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At least 145 records · Page 8

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DOE OSTI2026

Lithographic crystallinity regulation in additive fabrication of thermoplastics (CRAFT)

For semicrystalline polyolefin thermoplastics, the balance between interconnected ordered crystalline and disordered amorphous regions is paramount to their performance and processability. However, contemporary manufacturing strategies, from injection molding to three-dimensional (3D) printing, result in monolithic objects, unable to spatially encode crystallinity. We develop a light-based approach for fabricating mechanically robust polyolefin thermoplastics with microscopic control over crystallinity in 3D space. Light dosage governs polymer stereochemistry giving access to a continuum of materials, from strong rigid plastics, such as high-density polyethylene, to more extensible materials akin to low-density polyethylene, all at the flick of a switch. Leveraging this finding in lithographic grayscale 3D printing enables rapid multimaterial fabrication with voxel-level control over optical and mechanical properties, opening avenues in information storage, soft robotics, and energy damping.

36 MATERIALS SCIENCE↗

DOE OSTI2024

A Bottom-Up Approach to Rational Design of Crystalline Materials: Investigation of Vibronic Coherences Underlying Exciton Dynamics in Semiconductors

In this project we uncovered structure-function relationships of donor-acceptor co-crystals used to develop next-generation optoelectronic devices. Unraveling the photodynamics of molecular crystalline materials poses many challenges for spectroscopy due to broad, overlapping features representing numerous underlying dynamical processes. This leads researchers to make many assumptions about the dynamics of a system in choosing an appropriate kinetic fitting model. Computationally, electronic structure methods are either prohibitively expensive or underdeveloped for computing the excited state structure of molecular materials, especially states that exhibit charge transfer. Researchers must therefore perform calculations of excited electronic states using truncated models of molecular materials. Here we present a joint experimental-theoretical approach to bridging the gap between the photodynamics of a molecular material and its constituent molecules. We focus our efforts on quantifying the timescales and mechanisms of photoexcitation in donor-acceptor co-crystals and donor-acceptor dimers where the lowest-lying excited state is characterized by charge transfer from the donor to the acceptor. We employ ultrafast UV pump, UV-Vis probe transient absorption spectroscopy to unravel the time-resolved spectroscopic signatures of the photodynamics in both the crystalline material and donor-acceptor dimers in solution. We perform electronic structure and excited state dynamics calculations of the dimers to inform kinetic fitting models and assign the spectral features. The photodynamics of the crystal vs. dimer systems have many similarities, enabling unprecedented insights into the formation and evolution of charge transfer excitons in the crystalline systems.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Interface-enhanced conductivities in surfactant-mediated, solution-grown ionic crystalline complexes

Renewable energy is increasingly relying on optimized electrolytes and interfaces. In this work, Tween 20 and sodium chloride are selected as a model system to reveal the effects of surfactants on salt crystallization in the context of ionic conductivity and interface optimization. At a varied crystallization speed and mix ratio, it is demonstrated that the resultant solution-grown ionic crystalline complexes can achieve a highly tunable ion transport with a controllable crystalline interface. X-ray diffraction results rule out the possibility of polymorphism in the NaCl/Tween 20 systems, which further supports the importance of an optimized crystalline network for optimizing permittivity or ionic conductivity. Raman mapping and machine learning techniques are used to perform semantic segmentation on highly heterogeneous NaCl/Tween 20 complexes. Furthermore, FTIR measurements demonstrate that inter- and intra-molecular interactions play critical roles in the formation of these crystals. This work lays a foundation toward future optimization of such complex ion systems for a specific salt or crystallization modifier in energy storage or ion transport applications.

36 MATERIALS SCIENCE↗

NASA NTRS1969

Production of crystalline polymers via liquid crystal monomers

Method produces crystalline polymers through a liquid crystalline phase of monomers. The monomer is polymerized while held in the liquid crystalline phase either thermally, photolytically, catalytically, or by X-ray or gamma ray irradiation, and can be performed in an electric or magnetic field that influences the molecular orientation.

Labes, M.↗

NASA NTRS1971

Thermodynamics of rock forming crystalline solutions

Analysis of phase diagrams and cation distributions within crystalline solutions as means of obtaining thermodynamic data on rock forming crystalline solutions is discussed along with some aspects of partitioning of elements in coexisting phases. Crystalline solutions, components in a silicate mineral, and chemical potentials of these components were defined. Examples were given for calculating thermodynamic mixing functions in the CaW04-SrW04, olivine-chloride solution, and orthopyroxene systems.

Saxena, S. K.↗

NASA NTRS1979

Crystalline polyimides

Aromatic crystalline polyimides are disclosed that are synthesized from polyamide-acid and when heated to 200 C to 300 C become cyclized to afford an opaque polymer. X-ray diffraction of the unoriented film exhibited 47 percent crystallinity. Differential scanning calorimetry reveals a melt at 425 C with no glass transition in these crystalline polyimides.

St.clair, T. L.↗

NASA NTRS1983

Transmittance and reflectance of crystalline quartz and highand low-water content fused silica from 2 microns to 1 mm

The transmittances and reflectances of cultured crystalline quartz, Suprasil, Suprasil W, and Infrasil were compared over the wavelength region from 2 to 1000 microns. The high-water content of Suprasil and the low-water content of cultured crystalline quartz, Suprasil W, and Infrasil were determined by their transmittances measured at 2.73 microns where water content causes high absorption in optical materials. The fact that the fused silicas, both with high- and low-water content, had identical far-IR transmittances and that their transmittances were greatly inferior to that of crystalline quartz led to the conclusion that their inferior transmittance is due to their amorphous structure and not to their water content.

Heaney, J. B.↗

NASA NTRS1985

Crystalline-silicon reliability lessons for thin-film modules

The reliability of crystalline silicon modules has been brought to a high level with lifetimes approaching 20 years, and excellent industry credibility and user satisfaction. The transition from crystalline modules to thin film modules is comparable to the transition from discrete transistors to integrated circuits. New cell materials and monolithic structures will require new device processing techniques, but the package function and design will evolve to a lesser extent. Although there will be new encapsulants optimized to take advantage of the mechanical flexibility and low temperature processing features of thin films, the reliability and life degradation stresses and mechanisms will remain mostly unchanged. Key reliability technologies in common between crystalline and thin film modules include hot spot heating, galvanic and electrochemical corrosion, hail impact stresses, glass breakage, mechanical fatigue, photothermal degradation of encapsulants, operating temperature, moisture sorption, circuit design strategies, product safety issues, and the process required to achieve a reliable product from a laboratory prototype.

Ross, R. G., Jr.↗

NASA NTRS1987

An overview of the DOE terrestrial crystalline solar cell research program

There has been significant progress in the crystalline solar cell area in the past two years that has rejuvenated interest in the high efficiency devices for terrestrial photovoltaic systems. The most significant developments have been in the crystalline solar cell area, but progress in the III-V area has also been recorded. A review of terrestrial crystalline cell research is presented along with a description of future research directions.

Gee, James M.↗

NASA NTRS1987

Preliminary analysis of recent 2.2-4.2 micrometers telescopic observations of Elysium, Mars: Implications for crystallinity and hydration state of surface materials

Comparisons of the telescopic reflectance spectrum of a Martian bright region, in the 2.2 to 4.2 micrometers region, with recent laboratory studies of materials in this same wavelength range are consistent with: terrestrial materials which are dehydrated relative to the terrestrial environment, and terrestrial materials which exhibit spectral behavior indicative of some degree of sample crystallinity which is greater than that of amorphous palagonites. This second conclusion is in agreement with recent suggestions concerning the Martian bright regions. However, additional laboratory research is required in order to constrain: the degree of crystallinity required to result in the 2.8 to 2.9 micrometers spectral behavior seen in the terrestrial samples, and the limit of crystalline material which can be accommodated in a mixture with measured telescopic data of Mars (0.3 to 4.2 micrometers).

Roush, T. L.↗

NASA NTRS1989

Infrared spectra of crystalline and glassy silicates and application to interstellar dust

The infrared spectra of crystalline minerals predicted in theoretical condensation sequences do not match the astronomical observations. Since the astronomical spectra are a closer match to glassy silicates, the authors undertook a study to measure the infrared spectra of glassy silicates that have compositions similar to silicate minerals predicted in theoretical condensation sequences. The data should support observations aimed at elucidating condensation chemistry in dust forming regions. The authors measured the mass absorption coefficients, from 2.5 to 25 microns, of ground samples of olivine, diopside, and serpentine and also smoke samples that were prepared from these minerals. The smoke samples prepared in this way are predominantly glassy with nearly the same composition as the parent minerals. The crystalline samples consisted of pure olivine ((Fe(0.1)Mg(0.9))(2)SiO(4)), serpentine, diopside. Sample purity was confirmed by x ray diffraction. Each mineral was ground for 10 hours and a measured mass of the powder was mixed with KBr powder for absorption measurements using the method of Borghesi et a. (1985). The smoke samples were prepared from the same samples used for grinding by vaporizing the minerals using pulsed laser radiation in air. The smoke samples formed by condensation of the resulting vapor. The smoke settled onto infrared transparent KRS-5 substrates and onto a quartz crystal microbalance used to obtain mass measurements. A description of the preparation method is given in Stephens (1980). The glassy diopside showed only diffuse electron diffraction peaks and hence was nearly amorphous, while the serpentine smoke showed a weak diffraction pattern corresponding to MgO. The smoke from olivine showed a weak diffraction pattern corresponding to Fe2O3 and/or Fe3O4. The mass absorption coefficients, from 2.5 to 25 microns, of crystalline diopside, olivine, and serpentine and their corresponding smoke samples are shown in figures.

Stephens, John R.↗

NASA NTRS1989

A comparative study of the continuum and emission characteristics of comet dust. 1: Are the silicates in Comet Halley and Kohoutek amorphous or crystalline

A continuum emission was subtracted from the 10 micron emission observed towards comets Halley and Kohoutek. The 10 micron excess emissions were compared with BN absorption and laboratory amorphous silicates. The results show that cometary silicates are predominantly amorphous which is consistent with the interstellar dust model of comets. It is concluded that cometary silicates are predominantly similar to interstellar silicates. For a periodic comet like Comet Halley, it is to be expected that some of the silicate may have been heated enough to convert to crystalline form. But apparently, this is only a small fraction of the total. A comparison of Comet Halley silicates with a combination of the crystalline forms observed in interplanetary dust particles (IPDs) seemed reasonable at first sight (Walker 1988, Brownlee 1988). But, if true, it would imply that the total silicate mass in Comet Halley dust is lower than that given by mass spectrometry data of Kissel and Krueger (1987). They estimated m sub org/m sub sil = 0.5 while using crystalline silicate to produce the 10 micron emission would give m sub org/m sub sil = 5 (Greenberg et al. 1988). This is a factor of 10 too high.

Nansheng, Zhao↗

NASA NTRS1992

Evidence for crystalline hematite as an accessory phase in Martian soils

Based on visible and near-IR spectral images of Mars obtained by us in 1988, we have confirmed the occurrence of bulk crystalline hematite as a minor or accessory phase on the surface. This hematite is not uniformly distributed, being less abundant or absent in certain northern low-albedo regions. Even where most abundant, bulk hematite is not the primary coloring agent of heavily weathered materials on Mars. The primary coloring agent is apparently an amorphous or nanophase Fe3(+) phase, analogous to the coloring agent in certain Hawaiian palagonites (e.g. Adams and Evans, 1980; Singer, 1982; Morris et al, 1989). Based on these results, we can say with considerable certainty that bulk crystalline hematite exists on Mars in small amounts, in addition to the more ubiquitous nanophase or poorly crystalline ferric oxide phase(s). We conclude that Type 2 low-albedo regions (typified by Acidalia Planitia) contain less of this hematite than Type 1 regions (typified by Meridiani Sinus). Oxia Palus shows indication of slightly more oxidation and bulk hematite than Acidalia. This may be a real compositional difference, indicating that Oxia is in some sense transitional between Type 2 and Type 1 regions, but we cannot rule out the possibility of some optical mixing with surrounding higher-albedo regions. We are currently investigating the relationship of ferric-oxides in high-albedo regions to both types of low-albedo regions. As expected, spectral ratios of data from western Arabia to dark regions show considerably greater Fe3(+) in Arabia. There are not obvious spectral indications of a difference in ferric-oxide composition between Arabia and Type 1 low-albedo regions, implying that Arabia also contains minor bulk hematite.

Singer, R. B.↗

NASA NTRS1992

Thin film growth of the 2122-phase of BCSCO superconductor with high degree of crystalline perfection

Thin films of the 80 K-phase of BiCaSrCu-oxide superconductor having the composition of Bi2Ca1.05Sr2.1Cu2.19O(x) and high degree of crystalline perfection have been grown on c-axis oriented twin free single crystal substrates of NdGaO3. This has been achieved by carefully establishing the growth conditions of the LPE experiments. The temperature regime of 850 to 830 C and quenching of the specimens on the termination of the growth period are found to be pertinent for the growth of quasi-single crystalline superconducting BCSCO films on NdGaO3 substrates. The TEM analysis reveals a single crystalline nature of these films which exhibit 100 percent reflectivity in infrared regions at liquid nitrogen temperature.

Raina, K. K.↗

NASA NTRS1992

The crystallization and crystalline properties of LARC-TPI

LARC-TPI, a thermoplastic polyimide, has been studied in order to develop an understanding of its crystalline phase transition. Our experiments suggest that samples synthesized in different laboratories apparently had different degrees of imidization and their thermal behaviors differed accordingly. When the most crystalline of these polyimides was studied in some detail, we found that it melted irreversibly in that once a sample was completely melted it would not recrystallize. A polymer that did not recrystallize displayed a glass transition, which increased in temperature upon subsequent cooling and reheating. Solubility experiments indicated that heating above the crystalline melting temperature led to network formation in the polymer, a conclusion that is consistent with other behavior just mentioned. Differential calorimetric studies revealed that annealing at slow heating rates or under isothermal conditions resulted in dual melting transitions. These studies, supported by X-ray diffraction results, strongly indicate that the annealing process involves a solid-liquid-solid transformation. From an existing phenomenological model for the kinetics of phase transitions, kinetic parameters for these crystallizations have been evaluated. The Avrami exponents n increased with the annealing temperature in the protocol used in this study. Their values were about 2 or lower, thus indicating that crystallization may have followed a mechanism that included heterogeneous nucleation of a low dimensional order in which all the embryonic crystallites formed at the beginning of the process. A positive temperature coefficient for these crystallizations indicated that diffusion may have had a rate controlling influence and affected the values of n.

Theil, Michael H.↗

NASA NTRS1992

Far infrared spectra of amorphous and crystalline water ice and changes in these phases as the result of proton irradiation

Far infrared spectra from 20 microns (500 cm(sup -1)) to 100 microns (100 cm(sup -1)) of water ice were measured. Amorphous ice deposited at 13 K has one absorption band at 45 microns (220 cm(sup -1)). Amorphous ice evolves into a crystalline form with absorptions at 44 microns (229 cm(sup -1)) and 62 microns (162 cm(sup -1)) as the temperature is increased to 155 K. Spectra documenting this phase change are presented as well as spectra of crystalline ice at temperatures between 13 K and 155 K. Far infrared spectra of amorphous and crystalline water ice before and after proton irradiation are also presented. Changes in these two forms are discussed in relation to ices in comets, grains, and planetary satellites in various radiation environments. Observations of non-terrestrial clathrate hydrates are still lacking despite the fact that clathrates first were suggested to exist in cometary and interstellar ices over forty years ago. Spectroscopy, the most direct method of astronomical detection, has been hampered by the similarity of clathrate hydrate spectra to those of unenclathrated guest molecules and solid H2O. A methanol (CH3OH) clathrate hydrate, using a recently published procedure, was prepared and its far-IR spectrum investigated. The spectrum is quite differenct from that of either unenclathrated CH3OH or solid H2O and so should be of value in astronomical searches for this clathrate.

Hudson, Reggie L.↗

NASA NTRS1993

Liquid crystalline order in mucus

Mucus plays an exceptionally wide range of important biological roles. It operates as a protective, exchange, and transport medium in the digestive, respiratory, and reproductive systems of humans and other vertebrates. Mucus is a polymer hydrogel. It is secreted as discrete packages (secretory granules) by specialized secretory cells. Mucus hydrogel is stored in a condensed state inside the secretory granules. Depending upon the architecture of their constituent macromolecules and on the composition of the solvent, polymer gels can form liquid crystalline microstructures, with orientational order being exhibited over optically resolvable distances. Individual mucin molecules consist of alternating rigid segments (heavily glycosylated; hydrophilic) and flexible segments (nonglycosylated; hydrophobic). Polymer molecules consisting of rigid units linked by flexible spacers are frequently associated with liquid crystalline behavior, which again raises the possibility that mucus could form anisotropic fluid phases. Suggestions that mucins may be self-associating in dilute solution have previously been challenged on the basis of sedimentation-equilibrium studies performed on mucus in which potential sites of association were competitively blocked with inhibitors. However, the formation of stable liquid crystalline phases does not depend on the existence of inter- or intramolecular associations; these phases can form on the basis of steric considerations alone.

NASA Discipline Number 40-20↗

NASA NTRS1993

Association of actin with alpha crystallins

The alpha crystallins are cytosolic proteins that co-localize and co-purify with actin-containing microfilaments. Affinity column chromatography employing both covalently-coupled actin or alpha crystallin was used to demonstrate specific and saturable binding of actin with alpha crystallin. This conclusion was confirmed by direct visualization of alpha aggregates bound to actin polymerized in vitro. The significance of this interaction in relation to the functional properties of these two polypeptides will be discussed.

NASA Program NSCORT↗