access opening

A method and system of additively-manufacturing a structure having a reinforced access opening includes printing, via an additive printing device having at least one printer head, a portion of the structure adjacent to a support surface. The portion of the structure is printed of a cementitious material, and the printed portion of the structure defines an access opening for the structure. Moreover, the method includes providing a void of the cementitious material at a top boundary of the access opening, placing one or more reinforcement members in the void such that the one or more reinforcement members extend across the void, and continuing to print the printed portion of the structure around the void to build up the structure. Thus, the method also includes backfilling the void with a backfill material to incorporate the one or more reinforcement members within the void into the printed portion of the structure.

Li, Xiaopeng↗
DOE OSTI2024

Development of Lightweight Structural Materials with Improved Properties for Fission Batteries

The notion of a “fission battery” conveys a vision focused on realizing very simple “plug-and-play” nuclear systems that can be integrated into a variety of applications requiring affordable, reliable energy in the form of electricity and/or heat and function without operations and maintenance staff. Fission batteries require lightweight structural materials to increase their mobility, and the lightweight materials must demonstrate structural resilience under various conditions. The objective of this work is to develop lattice structured lightweight structural material featuring a good combination of mechanical properties using advanced modeling and simulation together with an advanced additive manufacturing technique such as laser powder bed fusion. The preliminary results show that different lattice structures and types can be successfully meshed using nTopology software, and the lattice structure data can be successfully transformed to Multiphysics Object-Oriented Simulation (MOOSE) Environment input. Finite Element Analysis (FEA) displays that, at macro/engineering scale simulation, the weight saving design has an obvious effect on tensile behavior such as effective elastic modulus and yield stress. The novel approaches of this work are (1) development of lattice structures for improved mechanical properties using advanced simulation and modeling techniques; and (2) model predictions of the mechanical properties (e.g., strength and stress distribution) of macroscopic materials in order to preliminarily select a lattice structure for additive manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Symmetry-Based Structured Matrices for Efficient Approximately Equivariant Networks

There has been much recent interest in designing symmetry-aware neural networks (NNs) exhibiting relaxed equivariance. Such NNs aim to interpolate between being exactly equivariant and being fully flexible, affording consistent performance benefits. In a separate line of work, certain structured parameter matrices -- those with displacement structure, characterized by low displacement rank (LDR) -- have been used to design small-footprint NNs. Displacement structure enables fast function and gradient evaluation, but permits accurate approximations via compression primarily to classical convolutional neural networks (CNNs). In this work, we propose a general framework -- based on a novel construction of symmetry-based structured matrices -- to build approximately equivariant NNs with significantly reduced parameter counts. Our framework integrates the two aforementioned lines of work via the use of so-called Group Matrices (GMs), a forgotten precursor to the modern notion of regular representations of finite groups. GMs allow the design of structured matrices -- resembling LDR matrices -- which generalize the linear operations of a classical CNN from cyclic groups to general finite groups and their homogeneous spaces. We show that GMs can be employed to extend all the elementary operations of CNNs to general discrete groups. Further, the theory of structured matrices based on GMs provides a generalization of LDR theory focussed on matrices with cyclic structure, providing a tool for implementing approximate equivariance for discrete groups. We test GM-based architectures on a variety of tasks in the presence of relaxed symmetry. We report that our framework consistently performs competitively compared to approximately equivariant NNs, and other structured matrix-based compression frameworks, sometimes with a one or two orders of magnitude lower parameter count.

Samudre, Ashwin↗
DOE OSTI2024

COMPUTER-AIDED LATTICE DESIGN AND ADVANCED MODELING FOR THE DEVELOPMENT OF LIGHTWEIGHT STRUCTURAL MATERIALS

The notion of a “fission battery” conveys a vision focused on realizing very simple “plug-and-play” nuclear systems that can be integrated into a variety of applications requiring affordable, reliable energy in the form of electricity and/or heat and function without operations and maintenance staff. Fission batteries require lightweight structural materials to increase their mobility, and the lightweight materials must demonstrate structural resilience under various conditions. The objective of this work is to develop lattice structured lightweight structural material featuring a good combination of mechanical properties using advanced modeling and simulation together with an advanced additive manufacturing technique such as laser powder bed fusion. The preliminary results show that different lattice structures and types can be successfully meshed using nTopology software, and the lattice structure data can be successfully transformed to Multiphysics Object-Oriented Simulation (MOOSE) Environment input. Finite Element Analysis (FEA) displays that, at macro/engineering scale simulation, the weight saving design has an obvious effect on tensile behavior such as effective elastic modulus and yield stress. The novel approaches of this work are (1) development of lattice structures for improved mechanical properties using advanced simulation and modeling techniques; and (2) model predictions of the mechanical properties (e.g., strength and stress distribution) of macroscopic materials in order to preliminarily select a lattice structure for additive manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Dissecting the structural heterogeneity of proteins by native mass spectrometry

Abstract A single gene yields many forms of proteins via combinations of posttranscriptional/posttranslational modifications. Proteins also fold into higher‐order structures and interact with other molecules. The combined molecular diversity leads to the heterogeneity of proteins that manifests as distinct phenotypes. Structural biology has generated vast amounts of data, effectively enabling accurate structural prediction by computational methods. However, structures are often obtained heterologously under homogeneous states in vitro. The lack of native heterogeneity under cellular context creates challenges in precisely connecting the structural data to phenotypes. Mass spectrometry (MS) based proteomics methods can profile proteome composition of complex biological samples. Most MS methods follow the “bottom‐up” approach, which denatures and digests proteins into short peptide fragments for ease of detection. Coupled with chemical biology approaches, higher‐order structures can be probed via incorporation of covalent labels on native proteins that are maintained at the peptide level. Alternatively, native MS follows the “top‐down” approach and directly analyzes intact proteins under nondenaturing conditions. Various tandem MS activation methods can dissect the intact proteins for in‐depth structural elucidation. Herein, we review recent native MS applications for characterizing heterogeneous samples, including proteins binding to mixtures of ligands, homo/hetero‐complexes with varying stoichiometry, intrinsically disordered proteins with dynamic conformations, glycoprotein complexes with mixed modification states, and active membrane protein complexes in near‐native membrane environments. We summarize the benefits, challenges, and ongoing developments in native MS, with the hope to demonstrate an emerging technology that complements other tools by filling the knowledge gaps in understanding the molecular heterogeneity of proteins.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Electronic structure and magnetism of pristine, defected, and strained $\mathrm{Ti_2N}$ $\mathrm{MX}$ene

Here, from first principles electronic structure calculations, we unravel the evolution of structural, electronic, and magnetic properties of pristine, defected, and strained titanium nitride MXene with different functional groups (-F, -O, -H, and -OH). The formation and cohesive energies reveal their chemical stability. The dynamical stability of Ti 2 N mono-layer is also confirmed by phonon calculations. The MAX phase and defect free functionalized MXenes are metallic except for oxygen terminated (Ti 2 NO 2 ) one which is 100% spin polarized half-metallic ferromagnet. The spin–orbit coupling significantly influences the bare MXene (Ti 2 N) to exhibit Dirac topology and band inversion near the high symmetry directions. The strain effect sways the Fermi level thereby shifting it towards lower energy state under compression and towards higher energy state under tensile strain in Ti 2 NH 2 . The Ti 2 NO 2 exhibits exotic electronic structure not only in pristine but also in strained and defected structures. Its half-metallic nature changes to semi-metallic under 1% compression and it is completely destroyed under 2% compression. In single vacancy defect, its band structure remarkably transforms from half-metallic to semi-conducting with large band gap in 12.5% Ti, weakly semi-conducting in 5.5% Ti, and semi-metallic in 12.5% O. The 25% N defect changes its half-metallic characteristic to metallic. Further, the 12.5% Co substitution preserves its half-metallic character, whereas Mn substitution allows it to convert half-metallic characteristic into weak semi-metallic characteristic preserving ferromagnetism. However, Cr substitution converts half-metallic ferromagnetic state to half-metallic anti-ferromagnetic state. The understanding made here on collective structural stability, and electronic band structure, and magnetic phenomena in novel 2D Ti 2 N derived MXenes open up their possibility in designing them for synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

On the Effects of Aliovalent Substitutions in Thermoelectric Zintl Pnictides. Varied Polyanionic Dimensionality and Complex Structural Transformations–The Case of Sr 3 ZnP 3 vs Sr 3 Al x Zn 1– x P 3

The structures and the transport properties of a novel family of Zintl phosphides and arsenides with the formula AE 3 ZnPn 3 and the solid solutions AE 3 Al x Zn 1–x Pn 3 , AE 3 ZnAs y P 1–y (AE = Sr, Eu; Pn = P, As) are reported. Crystals of nine new phases have been obtained via Pb-flux reactions and used for structural work by means of single-crystal X-ray diffraction methods. The derived orthorhombic structure is without a direct analog, and features unusual structural units, where the Zn atoms are in both distorted tetrahedral and trigonal-planar coordination of pnictogens. Electronic structure calculations reveal moderately wide bandgaps for Sr 3 ZnP 3 and Sr 3 ZnAs 3 , on the order of 0.70 and 0.63 eV, respectively. Electrical transport measurements above room temperature indicate relatively high resistivity values above 500 K (ρ ≈ 4.8 Ω cm and above), but some of the samples exhibit very high Seebeck coefficients, as large as 300 μV/K at 560 K for Sr 3 ZnAs 3 . Aliovalent substitutions in AE 3 ZnPn 3 , achieved by the partial replacement of Zn 2+ with Al 3+ cations promote occupational and positional disorder, which causes structural transformation towards the disordered variant of the Sr 5 Al 2 Sb 6 structure type. Such substitutions also change the dimensionality of the polyanionic sub-lattice in the resulting quaternary AE 3 Al x Zn 1–x Pn 3 phases. Furthermore, preliminary transport property data on the latter reveal nine times lower electrical resistivity (ρ 500 ≈ 0.5 Ω cm) together with a significantly enhanced Seebeck coefficient, αmax ≈ 430 μV/K at 560 K.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Cubic Crystal Structure Formation and Optical Properties within the Ag–B II –M IV –X (B II = Sr, Pb; M IV = Si, Ge, Sn; X = S, Se) Family of Semiconductors

Quaternary chalcogenide semiconductors are promising materials for energy conversion and nonlinear optical applications, with properties tunable primarily by varying the elemental composition and crystal structure. Here, we first analyze the connections among several cubic crystal structure types, as well as the orthorhombic Ag 2 PbGeS 4 -type structure, reported for select members within the Ag–B II –M IV –X (B II = Sr, Pb; M IV = Si, Ge, Sn; X = S, Se) compositional space. Focusing on the Ag–Pb–Si–S and Ag–Sr–Sn–S systems, we show that one structure type, with the formulas Ag 2 Pb 3 Si 2 S 8 and Ag 2 Sr 3 Sn 2 S 8 , is favored. We have prepared powder and single-crystal samples of Ag 2 Pb 3 Si 2 S 8 and Ag 2 Sr 3 Sn 2 S 8 , showing that each takes on the noncentrosymmetric cubic space group I$\bar{43}$d and is isostructural to the previously reported compound Ag 2 Sr 3 Ge 2 Se 8 . Through hybrid density functional theory calculations, these cubic compounds are demonstrated to be (quasi-)direct band gap semiconductors with high densities of states at the band maxima. Furthermore, the band-gap energies are measured by reflectance spectroscopy as 1.95(3) and 2.66(4) eV for Ag 2 Pb 3 Si 2 S 8 and Ag 2 Sr 3 Sn 2 S 8 , respectively. We further measure the optical properties and show the electronic band structures of three other isostructural A I –B II –M IV –X-type materials, i.e., Ag 2 Sr 3 Si 2 S 8 , Ag 2 Sr 3 Ge 2 S 8 , and Ag 2 Sr 3 Ge 2 Se 8 , showing that the band gaps can be predictably tuned by element substitution. Detailed visual analyses of the different structures and of their relationships with other members of the Ag–B II –M IV –X compositional family provide a basis for a broader understanding of the structure formation and optoelectronic properties within the quaternary chalcogenide semiconductor family.

14 SOLAR ENERGY↗