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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 541 records · Page 30

Novel Directional Solidification of Hypermonotectic Alloys

There are many metal alloy systems that separate into two different liquids upon cooling from a higher temperature. Uniform microstructural development during solidification of these immiscible liquids on Earth is hampered by inherent density differences between the phases. Microgravity processing minimizes settling but segregation still occurs due to gravity independent wetting and coalescence phenomena. Experiments with the transparent organic, metal analogue, succinonitrile-glycerol system were conducted in conjunction with applied ultrasonic energy. The processing parameters associated with this technique have been evaluated in view of optimizing dispersion uniformity. Characterization of the experimental results in terms of an initial modeling effort will also be presented.

Grugel, R. N.↗

Collaboration for the Advancement of Indirect 3D Printing Technology

Amorphous powders often possess high hardness values and other useful mechanical properties. However, densifying these powders into complex shapes while retaining their unique properties is a challenge with standard processing routes. Pressureless sintering, for example, can densify intricate green parts composed of rapidly-solidified powders. But this process typically involves long exposures to elevated temperatures, during which the non-equilibrium microstructure of the powder can evolve towards lower energy configurations with inferior properties. Pressure-assisted compaction techniques, by contrast, can consolidate green parts with simple shapes while preserving the microstructure and properties of the powder feedstock. But parts made with these processes generally require additional post-processing, including machining, which introduces new challenges due to the high hardness of these materials. One processing route that can potentially avoid these issues is Indirect 3D Printing (I-3DP; aka Binder Jetting) followed by melt infiltration. In I-3DP, an organic binder is used to join powder feedstock, layer-by-layer, into a green part. In melt infiltration, this green preform is densified by placing it in contact with a molten alloy that wets the preform and wicks into the pores as a result of capillary forces. When these processes are paired together, they offer two key advantages for the densification of rapidly-solidified powders. The first advantage is that the timescale associated with melt infiltration is on the order of seconds for parts with cm-scale dimensions. So in many instances, infiltration requires only a brief thermal excursion that does not degrade the feedstock’s microstructure. The second advantage is that the combination of binder-jet 3D printing and melt infiltration gives fully-dense net shape objects, minimizing the need for subsequent post-processing. In this work, fully-dense, net shape objects have been fabricated from an amorphous powder using I-3DP and molten bronze infiltration while maintaining the amorphous microstructure. X-ray diffraction, scanning electron microscopy, and differential thermal analysis were used to characterize the structural evolution of the powder feedstock during an infiltration heating cycle. Microindentation and bend tests were performed on the infiltrated material to evaluate its mechanical properties. It was found that infiltration improved both the ductility and strength of the sintered preforms by eliminating the stress concentration at the interparticle necks. The infiltrated material had an 11 GPa Vickers hardness and moderate damage tolerance, making it well-suited for applications requiring hard, net shape parts.

42 ENGINEERING↗

Atomic scale observation of phase separation and formation of silicon clusters in Hf higk-{kappa} silicates

Hafnium silicate films were fabricated by RF reactive magnetron sputtering technique. Fine microstructural analyses of the films were performed by means of high-resolution transmission electron microscopy and atom probe tomography. A thermal treatment of as-grown homogeneous films leads to a phase separation process. The formation of SiO{sub 2} and HfO{sub 2} phases as well as pure Si one was revealed. This latter was found to be amorphous Si nanoclusters, distributed uniformly in the film volume. Their mean diameter and density were estimated to be about 2.8 nm and (2.9 {+-} 0.4) x 10{sup 17} Si-ncs/cm{sup 3}, respectively. The mechanism of the decomposition process was proposed. The obtained results pave the way for future microelectronic and photonic applications of Hf-based high-{kappa} dielectrics with embedded Si nanoclusters.

36 MATERIALS SCIENCE↗

In-situ visualization of corrosion behavior of Al CoCrFeNi high-entropy alloys during electrochemical polarization

In this study, the corrosion behavior of the Al x CoCrFeNi (x = 0.3, 0.5, 0.7) high-entropy alloys (HEAs) is investigated by an in-situ visualization system. Surface morphology changes on both micro-spatial and temporal scales are monitored in the 3.5 wt% NaCl solution during the potentiodynamic polarization. The microstructures of the Al x CoCrFeNi HEAs are characterized by SEM, EBSD, and EDS. The results show that the microstructure evolves from singe face-centered cubic (FCC) phase to multi-phases by increasing the Al content. The in-situ observations directly reveal the different localized corrosion processes in the AlxCoCrFeNi HEAs. In the single FCC phase Al 0.3 CoCrFeNi HEA, localized corrosion shows in the form of pitting. In the Al 0.5 CoCrFeNi and Al 0.7 CoCrFeNi alloys, which possess FCC and body-centered cubic (BCC) phases, the localized corrosion initiates and propagates in the Cr-depleted BCC phase. In addition, the in-situ visualization uncovers the evolution of current serration, which represents the propagation and repassivation of metastable pit during the polarization. The frequent occurrence of metastable pits indicates distinct repassivation ability of the Al 0.3 CoCrFeNi HEA.

36 MATERIALS SCIENCE↗

Visualization of Hierarchical Nanodomains in Polymer/Fullerene Bulk Heterojunction Solar Cells

Here, traditional electron microscopy techniques such as bright-field imaging provide poor contrast for organic films and identification of structures in amorphous material can be problematic, particularly in high-performance organic solar cells. By combining energy-filtered corrected transmission electron microscopy, together with electron energy loss and X-ray energy-dispersive hyperspectral imaging, we have imaged PTB7/ PC 61 BM blended polymer optical photovoltaic films, and were able to identify domains ranging in size from several hundred nanometers to several nanometers in extent. This work verifies that microstructural domains exist in bulk heterojunctions in PTB7/PC 61 BM polymeric solar cells at multiple length scales and expands our understanding of optimal device performance providing insight for the design of even higher performance cells.

14 SOLAR ENERGY↗

Mechanical, Morphological, and Charge Transport Properties of NDI Polymers with Variable Built‐in Π‐Conjugation Lengths Probed by Simulation and Experiment

Abstract Mechanically deformable polymeric semiconductors are a key material for fabricating flexible organic thin‐film transistors (FOTFTs)—the building block of electronic circuits and wearable electronic devices. However, for many π‐conjugated polymers achieving mechanical deformability and efficient charge transport remains challenging. Here the effects of polymer backbone bending stiffness and film microstructure on mechanical flexibility and charge transport are investigated via experimental and computational methods for a series of electron‐transporting naphthalene diimide (NDI) polymers having differing extents of π‐conjugation. The results show that replacing increasing amounts of the π‐conjugated comonomer dithienylvinylene (TVT) with the π‐nonconjugated comonomer dithienylethane (TET) in the backbone of the fully π‐conjugated polymeric semiconductor, PNDI‐TVT 100 (yielding polymeric series PNDI‐TVT x , 100 ≥x≥ 0), lowers backbone rigidity, degree of texturing, and π–π stacking interactions between NDI moieties. Importantly, this comonomer substitution increases the mechanical robustness of PNDI‐TVT x while retaining efficient charge transport. Thus, reducing the TVT content of PNDI‐TVT x suppresses film crack formation and dramatically stabilizes the field‐effect electron mobility upon bending (e.g., 2 mm over 2000 bending cycles). This work provides a route to tune π–π stacking in π‐conjugated polymers while simultaneously promoting mechanical flexibility and retaining good carrier mobility in FOTFTs.

Chemistry↗

The sequence of intermetallic formation and solidification pathway of an Al–13Mg–7Si–2Cu in-situ composite

The phase transformation sequence and solidification behaviour of an Al–13Mg–7Si–2Cu in-situ composite was examined using a combination of computer-aided cooling curve thermal analysis and interrupted quenching techniques. Five different phases were identified by analysing the derivative cooling curves, the X-ray diffraction profile, optical and scanning electron microscopy images and the corresponding energy dispersive spectroscopy. It has been found that the solidification of this alloy begins with primary Mg{sub 2}Si precipitation and continues with the formation of eutectic Al–Mg{sub 2}Si, followed by Al{sub 5}FeSi and simultaneous precipitation of Al{sub 5}Cu{sub 2}Mg{sub 8}Si{sub 6} and Al{sub 2}Cu complex intermetallic phases. The formation of the last three intermetallic compounds changes the solidification behaviour of these composites remarkably due to their complex eutectic formation reactions. The solidification of the alloy, calculated using the Factsage thermochemical analysis software, has demonstrated a good agreement with the experiments in terms of compound prediction, their weight fractions and reaction temperatures. - Highlights: • Solidification path of a commercial Al-13Mg-7Si-2Cu composite was characterized. • Five different phases were identified and then confirmed with EDS and XRD results. • Mg{sub 2}Si, Al-Mg{sub 2}Si,Al{sub 5}FeSi (β),Al{sub 5}Cu{sub 2}Mg{sub 8}Si{sub 6} (Q) and Al{sub 2}Cu(θ) precipitated respectively. • Solidification was predicted using the Factsage thermochemical analysis software.

36 MATERIALS SCIENCE↗

Unraveling the Unconventional Order of a High-Mobility Indacenodithiophene-Benzothiadiazole Copolymer

We report a new class of donor–acceptor (D-A) copolymers found to produce high charge carrier mobilities competitive with amorphous silicon (>1 cm 2 V –1 s –1 ) exhibit the puzzling microstructure of substantial local order, however lacking long-range order and crystallinity previously deemed necessary for achieving high mobility. Here, we demonstrate the application of low-dose transmission electron microscopy to image and quantify the nanoscale and mesoscale organization of an archetypal D-A copolymer across areas comparable to electronic devices (≈9 μm 2 ). The local structure is spatially resolved by mapping the backbone (001) spacing reflection, revealing nanocrystallites of aligned polymer chains throughout nearly the entire film. Analysis of the nanoscale structure of its ordered domains suggests significant short- and medium-range order and preferential grain boundary orientations. Moreover, we provide insights into the rich, interconnected mesoscale organization of this new family of D-A copolymers by analysis of the local orientational spatial autocorrelations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of Sr doping on structure and microstructural properties of LaFeO{sub 3}

The doping of Strontium in LaFeO{sub 3} and its influence on the structural and microstructure properties were studied thoroughly. A few sets of Sr doping in La{sub (1-x)}Fe{sub x}O{sub 3}, where x=0.00, 0.02, and 0.06 were made through the solution combustion synthesis method using urea as fuel. X-ray diffraction was applied to get information about the structure and purity. The Rietveld refinement on X-ray diffraction peaks have been done, in order to calculate various structural parameters. The morphology of La{sub (1-x)}Sr{sub x}FeO{sub 3} nanoscale particles has been confirmed by field emission scanning electron microscopy (FESEM) technique. Differential scanning calorimetry (DSC) signals demonstrated the antiferromagnetic to paramagnetic transition (T{sub N}). The FTIR spectra was provided the information about various vibration modes in samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The interplay of microstructure and magnetism in La{sub 3}Ni{sub 2}SbO{sub 9}

La{sub 3}Ni{sub 2}SbO{sub 9} adopts a perovskite-related structure in which the six-coordinate cation sites are occupied alternately by Ni{sup 2+} and a disordered arrangement of Ni{sup 2+}/Sb{sup 5+}. A polycrystalline sample has been studied by neutron diffraction in applied magnetic fields of 0≤H/kOe≤50 at 5 K. In 0 kOe, weak magnetic Bragg scattering consistent with the adoption of a G-type ferrimagnetic structure is observed; the ordered component of the magnetic moment was found to be 0.89(7) µ{sub B} per Ni{sup 2+} cation. This increased to 1.60(3) µ{sub B} in a field of 50 kOe. Transmission electron microscopy revealed variations in the Ni:Sb ratio across crystallites of the sample. It is proposed that these composition variations disrupt the magnetic superexchange interactions within the compound, leading to domain formation and a reduced average moment. The application of a magnetic field aligns the magnetisation vectors across the crystal and the average moment measured by neutron diffraction increases accordingly. The role played by variations in the local chemical composition in determining the magnetic properties invites comparison with the behaviour of relaxor ferroelectrics. - Graphical abstract: Composition variations across a crystal of La3Ni2SbO9 result in anomalous magnetic behavior. - Highlights: • Ordered magnetic moment of Ni{sup 2+} increases in an applied magnetic field. • Composition variations detected by electron microscopy. • Increase in magnetic moment can be explained by presence of composition variations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermal and electronic charge transport in bulk nanostructured Zr{sub 0.25}Hf{sub 0.75}NiSn composites with full-Heusler inclusions

Bulk Zr{sub 0.25}Hf{sub 075}NiSn half-Heusler (HH) nanocomposites containing various mole fractions of full-Heusler (FH) inclusions were prepared by solid state reaction of pre-synthesized HH alloy with elemental Ni at 1073 K. The microstructures of spark plasma sintered specimens of the HH/FH nanocomposites were investigated using transmission electron microscopy and their thermoelectric properties were measured from 300 K to 775 K. The formation of coherent FH inclusions into the HH matrix arises from solid-state Ni diffusion into vacant sites of the HH structure. HH(1-y)/FH(y) composites with mole fraction of FH inclusions below the percolation threshold, y{approx}0.2, show increased electrical conductivity, reduced Seebeck coefficient and increased total thermal conductivity arising from gradual increase in the carrier concentration for composites. A drastic reduction ({approx}55%) in {kappa}{sub l} was observed for the composite with y=0.6 and is attributed to enhanced phonon scattering due to mass fluctuations between FH and HH, and high density of HH/FH interfaces. - Graphical abstract: Large reduction in the lattice thermal conductivity of bulk nanostructured half-Heusler/full-Heusler (Zr{sub 0.25}Hf{sub 075}NiSn/ Zr{sub 0.25}Hf{sub 075}Ni{sub 2}Sn) composites, obtained by solid-state diffusion at 1073 K of elemental Ni into vacant sites of the half-Heusler structure, arising from the formation of regions of spinodally decomposed HH and FH phases with a spatial composition modulation of {approx}2 nm. Highlights: > Bulk composites from solid state transformation of half-Heusler matrix through Ni diffusion. > Formation of coherent phase boundaries between half-Heusler matrix and full-Heusler inclusion. > Alteration of thermal and electronic transports with increasing full-Heusler inclusion. > Enhanced phonon scattering at half-Heusler/ full-Heusler phase boundaries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectroscopic and theoretical studies of potassium sodium L-(+)-tartrate tetrahydrate and L-tartaric acid used as precursors for in situ laser-induced deposition of the catalytically active copper microstructures

In this work we study the influence of L-(+)-КNaC{sub 4}H{sub 4}O{sub 6} × 4H{sub 2}O (KNaT) and L-H{sub 2}C{sub 4}H{sub 4}O{sub 6} (H{sub 2}T) on the complexation processes occurring during in situ laser-induced catalytic destruction of the organic components of the aqueous solutions with formation of the unsaturated hydrocarbons. For that purpose, ATR-FTIR, Raman, IR, and NIR spectroscopy as well as quantum chemical calculations were implemented. It was observed that hydration of T{sup 2−} anion via carboxylate groups is stronger than that via hydroxyl groups. We also established the changes in the spectral characteristics of the absorption bands corresponding to vibrations of T{sup 2−}, HT{sup −}, and H{sub 2}T, at solid state-liquid and acid-salt transitions, depending on concentration of the solution components and the [OH{sup −}]/[H{sub 2}T] ratio. Finally, it was shown that ethylene is a main product of the catalytic destruction of the copper tartrate complexes.

36 MATERIALS SCIENCE↗

Influence of the molecular weight and size distribution of PSS on mixed ionic-electronic transport in PEDOT:PSS

The commercially available polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is ubiquitous in organic and hybrid electronics. As such, it has often been used as a benchmark material for fundamental studies and the development of new electronic devices. Yet, most studies on PEDOT:PSS have focused on its electronic conductivity in dry environments, with less consideration given to its ion transport, coupled ionic-electronic transport, and charge storage properties in aqueous environments. These properties are essential for applications in bioelectronics (sensors, actuators), charge storage devices, and electrochromic displays. Importantly, past studies on mixed ionic-electronic transport in PEDOT:PSS neglected to consider how the molecular structure of PSS affects mixed ionic-electronic transport. Herein, we therefore investigated the effect of the molecular weight and size distribution of PSS on the electronic properties and morphology of PEDOT:PSS both in dry and aqueous environments, and overall performance in organic electrochemical transistors (OECTs). Using reversible addition–fragmentation chain transfer (RAFT) polymerization with two different chain transfer agents, six PSS samples with monomodal, narrow (D = 1.1) and broad (D = 1.7) size distributions and varying molecular weights were synthesized and used as matrices for PEDOT. We found that using higher molecular weight of PSS (Mn = 145 kg mol –1 ) and broad dispersity led to OECTs with the highest transconductance (up to 16 mS) and [μC*] values (~140 F cm –1 V –1 s –1 ) in PEDOT:PSS, despite having a lower volumetric capacitance (C* = 35 ± 4 F cm –3 ). The differences were best explained by studying the microstructure of the films by atomic force microscopy (AFM). We found that heterogeneities in the PEDOT:PSS films (interconnected and large PEDOT- and PSS-rich domains) obtained from high molecular weight and high dispersity PSS led to higher charge mobility (μOECT ~4 cm 2 V –1 s –1 ) and hence transconductance. Furthermore, these studies highlight the importance of considering molecular weight and size distribution in organic mixed ionic-electronic conductor, and could pave the way to designing high performance organic electronics for biological interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

3D Printing of Advanced Biocomposites on Earth and Beyond

Human exploration off planet is severely limited by the cost of launching materials into space and re-supply. Thus materials brought from earth must be light, stable and reliable at destination. Using traditional approaches a lunar or Mars base would require either transporting a hefty store of metals or heavy manufacturing equipment and construction materials for in situ extraction; both would severely limit any other mission objectives. Long-term human space presence requires periodic replenishment, adding a massive cost overhead. Even robotic missions often sacrifice science goals for heavy radiation and thermal protection. Biology has the potential to solve these problems because it can replicate and repair itself, and do a wide variety of chemical reactions including making food, fuel and materials. Synthetic biology can greatly enhance and expand life's evolved repertoire. Using natural and synthetically altered organisms as the feedstock for additive manufacturing could one day make possible the dream of producing bespoke tools, food, smart fabrics and even replacement organs on demand. To this end our lab has produced a proof-of-concept bioprinter with nearly one-cell resolution. Genetically engineering yeast cells to secrete bioproducts subsequent to printing allows the potential to make biomaterials with a fine microstructure. Imagine a production system that, at a few micron scale resolution, can add mollusk shell for compressive strength per unit mass, spider silk or collagen for tensile strength per unit mass, and potentially biologically-deposited wires. Now imagine what new products can be enabled by such a technology, on earth or beyond

Metals↗

3D Printing of Advanced Biocomposites on Earth and Beyond

Human exploration off planet is severely limited by the cost of launching materials into space and re-supply. Thus materials brought from earth must be light, stable and reliable at destination. Using traditional approaches a lunar or Mars base would require either transporting a hefty store of metals or heavy manufacturing equipment and construction materials for in situ extraction; both would severely limit any other mission objectives. Long-term human space presence requires periodic replenishment, adding a massive cost overhead. Even robotic missions often sacrifice science goals for heavy radiation and thermal protection. Biology has the potential to solve these problems because it can replicate and repair itself, and do a wide variety of chemical reactions including making food, fuel and materials. Synthetic biology can greatly enhance and expand life's evolved repertoire. Using natural and synthetically altered organisms as the feedstock for additive manufacturing could one day make possible the dream of producing bespoke tools, food, smart fabrics and even replacement organs on demand. To this end our lab has produced a proof-of-concept bioprinter with nearly one-cell resolution. Genetically engineering yeast cells to secrete bioproducts subsequent to printing allows the potential to make biomaterials with a fine microstructure. Imagine a production system that, at a few micron scale resolution, can add mollusk shell for compressive strength per unit mass, spider silk or collagen for tensile strength per unit mass, and potentially biologically-deposited wires. Now imagine what new products can be enabled by such a technology, on earth or beyond.

Biology↗

High‐Speed Embedded Ink Writing of Anatomic‐Size Organ Constructs

Embedded ink writing (EIW) is an emerging 3D printing technique that fabricates complex 3D structures from various biomaterial inks but is limited to a printing speed of ∼10 mm s −1 due to suboptimal rheological properties of particulate-dominated yield-stress fluids when used as liquid baths. In this work, a particle-hydrogel interactive system to design advanced baths with enhanced yield stress and extended thixotropic response time for realizing high-speed EIW is developed. In this system, the interactions between particle additive and three representative polymeric hydrogels enable the resulting nanocomposites to demonstrate different rheological behaviors. Accordingly, the interaction models for the nanocomposites are established, which are subsequently validated by macroscale rheological measurements and advanced microstructure characterization techniques. Filament formation mechanisms in the particle-hydrogel interactive baths are comprehensively investigated at high printing speeds. To demonstrate the effectiveness of the proposed high-speed EIW method, an anatomic-size human kidney construct is successfully printed at 110 mm s −1 , which only takes ∼4 h. This work breaks the printing speed barrier in current EIW and propels the maximum printing speed by at least 10 times, providing an efficient and promising solution for organ reconstruction in the future.

36 MATERIALS SCIENCE↗