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At least 631 records · Page 35

Chapter 7: Active patterning and structure formation—self-limiting assembly, actuation, and integration

At the suggestion of NASA’s Physical Science Research Program in the Space Life and Physical Science Research and Application Division, Paul Chaikin, Noel Clark, and Sidney Nagel organized a focus session and workshop for the 2020 American Physical Society (APS) March meeting under the auspices of the Division of Soft Matter. Three overarching themes emerged from the workshop and are presented with additional details: • Machines made out of machines • Scalable self-sustaining ecosystems • Active materials and metamaterials This report lays out only some of the potential directions for soft matter dynamics over the next two decades. It also lays out the role that gravity plays in the organization of the basic building blocks of matter. Not only will research on soft matter have tremendous application towards understanding its behavior in our terrestrial environment, but also potentially in other NASA programs such as planetary science, exploration, robotics, etc. Attached is a White Paper for the Decadal Survey that consists of an extended Title along with the previous Introduction and Chapter 2.7 from NASA/CP-20205010493.

Soft matter↗

Chapter 8: Fluids: liquid crystals—self-assembly of the superlarge and superweak active clothing

At the suggestion of NASA’s Physical Science Research Program in the Space Life and Physical Science Research and Application Division, Paul Chaikin, Noel Clark, and Sidney Nagel organized a focus session and workshop for the 2020 American Physical Society (APS) March meeting under the auspices of the Division of Soft Matter. Three overarching themes emerged from the workshop and are presented with additional details: • Machines made out of machines • Scalable self-sustaining ecosystems • Active materials and metamaterials This report lays out only some of the potential directions for soft matter dynamics over the next two decades. It also lays out the role that gravity plays in the organization of the basic building blocks of matter. Not only will research on soft matter have tremendous application towards understanding its behavior in our terrestrial environment, but also potentially in other NASA programs such as planetary science, exploration, robotics, etc. The attached is a White Paper for the Decadal Survey that consists of an extended Title along with the previous Introduction and Chapter 2.8 from NASA/CP-20205010493.

Soft matter↗

Accelerated simulation of near-Earth-orbit polymer degradation

There is a need to simulate the near-Earth-orbit environmental conditions, and it is useful to be able to monitor the changes in physical properties of spacecraft materials. Two different methods for simulating the vacuum-ultraviolet (VUV) and soft X-ray near-Earth-orbit flux are presented. Also, methods for monitoring the changes in optical ultraviolet transmission and mass loss are presented. The results of exposures to VUV photons and charged particles on these materials are discussed.

Laue, Eric↗

Peptide-assisted supramolecular polymerization of the anionic porphyrin meso-tetra(4-sulfonatophenyl)porphine

Electronics made from biological materials are desirable for use in medical devices, biosensors, and soft robotics because they have properties inaccessible to current inorganic technologies. Here, a series of cationic peptides were developed to self-assemble with the anionic porphyrin meso-tetra(4-sulfonatophenyl)porphine (TPPS4) into supramolecular light-harvesting wires known as J-aggregates were developed. In addition to quantifying the binding events between each peptide and TPPS 4 , we found co-incubation with mixed peptides allowed TPPS 4 to bridge two different peptides at their terminal porphyrin-binding regions. The J-aggregates formed on macroscopic scale in near quantitative yield within similar to 3 h and readily interconverted with the soluble monomers upon cycling the pH; to our knowledge, this is the first report of a peptide-porphyrin system with such properties. This work has practical and conceptual relevance to the development of new bioelectronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial microstructure and mechanical properties of rotary inertia friction welded dissimilar 422 martensitic stainless steel to 4140 low alloy steel joints

In this work, dissimilar rotary inertia friction welds between 422 martensitic stainless steel and 4140 martensitic low-alloy steel were made to fabricate prototype heavy-duty diesel engine pistons. The influence of the inertia friction welding process and post weld heat treatment (PWHT) temperature on the interfacial microstructure evolutions and corresponding effects on mechanical properties of the 422/4140 welds were evaluated in detail. Carbon diffused from the 4140 side to the 422 side during PWHT at 650 °C for 1.5 h, causing the formation of a hard carbide-rich layer on the 422 side, and a softer but discontinuous C-depleted layer the 4140 side. PWHT at 700 °C for 1.5 h greatly accelerated C diffusion across the interface relative to 650 °C, resulting in a thicker hard carbide-rich layer and a relatively thick and continuous layer of coarse C-depleted grains (ferrite) on the 4140 side. In addition, the PWHT temperature greatly influenced the tensile properties and fracture behavior of the welds, with the 650 °C PWHT-ed samples failing predominately in a ductile manner in the 4140 heat affected zone during tensile testing. Conversely, the 700 °C PWHT specimens exhibited a strength reduction compared with the 650 °C PWHT specimens because of additional coarsening of the interfacial ferrite layer and softening of the base materials during PWHT, with brittle fracture between the hard and soft layers the predominate failure mechanism. Based on the findings, a reduced PWHT temperature and/or time, minimizing the hardness differential of the base metals, and pre-heating the 422 steel prior to welding are the potential pathways to achieve a more optimal balance between desirable tempering and stress relief of the weld microstructure and undesirable C migration across the weld interface, and to reduce the strength mismatch across the weld.

36 MATERIALS SCIENCE↗

Data-Driven Mapping of the Cesium Cadmium Bromide Phase Space Utilizing a Soft-Chemistry Approach

Soft-chemistry techniques provide a versatile approach to synthesizing inorganic materials under mild conditions, enabling access to compositions and structures that are challenging to achieve through traditional thermodynamically driven solid-state methods. However, these solution-based routes often result in phase competition, requiring precise control over reaction conditions to achieve selective product formation. While one-variable-at-a-time (OVAT) approaches have traditionally been used for phase selection, data-driven strategies are emerging as more efficient methods for navigating complex synthetic spaces. Ternary metal halides, such as cesium cadmium bromides (Cs–Cd–Br), are of growing interest due to their potential in wide and ultrawide band gap applications. Unlike the well-studied cesium lead halide phases, the compositional diversity and solution-based synthesis of ternary Cs–Cd–Br phases remain largely unexplored. This study systematically investigates the synthetic phase space of the Cs–Cd–Br system by constructing a data-driven phase map. Using a common set of precursors and a standardized experimental procedure, we successfully synthesize all four known Cs–Cd–Br phases—CsCdBr 3 , Cs 2 CdBr 4 , Cs 3 CdBr 5 , and Cs 7 Cd 3 Br 13 —each exhibiting distinct structures, morphologies, and optical properties. Our findings highlight the potential of soft-chemistry methods for expanding the library of ternary metal halides and provide key insights into the thermodynamic and kinetic factors governing phase formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hard-to-soft transition-enhanced piezoelectricity in poly(vinylidene fluoride) via relaxor-like secondary crystals activated by high-power ultrasonication

We report although high piezoelectric coefficients have recently been observed in poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] random copolymers, they have low Curie temperatures, which makes their piezoelectricity thermally unstable. It has been challenging to achieve high piezoelectric performance from the more thermally stable PVDF homopolymer. In this report, we describe how high-power ultrasonic processing was used to induce a hard-to-soft piezoelectric transition and improve the piezoelectric coefficient d 31 in neat PVDF. After high-power ultrasonication for 20 min, a uniaxially stretched and poled PVDF film exhibited a high d 31 of 50.2 ± 1.7 pm V -1 at room temperature. Upon heating to 65 °C, the d 31 increased to a maximum value of 76.2 ± 1.2 pm V -1 , and the high piezoelectric performance persisted up to 110 °C. The enhanced piezoelectricity was attributed to the relaxor-like secondary crystals in the oriented amorphous fraction, broken off from the primary crystals by ultrasonication, as suggested by differential scanning calorimetry and broadband dielectric spectroscopy studies.

relaxor-like secondary crystals↗

Hybrid Additive and Subtractive Manufacturing of Dual‐Wavelength Photopolymer Thermosets

Additive manufacturing (AM) techniques such as digital light processing (DLP) AM and stereolithography enable the production of highly complex structures with speed and ease as not previously possible. However, many traditional thermosetting photopolymers used in these processes result in a permanently crosslinked structure incapable of being broken down or modified without the use of energy-intensive processes such as mechanical machining or ablation. To overcome this limitation, this production is described of thiol-ene photopolymer thermosets with dual-wavelength photopolymerization and photodegradation reaction pathways. The dual wavelength selectivity of the polymerization (405 nm) and degradation (365 nm) processes, combined with dual-wavelength DLP AM technology, enables hybrid manufacturing with the ability to add and sequentially subtract material with excellent spatiotemporal control. 2D lithographs and complex 3D architectures with soft elastomeric properties are produced with resolutions as small as 50 µm. Furthermore, the ability to selectively subtract supports from 3D printed structures with deliberate and accurate control is demonstrated. In conclusion, the ability to correct or modify existing structures enables a new paradigm of adaptable materials for corrective manufacturing techniques and temporary structures.

3D Printing↗

Dynamics and X-ray emission of a galactic superwind interacting with disk and halo gas

There is a general agreement that the conspicuous extranuclear X-ray, optical-line, and radio-contiuum emission of starbursts is associated with powerful galactic superwinds blowing from their centers. However, despite the significant advances in observational studies of superwinds, there is no consensus on the nature of the emitting material and even on the emission mechanisms themselves. This is to a great extent a consequence of a poor understanding of dynamical processes in the starburst superwind regions. To address this issue, we have conducted two-dimensional hydrodynamical simulations of galactic superwinds. While previous similar studies have used a single (disk) component to represent the ISM of the starburst galaxy, we analyze the interaction of the wind with a two-component disk-halo ambient interstellar medium and argue that this two-component representation is crucial for adequate modeling of starbursts. The emphasis of this study is on the geometry and structure of the wind region and the X-ray emission arising in the wind material and the shocked gas in the disk and the halo of the galaxy. The simulation results have shown that a clear-cut bipolar wind can easily develop under a range of very different conditions. On the other hand, a complex 'filamentary' structure associated with the entrained dense disk material is found to arise within the hot bubble blown out by the wind. The flow pattern within the bubble is dominated equally by the central biconic outflow and a system of whirling motions r elated to the origin and development of the 'filaments'. The filament parameters make them a good candidate for optical-emission-line filamentary gas observed in starburst halos. We find that the history of mass and energy deposition in the starburst region of the galaxy is crucial for wind dynamics. A 'mild' early wind, which arises as a result of the cumulative effect of stellar winds from massive stars, produces a bipolar vertical cavity in the disk and halo gas without strongly affecting the gaseous disk, thus creating conditions for virtually free vertical escape of the hot gas at the later, much more violent supernova-dominated phases of the starburst. We calculate the luminosity, mass, and effective temperature of the X-ray emitting gas in the 'soft' (0.1 to 0.7 keV, 0.7 to 2.2 keV, and 0.1 to 2.2 keV) and 'hard' (1.6 to 8.3 keV) energy bands and estimate the contribution of different gaseous components to the X-ray flux in these bands. Analysis of these parameters enables us to make conclusions regarding the nature of the X-ray-emitting material. We have inferred that the bulk of the soft thermal X-ray emission from starbursts arises in the wind-shocked material of the disk and halo gas rather than in the wind material itself. This enables us to predict that the integrated soft X-ray spectra of starbursts need not show an overabundance of heavy elements which are believed to be produced copiously in the centers of starbursts. Unlike soft X-ray emission, the hard component of thermal X-ray emission is found to originate in the wind material ejected from the starburst region. However, the derived ratio of hard-to-soft X-ray luminosities is too small compared to that observed in starbursts. We conclude therefore that the observed hard X-ray emission of starbursts is probably not associated with the thermal emission of hot wind or ambient shocked gas. Typical temperatures of the bulk of the soft X-ray-emitting material in our very different models have been found to agree well with the ones estimated on the basis of the ROSAT data for the soft component of X-ray emission of nearby starbursts. We predict that temperatures of the extranuclear soft X-ray-emitting gas in starburst galaxies with heavy element abundances near solar should be close to T(sub Xs = 2 to 5 x 10(exp 6)K.

Suchkov, Anatoly A.↗

MnEdgeNet for accurate decomposition of mixed oxidation states for Mn XAS and EELS L2,3 edges without reference and calibration

Accurate decomposition of the mixed Mn oxidation states is highly important for characterizing the electronic structures, charge transfer and redox centers for electronic, and electrocatalytic and energy storage materials that contain Mn. Electron energy loss spectroscopy (EELS) and soft X-ray absorption spectroscopy (XAS) measurements of the Mn L2,3 edges are widely used for this purpose. To date, although the measurements of the Mn L2,3 edges are straightforward given the sample is prepared properly, an accurate decomposition of the mix valence states of Mn remains non-trivial. For both EELS and XAS, 2+, 3+, and 4+ reference spectra need to be taken on the same instrument/beamline and preferably in the same experimental session because the instrumental resolution and the energy axis offset could vary from one session to another. To circumvent this hurdle, in this study, we adopted a deep learning approach and developed a calibration-free and reference-free method to decompose the oxidation state of Mn L2,3 edges for both EELS and XAS. A deep learning regression model is trained to accurately predict the composition of the mix valence state of Mn. To synthesize physics-informed and ground-truth labeled training datasets, we created a forward model that takes into account plural scattering, instrumentation broadening, noise, and energy axis offset. With that, we created a 1.2 million-spectrum database with 1-by-3 oxidation state composition ground truth vectors. The library includes a sufficient variety of data including both EELS and XAS spectra. By training on this large database, our convolutional neural network achieves 85% accuracy on the validation dataset. We tested the model and found it is robust against noise (down to PSNR of 10) and plural scattering (up to t/λ = 1). We further validated the model against spectral data that were not used in training. In particular, the model shows high accuracy and high sensitivity for the decomposition of Mn 3 O 4 , MnO, Mn 2 O 3 , and MnO 2 . The accurate decomposition of Mn 3 O 4 experimental data shows the model is quantitatively correct and can be deployed for real experimental data. Our model will not only be a valuable tool to researchers and material scientists but also can assist experienced electron microscopists and synchrotron scientists in the automated analysis of Mn L edge data.

25 ENERGY STORAGE↗

Carbon Fiber and Polymer Composites

Tooling is an integral part of composites manufacturing. Composite tools, also called ‘soft’ tools, are more easily constructed than ‘hard’ metal tools and, because they are made from materials similar to the manufactured composite part, they can be made in-house and have a good co-efficient of thermal expansion match. However, as the ‘soft’ designation suggests, they are more vulnerable to wear and typically find application in relatively low-volume production. Additive manufacturing of thermoplastics has proven to be a lucrative option that can help improve the tooling functionalities, as it offers more design flexibility. Owing to the inherent nature of additive manufacturing, the possibility of printing sensors within the tool material and at proximity to otherwise inaccessible areas of the tool become a reality. Continuous carbon fiber (CCF)-reinforced three-dimensional (3D) printing of engineering thermoplastics has proven to be a viable option to strengthen a part well beyond the ideal moduli of unmodified thermoplastic. Furthermore, adding nanotubes or graphene to the thermoplastic matrix will also improve both the thermal conductivity and interlaminar shear strength within the tool. Carbon nanotubes (CNTs) and carbon fibers (CFs) are microwave susceptors; exploiting the physics of Joule heating to increase the energy efficiency of tool hardening and cure rates is a core goal of this project. Because of the rapid volumetric heating enabled by the absorption of microwave or radio frequency energy and electromagnetic (EM) annealing presents an attractive opportunity to significantly reduce manufacturing cycle times while improving part performance.

Craps, Matthew G.↗

Characterizing electronic and atomic structures for amorphous and molecular metal oxide catalysts at functional interfaces by combining soft X-ray spectroscopy and high-energy X-ray scattering

Amorphous thin film materials and heterogenized molecular catalysts supported on electrode and other functional interfaces are widely investigated as promising catalyst formats for applications in solar and electrochemical fuels catalysis. However the amorphous character of these catalysts and the complexity of the interfacial architectures that merge charge transport properties of electrode and semiconductor supports with discrete sites for multi-step catalysis poses challenges for probing mechanisms that activate and tune sites for catalysis. This minireview discusses advances in soft X-ray spectroscopy and high-energy X-ray scattering that provide opportunities to resolve interfacial electronic and atomic structures, respectively, that are linked to catalysis. This review discusses how these techniques can be partnered with advances in nanostructured interface synthesis for combined soft X-ray spectroscopy and high-energy X-ray scattering analyses of thin film and heterogenized molecular catalysts. Further, these combined approaches enable opportunities for the characterization of both electronic and atomic structures underlying fundamental catalytic function, and that can be applied under conditions relevant to device applications.

14 SOLAR ENERGY↗

Roadmap on data-centric materials science

Science is and always has been based on data, but the terms ‘data-centric’ and the ‘4th paradigm’ of materials research indicate a radical change in how information is retrieved, handled and research is performed. It signifies a transformative shift towards managing vast data collections, digital repositories, and innovative data analytics methods. The integration of artificial intelligence and its subset machine learning, has become pivotal in addressing all these challenges. This Roadmap on Data-Centric Materials Science explores fundamental concepts and methodologies, illustrating diverse applications in electronic-structure theory, soft matter theory, microstructure research, and experimental techniques like photoemission, atom probe tomography, and electron microscopy. While the roadmap delves into specific areas within the broad interdisciplinary field of materials science, the provided examples elucidate key concepts applicable to a wider range of topics. The discussed instances offer insights into addressing the multifaceted challenges encountered in contemporary materials research.

36 MATERIALS SCIENCE↗

Reversible Polymer–Metal Mechanical Transitions Enabled by Electrochemical Modulation

The mechanical properties of materials, e.g., elastic modulus and hardness, are important for many engineering applications. Here, we introduce a hierarchically ordered structure (HOS) polymer system that exhibits exceptionally large, reversible changes in mechanical behavior upon electrochemical lithiation and delithiation. Full lithiation of the HOS polymer induces a substantial mechanical transition from polymer-like to metal-like attributes, yielding a 10-fold increase in elastic modulus and a 3-fold increase in hardness, with values comparable to those of aluminum. Upon removal of Li+ ions, the elastic modulus and hardness return to nearly pristine polymer levels, and this transformation remains highly repeatable over many electrochemical cycles. Reversible transitions between polymer-like and metal-like mechanical behaviors offer a new pathway for engineering materials for applications that require tunable mechanical properties, such as soft robotics and stimuli-responsive systems.

Thapa, Santosh↗

Environmental study of miniature slip rings

Investigation studied the long term operation of miniature slip ring assembles in high vacuum of space and included the influence of ring, brush, and insulator materials on electrical noise and mechanical wear. Results show that soft metal vapor plating and niobium diselenide miniature slip rings are beneficial.

Radnik, J. L.↗

Filters for soft X-ray solar telescopes

Soft X-ray telescopes require filters that block visible and infrared light and have good soft X-ray transmission. The optical properties of possible materials are discussed, and the fabrication and testing methods for the filters used in a 10-inch normal incidence telescope for 63 A are described. The best performances in the 44-114-A wavelength range are obtained with foils of carbon and rhodium.

Spiller, Eberhard↗

The x ray variability of NGC6814: Power spectra

Simulation techniques are used to obtain the X-ray variability power spectrum of unevenly sampled GINGA data from NGC6814. A simple power law is not an adequate description of the power spectrum, with the residuals showing excess power on timescales consistent with the periodicity seen in EXOSAT observations of this object. However the shape of the folded lightcurve is very different, with 3 main peaks, two of which are separated by an extremely sharp dip instead of the single peak and small harmonic structure observed by EXOSAT. Using the dip as a fiducial mark, a second GINGA observation of this source taken one year later is found to be consistent with being completely periodic and phase coherent with this first GINGA observation. Thus the period is consistent with being constant over a period of 6 years, but phase coherence is only maintained on timescales of approximately 1 year. Over 75 percent of the total source variability is due to the periodic component (r.m.s. amplitude of 36 percent). The residual variability can be described as the more usual 'flicker noise' f(exp -1.1) powerlaw. This shows no apparent high frequency break on timescales greater than 300 seconds. Subtle differences in the shape of the folded light curve with energy, and the very large amount of power in the periodic component suggest occultation as its origin, though amplification of variability from an X-ray emitting 'hot spot' at the disk inner radius through gravitational lensing is also possible. The former suffers from the very arbitrary nature of the periodic timescale, while the latter is unattractive as it cannot simply explain the lack of high frequency break in the residual power. That these models probably fail to provide an adequate explanation may be due to the added complexity of anisotropy of the X-ray emission, suggested by the discrepancy between the lack of soft photons implied by the flat spectrum and the copious source of soft photons available from reprocessing in the iron line producing material.

Done, C.↗