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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 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Phase Behavior of a Single Structured Ionomer Chain in Solution

Structured polymers offer a means to tailor transport pathways within mechanically stable manifolds. Here we examine the building block of such a membrane, namely a single large pentablock co-polymer that consist of a center block of a randomly sulfonated polystyrene, designed for transport, tethered to poly-ethylene-r-propylene and end-capped by poly-t-butyl styrene, for mechanical stability,using molecular dynamics simulations. The polymer structure in a cyclohexane-heptane mixture, a technologically viable solvent, and in water, a poor solvent for all segments and a ubiquitous substance is extracted. In all solvents the pentablock collapsed into nearly spherical aggregates where the ionic block is segregated. In hydrophobic solvents, the ionic block resides in the center, surrounded by swollen intermix of flexible and end blocks. In water all blocks are collapsed with the sulfonated block residing on the surface. Our results demonstrate that solvents drive different local nano-segregation, providing a gateway to assemble membranes with controlled topology.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Influence of laser cladding regimes on structural features and mechanical properties of coatings on titanium substrates

In this paper an influence of the tantalum content on the structure and properties of surface layers of the titanium alloy doped using a laser treatment technology was investigated. It was found that an increase of a quantity of filler powder per one millimeter of a track length contributed to a rise of the content of undissolved particles in coatings. The maximum thickness of a cladded layer was reached at the mass of powder per the length unit equaled to 5.5 g/cm. Coatings were characterized by the formation of a dendrite structure with attributes of segregation. The width of a quenched fusion zone grew with an increase in the rate of powder feed to the treated area. Significant strengthening of the titanium surface layer alloyed with tantalum was not observed; however, the presence of undissolved tantalum particles can decrease the hardness of titanium surface layers.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Imaging the surface morphology, chemistry and conductivity of LiNi 1/3 Fe 1/3 Mn 4/3 O 4 crystalline facets using scanning transmission X-ray microscopy

We have employed scanning transmission X-ray microscopy (STXM) using the X-ray fluorescence mode in order to elucidate the chemical structures at Ni, Fe, Mn and O sites from the (111) and (100) facets of micron-sized LiNi 1/3 Fe 1/3 Mn 4/3 O 4 energy material particles. Furthermore, STXM imaging using electron yield mode has mapped out the surface conductivity of the crystalline particles. Our study presents a novel approach that visualizes local element segregation, chemistry and conductivity variation among different crystal facets, which will assist further tailoring of the morphology and surface structure of this high voltage spinel lithium ion battery cathode material.

25 ENERGY STORAGE↗
DOE OSTI2023

Machine-to-machine variability of roughness and corrosion in additively manufactured 316L stainless steel

Numerous studies on the corrosion response of metal AM have been conducted. Nonetheless, the specimens being tested are commonly ground or polished to remove the outer as-built surface. If metal AM is truly going to be employed as a transformative technology that can produce complex shapes that do not require traditional machining, then the material needs to be evaluated in the as-built state. The reality is that AM alloys have shown significant inconsistencies regarding as-built surface texture, topology, and residual stress. One metric that has shown significant unpredictability in the literature is the susceptibility to localized corrosion of typically passive alloys, such as stainless steel (SS). There are a large number of studies that have attempted to understand the corrosion response of metal AM materials, but these studies are typically performed on materials that have been printed on a single machine and often mechanically polished to a smooth finish. This study compares the corrosion response of as-built AM, laser-beam powder bed fusion (LB-PBF), 316L SS parts that have been fabricated on five different machines. The majority of this work focused on understanding the susceptibility to localized corrosion of AM metals with respect to machine-dependent variables, namely surface roughness, and build angle. Surface roughness data was collected using scanning white light triangulation, laser scanning confocal microscopy, and coherence scanning interferometry. The results show that there is significant variability (p two-tail < 0.05) in the susceptibility to local corrosion initiation of LB-PBF 316L SS samples built on different machines. Surface oxides were probed with electron dispersive spectroscopy and revealed that variations in local corrosion susceptibility likely arise from differences in the stability of the passive film caused by chemical segregation, unique microstructure, and tortuous roughness features at the as-built surfaces. The variability of roughness and corrosion properties from test samples printed on different machines was corroborated by property measurements performed at five different testing sites, proving reproducibility of the data. Most importantly, this study shows that if the as-built surface layer is removed through grinding or electropolishing the machine-to-machine variation observed in the corrosion susceptibility is reduced.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Ices on the surface of Triton

The near-infrared spectrum of Triton reveals ices of nitrogen, methane, carbon monoxide, and carbon dioxide, of which nitrogen is the dominant component. Carbon dioxide ice may be spatially segregated from the other more volatile ices, covering about 10 percent of Triton's surface. The absence of ices of other hydrocarbons and nitriles challenges existing models of methane and nitrogen photochemistry on Triton.

Cruikshank, Dale P.↗
NASA NTRS1990

Containerless low gravity processing of glass forming and immiscible alloys

Under normal one-g conditions immiscible alloys segregate extensively during solidification due to sedimentation of the more dense of the immiscible liquid phases. Immiscible (hypermonotectic) gold-rhodium alloys were processed in the 100 meter drop tube under low gravity, containerless conditions to determine the feasibility of producing dispersed structures. Three alloy compositions were utilized. Alloys containing 10 percent by volume of the gold-rich hypermonotectic phase exhibited a tendency for the gold-rich liquid to wet the outer surface of the samples. This wetting tendency led to extensive segregation in several cases. Alloys containing 80 and 90 percent by volume of the gold-rich phase possessed completely different microstructures from the 10 percent samples when processed under low-g, containerless conditions. Several samples exhibited microstructures consisting of well dispersed 2 to 3 microns diameter rhodium-rich spheres in a gold-rich matrix.

Andrews, J. Barry↗
DOE OSTI2020

Charge regulation mechanism in end-tethered weak polyampholytes

Weak polyampholytes, containing oppositely charged dissociable groups, are expected to be responsive to changes in ionic conditions. Here, we determine structural and thermodynamic properties, including the charged groups’ degrees of dissociation, of end-tethered weak polyampholyte layers as a function of salt concentration, pH, and the solvent quality. For diblock weak polyampholytes grafted by their acidic blocks, we find that the acidic monomers increase their charge while the basic monomers decrease their charge with decreasing salt concentration for pH values less than the pK a value of both monomers and vice versa when the pH > pK a . This complex charge regulation occurs because the electrostatic attraction between oppositely charged blocks is stronger than the repulsion between monomers with the same charge in both good and poor solvents when the screening by salt ions is weak. This is shown by the retraction of the top block into the bottom layer. In the case of poor solvent conditions to the basic block (the top block), we find lateral segregation of basic monomers into micelles, forming a two-dimensional hexagonal pattern on the surface at intermediate and high pH values for monovalent salt concentrations from 0.01 to 0.1 M. When the solvent is poor to both blocks, we find lateral segregation of the grafted acidic block into lamellae with longitudinal undulations of low and high acidic monomer density. By exploiting weak block polyampholytes, our work expands the parameter space for creating responsive surfaces stable over a wide range of pH and salt concentration.

36 MATERIALS SCIENCE↗
DOE OSTI2017

High-indexed Pt 3 Ni alloy tetrahexahedral nanoframes evolved through preferential CO etching

Here, chemically controlling crystal structures in nanoscale is challenging, yet provides an effective way to improve catalytic performances. Pt-based nanoframes are a new class of nanomaterials that have great potential as high-performance catalysts. To date, these nanoframes are formed through acid etching in aqueous solutions, which demands long reaction time and often yields ill-defined surface structures. Herein we demonstrate a robust and unprecedented protocol for facile development of high-performance nanoframe catalysts using size and crystallographic facet-controlled PtNi 4 tetrahexahedral nanocrystals prepared through a colloidal synthesis approach as precursors. This new protocol employs the Mond process to preferentially dealloy nickel component in the <100> direction through carbon monoxide etching of carbon-supported PtNi 4 tetrahexahedral nanocrystals at an elevated temperature. The resultant Pt 3 Ni alloy tetrahexahedral nanoframes possess an open, stable, and high-indexed microstructure, containing a segregated Pt thin layer strained to the Pt–Ni alloy surfaces and featuring a down-shift d-band center as revealed by the density functional theory calculations. These nanoframes exhibit much improved catalytic performance, such as high stability under prolonged electrochemical potential cycles, promoting direct electro-oxidation of formic acid to carbon dioxide and enhancing oxygen reduction reaction activities. Because carbon monoxide can be generated from the carbon support through thermal annealing in air, a common process for pretreating supported catalysts, the developed approach can be easily adopted for preparing industrial scale catalysts that are made of Pt–Ni and other alloy nanoframes.

36 MATERIALS SCIENCE↗
DOE OSTI2013

A Level Set Evaporation Model for Heterogeneous Atom Probe Tip

With the development of local electrode atom probe tomography (LEAP), the materials systems feasible for atomic structure determination has expanded from predominantly metals to include heterogeneous materials with complex structure and compositions. This makes the 3D atomic structure determination possible for most energy materials in battery, fuel cell, semiconductor, and nuclear applications. Atom probe tomography (APT) has been utilized to study multiphase materials with segregation and interface problems. The unique and quantitative information retrieved from APT can provide a foundation for the study of kinetic pathways, nanoscale composition mapping, multilayer interfacial segregation, dislocations and grain boundaries. However, a new challenge surfaces when the materials systems expand into heterogeneous materials: the traditional structure reconstruction introduces false magnification and large artifacts due to the underlying assumption of uniform and isotropic evaporation.

Atom probe, heterogeneous structure, evporation mo↗
DOE OSTI2016

A mechanism of Cu work function reduction in CsBr/Cu photocathodes

Thin films of CsBr deposited on Cu(100) have been proposed as next-generation photocathode materials for applications in particle accelerators and free-electron lasers. However, the mechanisms underlying an improved photocathode performance remain poorly understood. We present density Functional Theory (DFT) calculations of the work function reduction following the application of CsBr thin film coatings to Cu photocathodes. The effects of structure and van der Waals forces are examined. Calculations suggest that CsBr films can reduce the work function by around 1.5 eV, which would explain the exponential increase in quantum efficiency (QE) of coated vs. uncoated photocathodes. In conclusion, a model explaining experimentally observed laser activation of photocathode is provided whereby the photo-induced creation of di-vacancies at the surface, and their subsequent diffusion throughout the lattice and segregation at the interface leads to a further increase in QE after a period of laser irradiation.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Ti 3 C 2 T x (MXene)–polyacrylamide nanocomposite films

Polymer nanocomposite films are of great interest due to their enhanced properties over base polymers. By incorporating 2D titanium carbide a representative of a new family of 2D materials, MXenes, as nanofillers into a water soluble polyacrylamide (PAM) matrix, the resulting films benefit from the flexibility, robustness, and processability of PAM, as well as the conductivity and mechanical properties of MXene fillers. We report on manufacturing and characterization of MXene-PAM nanocomposite films. Dimethylsulfoxide (DMSO) intercalation in-between the Ti 3 C 2 -based MXene layers led to full delamination of the MXene layers and hence a uniform dispersion of hydrophilic MXene nanosheets in aqueous PAM solutions was achieved. Moreover, the polymer composite solutions of up to 75 wt.% MXene loading were sonicated and cast onto large Teflon trays and dried at room temperature to produce shiny black films. The observation of reduced 0002 peaks of Ti 3 C 2 T x phase in X-ray diffraction patterns and TEM images indicate the presence of well dispersed nanoflakes. The as-prepared composite films are flexible and the conductivity was increased significantly to 3 x 10 -3 S cm -1 for 6 wt. % MXene-PAM films. With high MXene loading, some non-uniformity between the top and bottom surfaces was observed. This could be due to the segregation of MXene layers in composite films during drying. Finally, the power law dependence of conductivity above the percolation threshold is presented through detailed conductivity measurements.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Solvent controlled ion association in structured copolymers: Molecular dynamics simulations in dilute solutions

Tailoring the nature of individual segments within ion containing block co-polymers is one critical design tool to achieve desired properties. The local structure including the size and distribution of the ionic blocks, as well as the long range correlations, are crucial for their transport ability. Here, we present molecular dynamics simulations on the effects of varying the concentrations of the ionizable groups on the conformations of pentablock ionomer that consist of a center block of ionic sulfonated styrene tethered to polyethylene and terminated by a bulky substituted styrene in dilute solutions. Sulfonation fractions f (0 ≤ f ≤ 0.55), spanning the range from ionomer to polyelectrolytes, were studied. Results for the equilibrium conformation of the chains in water and a 1:1 mixture of cyclohexane and heptane are compared to that in implicit poor solvents with dielectric constants ε = 1.0 and 77.73. In water, the pentablock collapses with the sulfonated groups on the outer surface. As f increases, the ionic, center block increasingly segregates from the hydrophobic regions. In the 1:1 mixture of cyclohexane and heptane, the flexible blocks swell, while the center ionic block collapses for f > 0. For f = 0, all blocks swell. In both implicit poor solvents, the pentablock collapses into a nearly spherical shape for all f . In conclusion, the sodium counterions disperse widely throughout the simulation cell for both water and ε = 77.73, whereas for ε = 1.0 and mixture of cyclohexane and heptane, the counterions largely condense onto the collapsed pentablock.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2016

Vertical Phase Segregation Induced by Dipolar Interactions in Planar Polymer Brushes

In this paper, we present a generalized theory for studying structural properties of a planar dipolar polymer brush immersed in a polar solvent. We show that an explicit treatment of the dipolar interactions yields a macroscopic concentration dependent effective “chi” (the Flory–Huggins-like interaction) parameter. Furthermore, it is shown that the concentration dependent chi parameter promotes phase segregation in polymer solutions and brushes so that the polymer-poor phase consists of a finite/nonzero polymer concentration. Such a destabilization of the homogeneous phase by the dipolar interactions appears as vertical phase segregation in a planar polymer brush. In a vertically phase segregated polymer brush, the polymer-rich phase near the grafting surface coexists with the polymer-poor phase at the other end. Predictions of the theory are directly compared with prior reported experimental results for dipolar polymers in polar solvents. Excellent agreements with the experimental results are found, hinting that the dipolar interactions play a significant role in vertical phase segregation of planar polymer brushes. We also compare our field theoretical approach with the two-state and other models invoking ad hoc concentration dependence of the chi parameter. Interplay between the short-ranged excluded volume interactions and long-ranged dipolar interactions is shown to play an important role in affecting the vertical phase separation. Finally, effects of mismatch between the dipole moments of the polymer segments and the solvent molecules are investigated in detail.

36 MATERIALS SCIENCE↗
NASA NTRS1982

Quantitative determination of zero-gravity effects on electronic materials processing germanium crystal growth with simultaneous interface demarcation experiment MA-060, section 5

The crystal growth and segregation characteristics of a melt in a directional solidification configuration under near zero g conditions were investigated. The germanium (doped with gallium) system was selected because it was extensively studied on Earth and because it lends itself to a very detailed macroscopic and microscopic characterization. An extensive study was performed of the germanium crystals grown during the Apollo-Soyuz Test Project mission. It was found that single crystal growth was achieved and that the interface demarcation functioned successfully. On the basis of the results obtained to date, there is no indication that convection driven by thermal or surface tension gradients was present in the melt. The gallium segregation, in the absence of gravity, was found to be fundamentally different in its initial and its subsequent stages from that of the ground based tests. None of the existing theoretical models for growth and segregation can account for the observed segregation behavior in the absence of gravity.

Gatos, H. C.↗
NASA NTRS1977

Quantitative determination of zero-gravity effects on electronic materials processing germanium crystal growth with simultaneous interface demarcation. Experiment MA-060

Experiment MA-060 was designed to establish the crystal growth and segregation characteristics of a melt in a directional solidification configuration under near zero-g conditions. The interface demarcation technique was incorporated into the experiment since it constitutes a unique tool for recording the morphology of the growth rate throughout solidification, and for establishing an absolute time reference framework for all stages of the solidification process. An extensive study was performed of the germanium crystals grown during the Apollo-Soyuz Test Project mission. It was found that single crystal growth was achieved and that the interface demarcation functioned successfully. There was no indication that convection driven by thermal or surface tension gradients was present in the melt. The gallium segregation, in the absence of gravity, was found to be fundamentally different in its initial and its subsequent stages from that of the ground-based tests. None of the existing theoretical models for growth and segregation can account for the observed segregation behavior in the absence of gravity.

Gatos, H. C.↗
DOE OSTI2017

Diffusion and Clustering of Carbon Dioxide on Non-porous Amorphous Solid Water

Observations by ISO and Spitzer toward young stellar objects showed that CO{sub 2} segregates in the icy mantles covering dust grains. Thermal processing of the ice mixture was proposed as being responsible for the segregation. Although several laboratories studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO{sub 2} along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption and Reflection Absorption InfraRed Spectroscopy to study how CO{sub 2} molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO{sub 2} diffuses significantly on an np-ASW surface above 65 K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO{sub 2} on np-ASW is 2150 ± 50 K, assuming a diffusion pre-exponential factor of 10{sup 12} s{sup −1}. This energy should also apply to the diffusion of CO{sub 2} on the wall of pores. The binding energy of CO{sub 2} from CO{sub 2} clusters and CO{sub 2} from H{sub 2}O ice has been found to be 2415 ± 20 K and 2250 ± 20 K, respectively, assuming the same prefactor for desorption. CO{sub 2}–CO{sub 2} interaction is stronger than CO{sub 2}–H{sub 2}O interaction, in agreement with the experimental finding that CO{sub 2} does not wet the np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO–CO interaction is always weaker than CO–H{sub 2}O. As a result, CO wets the np-ASW surface. This study should be of help to uncover the thermal history of CO{sub 2} on the icy mantles of dust grains.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Changes in Aerosols, Meteorology, and Radiation in the Southeastern U.S. Warming Hole Region during 2000 to 2019

Abstract Surface air temperatures in the southeastern United States that did not change from the climatological mean from 1900 to 2000 have increased since the year 2000. Analyzed herein are factors modulating the surface air temperatures in the region for a 20-yr period (2000–19) using space- and surface-based observations, and output from a reanalysis model. The 20-yr period is segregated into two decades, 2000–09 and 2010–19, corresponding to different tropospheric chemical regimes. Changes in seasonal and decadal averages are examined. The later decade experienced higher average surface air temperatures with significant warming during summer and fall seasons. Decadal and seasonal averages of cloud properties, column water vapor, rain rates, and top-of-atmosphere outgoing longwave radiation did not exhibit statistically significant differences between the two decades. The region experienced strong warm and moist advection during the winter months and very weak advection during the summer months. The later decade exhibited higher low-level moisture advection during the winter months than the earlier decade with insignificant changes in the temperature advection between the two decades. The later decade had significantly lower aerosol dry and liquid water mass during all seasons, along with lower aerosol optical depth, higher single scattering albedo, and lower top-of-the-atmosphere outgoing shortwave radiation during cloud-free conditions in the summer season. Collectively, these results suggest that changes in the aerosol direct radiative forcing are responsible for warming during summer months that experience weak advection and highlight seasonal differences in the temperature controlling mechanisms in the region.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Support Induced Control of Surface Composition in Cu–Ni/TiO 2 Catalysts Enables High Yield Co-Conversion of HMF and Furfural to Methylated Furans

5-(hydroxymethyl)furfural (HMF) and furfural (FF) have been confirmed as valuable biomass-derived fuel precursors suitable for catalytic hydrodeoxygenation (HDO) to produce high octane fuel additives such dimethyl furan (DMF) and methyl furan (MF), respectively. In order to realize economically viable production of DMF and MF from biomass, catalytic processes with high yields, low catalyst costs, and process simplicity are needed. In this work, we demonstrate simultaneous co-processing of HMF and FF over Cu-Ni/TiO 2 catalysts, achieving 87.5% yield of DMF from HMF and 88.5% yield of MF from FF in a one pot reaction. The Cu-Ni/TiO 2 catalyst also exhibited improved stability and regeneration compared to Cu/TiO 2 and Cu/Al 2 O 3 catalysts for FF HDO, exhibiting a ~7% loss in FF conversion over 4 sequential recycles, compared to a ~50% loss in FF coversion for Cu/Al 2 O 3 and a ~30% loss in coversion for Cu/TiO 2 . Characterization of the Cu-Ni/TiO 2 catalyst by X-ray Photoelectron Spectroscopy, Scanning Transmission Electron Microscopy, and H 2 -Temperature Programmed Reduction and comparison to monometallic Cu and Ni on Al 2 O 3 and TiO 2 and bimetallic Cu-Ni/Al 2 O 3 catalysts suggest that the unique reactivity and stability of Cu-Ni/TiO 2 derives from support-induced metal segregation in which Cu is selectively enriched at the catalyst surface, while Ni is enriched at the TiO 2 interface. Our findings demonstrate that Cu-Ni/TiO 2 catalysts promise to be a catalyst system capable of integrating directly with a combined HMF and FF product stream from biomass processing to realize lower cost production of liquid fuels from biomass.

09 BIOMASS FUELS↗