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DOE OSTI2025

Probing Nanorod Assembly and Dynamics in Polymer Nanocomposites in Equilibrium and Shear

Coarse-grained molecular dynamics simulations are used to examine the structure and dynamics of nanorod assemblies in polymer melts under equilibrium and simple shear. We show that as the concentration of nanorods increases, there is a transition from an isotropic phase to a two-phase region in which the nanorods phase separate into a dilute phase and dense bundles of hexagonally packed nanorods. The onset of the two-phase region is below that predicted by Onsager theory, which we attribute to an effective increase in the diameter of nanorods due to a layer of polymer bound to the rod surfaces. Equilibrium simulations show that increasing polymer chain length N enhances nanorod bundling at fixed nanorod concentration. Simulations of systems undergoing simple shear show that flow enhances nanorod alignment and bundling relative to those of equilibrium systems with similar properties. Finally, simulations reveal that increasing nanorod length enhances nanorod alignment under shear at equivalent shear rates but not at equivalent Péclet numbers. Overall, our simulations highlight that polymer matrix-nanorod attraction (i.e., chemistry), shear rate, and matrix chain length are desirable design variables to control the structure of nanorod-containing soft materials under simple shear.

diffusion↗

NASA NTRS2001

STOP Analysis and Optimization of a Very-Low-Distortion Space Instrument: HST WFC3 Case Study

New generation optical instruments with very demanding stability requirements are being proposed and developed for space applications. STOP (Structural-Thermal-Optical Performance) analysis and optimization is crucial in meeting the very tight distortion budgets of these instruments. This presentation outlines STOP analysis and optimization approach in the context of WFC3 (Wide-Field Camera 3), which is a radial instrument designed to replace the Wide-Field Planetary Camera 2 (WFPC2) of the Hubble Space Telescope (HST). WFC3 houses two separate channels, UVIS and IR, and will have greater throughput and sensitivity than WFPC2. WFC3 line-of-sight alignment budget for the UVIS and IR channels are as small as 10 and 20 milli-arcsec, respectively. Its optical bench is the most critical subsystem effecting the optical stability of WFC3 hence our effort concentrates on the design and analysis of the bench and its interfaces. Structural analysis has accompanied the mechanical design of the bench since the initial concept study. A high fidelity structural Finite Element Model (FEM) of the bench has been developed and used for minimizing its thermally induced distortions as well as sizing it to meet the stiffness and strength requirements of a Shuttle launch. The bench is a composite honeycomb panel box structure with a very low planar Coefficient of Thermal Expansion (CTE) of approximately 0.1 ppm/C. Optic components are mounted to super-INVAR inserts bonded into the panels. The bench is kinematically supported on three HST latches via interface struts, which are tailored to exhibit negative CTE to cancel out the thermal motions of the latches. The interface struts also incorporate flexure elements to minimize the mechanical distortions coming into the bench from its enclosure. Bench FEM is coupled with the enclosure FEM to quantify these effects. Short term or on-orbit STOP analysis includes distortion due to the temperature variations of the bench, the struts, and the enclosure. Long term or ground-to-orbit STOP analysis includes distortional effects of gravity release, desorption, and assembly in addition to the ground-to-orbit temperature variations. A rigorous testing program has been implemented for verifying the material properties and the analysis predictions. STOP analysis results demonstrate that both the short-term and the long-term alignment budgets will be met. Presentation will cover design and analysis details that are critical to a successful implementation of the STOP analysis and optimization process.

Kunt, Cengiz↗

DOE OSTI2024

The Multiphasic Teeth of Chiton Articulatus , an Abrasion‐Resistant and Self‐Sharpening Tool for Hard Algae Collection

Abstract Chiton articulatus is a species of mollusk living in the tropical Pacific intertidal rocky shores of Mexico. This species feeds on solid waste organic sources, including hard crustose algae that grow on rocky substrates, by grazing on them with its radula, a flexible chitinous membrane lined with mineralized major lateral teeth. In this study, the composition, morphology, and resulting mechanics of the mature teeth of this species, which have yet to be examined, are revealed. The results show the presence of multiphasic mature teeth, each consisting of aligned hard magnetite nanoparticles on the leading edge of the tooth underneath which are magnetite lamellae, followed by goethite, lepidocrocite, and eventually hydroxyapatite near the trailing edge. This multiregional structure demonstrates a gradation in hardness as well as different microstructural features integrated with tough interfaces. The combination of these microstructural and phase arrangements results in an abrasion‐resistant tough structure with a self‐sharpening ability. The results of this work will help contribute to developing new bioinspired designs while also helping to understand the evolution and feeding habits of these intriguing invertebrates.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Evaluation of PbTe and SnTe as Ohmic Contact Layers in CdTe Solar Cell Devices

For solar cells based on CdTe, the choice of a suitable back contact material is limited by CdTe's deep work function. Here, we explored p-type PbTe and SnTe as ohmic contacts to CdTe. These contact layers were grown on single crystal CdTe substrates by molecular beam epitaxy, and the valence band offset between film and substrate was measured using X-ray photoemission spectroscopy. Polycrystalline device structures were also grown by sublimation to assess performance improvements. Doping was achieved in PbTe by thallium incorporation. Only the highest Tl doped PbTe resulted in a desirable band alignment with the CdTe, forming an electron reflector and no hole barrier. Time-resolved photoluminescence measurements also revealed significant photocarrier lifetime improvements for only the highest doped PbTe. Consequentially, devices incorporating the highest doped PbTe layers showed increased power conversion efficiency, primarily from increased fill factor. Doping of the PbTe was measured via Hall effect with variable magnetic field, which was required due to the formation of an n-type parasitic interface layer. To properly interpret the variable field Hall measurements, we derived an expression for the magnetic field-dependent conductivity tensor of an L-valley semiconductor.

anisotropic band valley↗

DOE OSTI2023

Photo-actuators via epitaxial growth of microcrystal arrays in polymer membranes

Photomechanical crystals composed of three-dimensionally ordered and densely packed photochromes hold promise for high-performance photochemical actuators. However, bulk crystals with high structural ordering are severely limited in their flexibility, resulting in poor processibility and a tendency to fragment upon light exposure, while previous nano- or microcrystalline composites have lacked global alignment. Here we demonstrate a photon-fuelled macroscopic actuator consisting of diarylethene microcrystals in a polyethylene terephthalate host matrix. These microcrystals survive large deformations and show a high degree of three-dimensional ordering dictated by the anisotropic polyethylene terephthalate, which critically also has a similar stiffness. Overall, these ordered and compliant composites exhibit rapid response times, sustain a performance of over at least hundreds of cycles and generate work densities exceeding those of single crystals. In conclusion, our composites represent the state-of-the-art for photochemical actuators and enable properties unattainable by single crystals, such as controllable, reversible and abrupt jumping (photosalient behaviour).

36 MATERIALS SCIENCE↗

DOE OSTI2024

Two-dimensional-lattice-confined single-molecule-like aggregates

Intermolecular distance largely determines the optoelectronic properties of organic matter. Conventional organic luminescent molecules are commonly used either as aggregates or as single molecules that are diluted in a foreigner matrix. They have garnered great research interest in recent decades for a variety of applications, including light-emitting diodes, lasers and quantum technologies, among others. However, there is still a knowledge gap on how these molecules behave between the aggregation and dilution states. Here we report an unprecedented phase of molecular aggregate that forms in a two-dimensional hybrid perovskite superlattice with a near-equilibrium distance, which we refer to as a single-molecule-like aggregate (SMA). By implementing two-dimensional superlattices, the organic emitters are held in proximity, but, surprisingly, remain electronically isolated, thereby resulting in a near-unity photoluminescence quantum yield, akin to that of single molecules. Moreover, the emitters within the perovskite superlattices demonstrate strong alignment and dense packing resembling aggregates, allowing for the observation of robust directional emission, substantially enhanced radiative recombination and efficient lasing. Molecular dynamics simulations together with single-crystal structure analysis emphasize the critical role of the internal rotational and vibrational degrees of freedom of the molecules in the two-dimensional lattice for creating the exclusive SMA phase. Furthermore, this two-dimensional superlattice unifies the paradoxical properties of single molecules and aggregates, thus offering exciting possibilities for advanced spectroscopic and photonic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Decoupling absorption and radiative cooling in mid-wave infrared bolometric elements

We present a spectrally selective, passively cooled mid-wave infrared bolometric absorber engineered to spatially and spectrally decouple infrared absorption and thermal emission. The structure leverages an antenna-coupled metal–insulator–metal resonance for mid-wave infrared normal incidence photon absorption and a long-wave infrared optical phonon absorption feature, aligned closer to peak room temperature thermal emission. The phonon-mediated resonant absorption enables a strong long-wave infrared thermal emission feature limited to grazing angles, leaving the mid-wave infrared absorption feature undisturbed. The two independently controlled absorption/emission phenomena demonstrate decoupling of the photon detection mechanism from radiative cooling and offer a new design approach enabling ultra-thin, passively cooled mid-wave infrared bolometers.

Ware, Alexander (ORCID:0009000256937727)↗

NASA NTRS1972

Solar sensor with autocollimator

Monolithic structure, consisting of fused quartz fabricated solar sensor and autocollimator, measures angle between reference surface on spacecraft and solar vector. Device compensates for errors caused by changes in the alignment of its mountings or component parts. Integrated concept is advantageous whenever sensor mounting errors constitute problems.

Fain, D. L.↗

NASA NTRS1981

Review of auroral particle precipitation

An attempt to establish the precipitation signal of an auroral arc based on data gathered by sounding rockets and satellites is presented. Rocket sounding is useful for altitudes up to a few thousand km, the S3-3 satellite from 4000-8000 km, and satellites in GEO for the equatorial plane. Inverted V structures have been observed down to a few km in width by rockets, and occur on open as well as closed field lines. Observations of bursts of field-aligned electrons, simultaneous ion and electron precipitation, counter-streaming electrons and conics have been interpreted as indicating ac phenomena. The S3-3 has recorded the presence of upward flowing ions, beams, and conics, downward flowing ions, and counter-streaming electrons in the 4000-8000 km region. Finally, plasma injections at synchronous orbit have been identified as the equatorial plane signature of any auroral substorm.

Arnoldy, R. L.↗

NASA NTRS1990

Structural monitoring of filamentary composites using embedded fiber optics

The feasibility of monitoring overall integrity of structural components made of filamentary composites, by embedding optical fibers between lamina of a composite beam, is investigated using a beam constructed of Kevlar/epoxy cloth with embedded optical fibers aligned with the longitudinal axis of the beam. Phase changes were monitored in three different optical fibers as the composite beam was subjected to pure bending, and the strain response of the fibers was compared to the strain gage readings taken at the surface, showing a strong correlation between the phase change and the applied deformation.

Cashon, John L.↗

NASA NTRS2001

Inexpensive Method for Growing Unidirectional Oriented Materials Using Friction-Transferred Poly(tetrafluoroethylene) Substrates

In recent years, there has been an increasing interest in properties of unidirectional materials grown on highly oriented polymer surfaces such as the poly(tetrafluoroethylene) (PTFE) films coated onto smooth glass surfaces. In this technique, a thin PTFE film is deposited by sliding or rubbing a Teflon bar over a heated glass surface at a specific temperature. Depending on the pressure, temperature and sliding rate the thickness of deposited layers can be varied from 30 A to 150 A. The PTFE-coated substrate is simple yet surprising versatile for oriented growth of many organic, inorganic and polymer. The significant aspect of PTFE films is their unusual ability to molecularly align a wide variety of materials grown onto them from solution, melt or vapor phase deposition, at temperature below the melting point of PTFE (approx. 340 C). The PTFE structure may be derived, in part, from the multitude of ridges forming in the film and these ridges can presumably provide effective nucleation sites to induce the unidirectional growth of variety of materials. Electron diffraction studies of these films revealed that the PTFE macromolecules are oriented parallel to each other along the sliding direction. Direct observation of the film thickness, molecular structure and individual fluorine atoms from these highly oriented films were achieved using atomic force microscopy (AFM). In this paper, we also report the first direct observation of individual fluorine atoms, and the measurement of the fluorine-helix and carbon-helix radii to be 1.70 A and 0.54 A, respectively.

Lee, Jonathan A.↗

DOE OSTI2025

Si content in methacrylamide-containing A- b -(B- r -C) block copolymers and its impact on reactive ion etching properties

Block copolymers (BCPs) of an A-block-(B-random-C) architecture have been explored as materials for nanolithography because the composition and chemistry of the random block enables modification of thermodynamic and wetting properties to meet manufacturing criteria. Here, in this study, A-b-(B-r-C) BCPs created by an amidation reaction of polystyrene-block-poly(pentafluorophenyl methacrylate) (PS-b-PPFMA) with controlled amounts of Si add insight to previous conclusions about the dual contributions of BCP chemistry and reactive ion etch (RIE) gas chemistry on etch properties. We focus on two RIE etch characteristics: organosilicon etch resistance in H 2 /N 2 plasma etching and enhanced removal of non-styrenic structures in an Ar/O 2 etch. Consistent with previous studies, higher amounts of Si result in greater etch resistance under H 2 /N 2 RIE, where at least ∼10 wt. % Si is necessary to exhibit sufficient etch resistance. By contrast, Ar/O 2 etching resulted in etch rates independent of Si content. We observe previously unreported surface roughening aligned with morphological domains during the H 2 /N 2 etch of modified PS-b-PPFMA BCPs. Limited in the amount of allowable Si to attain equal surface energy between blocks, these BCPs are further disqualified in forming a Si-containing mask. However, in an Ar/O 2 etch, the same BCPs exhibit suitable etch contrast and smooth domain structures, forming a uniform PS mask. Ultimately, this study uses the chemical flexibility of these materials to demonstrate the mechanisms of interactions between BCP and etch chemistry that must be considered to design effective materials for pattern transfer applications.

Eom, Christopher J. [University of Chicago, IL (Un↗

DOE OSTI2023

Extraction and selective promotion of zero-group velocity and cutoff frequency resonances in bi-dimensional waveguides using the electromechanical impedance method

This study showcases the electromechanical impedance (EMI) technique for extracting and promoting zero-group velocity (ZGV) and cutoff frequency resonances in a waveguide structure. Here, we identify the mechanisms of multiple resonances in the EMI spectra via a wave propagation perspective. Both simulation and experiments reveal the fact that sharp resonances in the conductance spectra are associated with either ZGV or cutoff frequency points. Consequently, we design four test configurations to enhance local resonances by aligning induced motions with considered mode shapes. Reasonable agreement between simulation and experiment results is observed. We evaluate the performance of considered configurations in terms of mode enhancement, and configurations that can selectively promote certain mode families are summarized. This study also shines the light on the EMI technique for quantitative non-destructive evaluation (NDE) by potentially supporting the inverse characterization of mechanical properties of host structures.

42 ENGINEERING↗

DOE OSTI2024

Self-Assembly of a Triblock Copolymer in the Presence of a Rigid Conjugated Polyelectrolyte

The properties of conducting polymers are strongly influenced by structural changes induced by long-range order, which can be achieved by using block copolymers that self-assemble into crystalline structures. These blends result in unique mesophases distinct from the pure components with self-assembly behavior modulated by solution conditions and polymer architectures. High-throughput small-angle X-ray scattering data of aqueous Pluronic P123 (PEO 20 –PPO 70 –PEO 20 ) and conjugated polyelectrolyte poly[3-(potassium-4-butanoate) thiophene-2,5-diyl] (PPBT) blends at various concentrations and temperatures were automatically classified into phase maps by autophasemap, an unsupervised statistical analysis algorithm. The outlined phase boundaries revealed that adding PPBT to high P123 concentrations induced a transition from cubicly ordered spherical micelles to hexagonally packed cylindrical micelles. Shear alignment via rheological small-angle neutron scattering of the blends produced monolithic oriented cubic and hexagonal crystal gels. Furthermore, these insights into the self-assembly of conductive polymer blends will aid in the design of soft materials with tunable structural and electronic properties.

36 MATERIALS SCIENCE↗

NASA NTRS2015

The Role of the Hall Effect in Global Structure and Dynamics of Planetary Magnetospheres: Ganymede as a Case Study

We present high-resolution Hall MHD simulations of Ganymede's magnetosphere demonstrating that Hall electric fields in ion-scale magnetic reconnection layers have significant global effects not captured in resistive MHD simulations. Consistent with local kinetic simulations of magnetic reconnection, our global simulations show the development of intense field-aligned currents along the magnetic separatrices. These currents extend all the way down to the moon's surface, where they may contribute to Ganymede's aurora. Within the magnetopause and magnetotail current sheets, Hall J x B forces accelerate ions to the local Alfven speed in the out-of-plane direction, producing a global system of ion drift belts that circulates Jovian magnetospheric plasma throughout Ganymede's magnetosphere. We discuss some observable consequences of these Hall-induced currents and ion drifts: the appearance of a sub-Jovian 'double magnetopause' structure, an Alfvenic ion jet extending across the upstream magnetopause, and an asymmetric pattern of magnetopause Kelvin-Helmholtz waves.

Magnetic Reconnection↗

NASA NTRS1985

Evaluation of Superplastic Forming and Weld-brazing for Fabrication of Titanium Compression Panels

The two titanium processing procedures, superplastic forming and weld brazing, are successfully combined to fabricate titanium skin stiffened structural panels. Stiffeners with complex shapes are superplastically formed using simple tooling. These stiffeners are formed to the desired configuration and required no additional sizing or shaping following removal from the mold. The weld brazing process by which the stiffeners are attached to the skins utilize spot welds to maintain alignment and no additional tooling is required for brazing. The superplastic formed/weld brazed panels having complex shaped stiffeners develop up to 60 percent higher buckling strengths than panels with conventional shaped stiffeners. The superplastic forming/weld brazing process is successfully scaled up to fabricate full size panels having multiple stiffeners. The superplastic forming/weld brazing process is also successfully refined to show its potential for fabricating multiple stiffener compression panels employing unique stiffener configurations for improved structural efficiency.

Royster, D. M.↗

DOE OSTI2023

Anisotropic magnetism and electronic structure of trigonal EuAl 2 Ge 2 single crystals

Understanding the interplay between magnetic and electronic degrees of freedom is of profound recent interest in different Eu-based magnetic topological materials. Here, we studied the magnetic and electronic properties of the layered Zintl-phase compound EuAl 2 Ge 2 crystallizing in the trigonal CaAl 2 Si 2 -type structure. We report zero-field neutron diffraction, temperature T - and magnetic-field H-dependent magnetic susceptibility χ(T, H), isothermal magnetization M(T, H), heat capacity C p (T, H), and electrical resistivity ρ(T, H) measurements, together with T-dependent angle-resolved photoemission spectroscopy (ARPES) measurements complemented with first-principle calculations. EuAl 2 Ge 2 undergoes second-order A-type antiferromagnetic (AFM) ordering below T N = 27.5(5) K, with the Eu moments (Eu 2+ , S = 7/2) aligned ferromagnetically in the ab plane while these layers are stacked antiferromagnetically along the c axis. The critical fields at which all moments become parallel to the field are 37.5(5) and 52.5(5) kOe for H ∥ ab and H ∥ c, respectively. The H = 0 magnetic structure consists of trigonal AFM domains associated with ab-plane magnetic anisotropy and a field-induced reorientation of the Eu spins in the domains is also evident at T = 2 K below the critical field H c1 = 2.5(1) kOe. The ρ(T) measurements reveal metallic behavior transforming into a slight resistivity increase on cooling towards T N . A pronounced loss of spin-disorder scattering is observed below T N . The ARPES results show that EuAl 2 Ge 2 is metallic both above and below T N , and the Fermi surface is anisotropic with two hole pockets at the zone center and one small electron pocket at each M point. In the AFM phase, we directly observe folded bands in ARPES due to the doubling of the magnetic unit cell along the c axis with an enhancement of quasiparticle weight due to the complex change in the coupling between the magnetic moments and itinerant electrons on cooling below T N . The observed electronic structure is well reproduced by first-principle calculations, which also predict the presence of nontrivial electronic states near the Fermi level in the AFM phase with Z 2 topological numbers 1;(000)

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Large-Area Periodic Arrays of Atomically Flat Single-Crystal Gold Nanotriangles Formed Directly on Substrate Surfaces

The advancement of nanoenabled wafer-based devices requires the establishment of core competencies related to the deterministic positioning of nanometric building blocks over large areas. Within this realm, plasmonic single-crystal gold nanotriangles represent one of the most attractive nanoscale components but where the formation of addressable arrays at scale has heretofore proven impracticable. In this work, a benchtop process is presented for the formation of large-area periodic arrays of gold nanotriangles. The devised growth pathway sees the formation of an array of defect-laden seeds using lithographic and vapor-phase assembly processes followed by their placement in a growth solution promoting planar growth and threefold symmetric side-faceting. The nanotriangles formed in this high-yield synthesis distinguish themselves in that they are epitaxially aligned with the underlying substrate, grown to thicknesses that are not readily obtainable in colloidal syntheses, and present atomically flat pristine surfaces exhibiting gold atoms with a close-packed structure. As such, they express crisp and unambiguous plasmonic modes and form photoactive surfaces with highly tunable and readily modeled plasmon resonances. The devised methods, hence, advance the integration of single-crystal gold nanotriangles into device platforms and provide an overall fabrication strategy that is adaptable to other nanomaterials.

42 ENGINEERING↗