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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 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
NASA NTRS1974

Apollo 17 orange glass - Textural and morphological characteristics of devitrification

Results of a study are presented concerning (1) the significance of nonexcentroradial growth textures in Apollo 17 orange glass and a comparison of these textures with those that develop in lunar and meteoritic chondrules, (2) the development and the nature of the crystalline-glass interface, and (3) the morphology and growth characteristics of olivine and of the opaque mineral oxides that result by devitrification of the orange glass. Observations of the orange glass soil are contrasted with subsequent partial melting of orange glass spherules that were incorporated into mildly metamorphosed breccias, and the quench textures that result in these larger cooling units are compared with the textures produced by supercooling of small particulate spherules. Results show that the expected changes in viscosity due to partial melting and recrystallization do not affect the shape of individual particles, and that neither the thermal gradients that need to be invoked across 20-100 micron spheres nor collision of glass particles during lava fountaining can account for the devitrification textures observed.

Haggerty, S. E.↗
DOE OSTI2018

Three-dimensional electronic resistivity mapping of solid electrolyte interphase on Si anode materials

Silicon is a promising candidate for the lithium ion battery (LIB) anode because of the order-of-magnitude improvement in capacity over current state-of-the-art graphite anodes. In systems featuring both C and Si anodes, electronic resistivity of the solid-electrolyte interphase (SEI) layer is a critical factor for preventing continuous electrolyte-decomposition reactions at the electrode/electrolyte interface. However, the in-situ measurement of SEI electronic resistance has been complicated by ion transport and electronic contributions from other parts of the battery circuit. Ex-situ measurements of SEI resistivity at microscopic scales are also lacking. We report on a nanometer-resolution three-dimensional technique that enables ex-situ mapping of electronic resistivity of SEI formed on a model single-crystalline wafer Si anode. Our novel experimental approach uses scanning spreading-resistance microscopy resistance imaging and mechanical depth profiling. In addition to resistance mapping, this method also provides an alternative technique for locating buried interfaces, where mechanical or electronic properties differ sufficiently between layers. Further validation of this method was obtained by resistance mapping of a reference sample with a designed a-Si:H layer stack of different doping concentrations. The results show relatively uniform lateral resistivity distribution of the SEIs but steep decreases in resistivity in the vertical direction. Resistivity vs. depth profiles are highly dependent on cycling conditions, but they generally show a resistivity decrease from the most superficial levels of SEI and a thickness increase with continued cycling prior to SEI stabilization. The most prominent resistivity increase was observed on SEI formed in Gen2 electrolyte (EC:EMC [3:7 by wt.] + 1.2 M LiPF6) with 10 wt% fluoroethylene carbonate additive; this result may partially explain the significant improvements of sustained electrochemical cycling and coulombic efficiency observed with this electrolyte additive. Our approach provides a novel and unparalleled three-dimensional approach in characterizing electronic resistivity, which contributes significantly to understanding SEI formation and the intrinsic properties critical to battery performance.

25 ENERGY STORAGE↗
NASA NTRS1972

Free adjustment of a geometric global satellite network (solution MPS-7)

The basic purpose of this experiment was to compute reduced normal equations from the observational data of several different systems described below to combine them eventually with the normal equations of the Wild BC-4 observations taken in the DOD/DOC cooperative worldwide geodetic satellite program and provide station coordinates from a single least squares adjustment. The solution described is a partial one obtained without the use of the BC-4 data. The observational systems combined were the Baker-Nunn simultaneous camera observational systems combined were the Baker-Nunn simultaneous camera observations from the SAO worldwide network, the MOTS and PC-1000 optical observations in North America, miscellaneous camera observations in Europe which were included in the SAO69 solution, and, lastly, a group of optical observations where Baker-Nunn cameras observed simultaneously with MOTS and/or PC-1000 cameras in the previously mentioned group.

Mueller, I. I.↗
DOE OSTI2020

Influence of hydrogenation on the vibrational density of states of magnetocaloric LaFe 11.4 Si 1.6 H 1.6

We report on the impact of magnetoelastic coupling on the magnetocaloric properties of LaFe 11.4 Si 1.6 H 1.6 in terms of the vibrational (phonon) density of states (VDOS), which we determined with 57 Fe nuclear resonant inelastic x-ray scattering (NRIXS) measurements and with density functional theory (DFT) based first-principles calculations in the ferromagnetic (FM) low-temperature and paramagnetic (PM) high-temperature phase. In experiments and calculations, we observe pronounced differences in the shape of the Fe-partial VDOS between nonhydrogenated and hydrogenated samples. Furthermore, this shows that hydrogen not only shifts the temperature of the first-order phase transition, but also affects the elastic response of the Fe subsystem significantly. In turn, the anomalous redshift of the Fe VDOS, observed by going to the low-volume PM phase, survives hydrogenation. As a consequence, the change in the Fe-specific vibrational entropy ΔS lat across the phase transition has the same sign as the magnetic and electronic contribution. DFT calculations show that the same mechanism, which is a consequence of the itinerant electron metamagnetism associated with the Fe subsystem, is effective in both the hydrogenated and the hydrogen-free compounds. Although reduced by 50% as compared to the hydrogen-free system, the measured change ΔS lat of 3.2 ± 1.9)J/ kg K across the FM-to-PM transition contributes with ~35 % significantly and cooperatively to the total isothermal entropy change ΔS iso . Hydrogenation is observed to induce an overall blueshift of the Fe VDOS with respect to the H-free compound; this effect, together with the enhanced Debye temperature observed, is a fingerprint of the hardening of the Fe sublattice by hydrogen incorporation. In addition, the mean Debye velocity of sound of LaFe 11.4 Si 1.6 H 1.6 was determined from the NRIXS and the DFT data.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Deviations from the Porter-Thomas Distribution due to Nonstatistical 𝛾 Decay below the 150 Nd Neutron Separation Threshold

We introduce a new method for the study of fluctuations of partial transition widths based on nuclear resonance fluorescence experiments with quasimonochromatic linearly polarized photon beams below particle separation thresholds. It is based on the average branching of decays of 𝐽=1 states of an even-even nucleus to the 2$^{+}_{1}$ state in comparison to the ground state. Between 5 and 7 MeV, a constant average branching ratio for 𝛾 decays from 1 − states of 0.490(16) is observed for the nuclide 150 Nd. Assuming 𝜒 2 -distributed partial transition widths, this average branching ratio is related to a degree of freedom of 𝜈 = 1.93⁢(12), rejecting the validity of the Porter-Thomas distribution, requiring 𝜈 = 1. The observed deviation can be explained by nonstatistical effects in the 𝛾-decay behavior with contributions in the range of 9.4(10)% up to 94(10)%.

150 ≤ A ≤ 189↗
NASA NTRS2023

Parker Solar Probe Observations of High Plasma β Solar Wind From the Streamer Belt

In general, slow solar wind from the streamer belt forms a high plasma β equatorial plasma sheet around the heliospheric current sheet (HCS) crossing, namely, the heliospheric plasma sheet (HPS). Current Parker Solar Probe (PSP) observations show that the HCS crossings near the Sun could be full or partial current sheet (PCS) crossings, and they share some common features but also have different properties. In this work, using the PSP observations from encounters 4–10, we identify streamer belt solar wind from enhancements in plasma β, and we further use electron pitch angle distributions to separate it into HPS solar wind around the full HCS crossings and PCS solar wind in the vicinity of PCS crossings. Based on our analysis, we find that the PCS solar wind has different characteristics as compared with HPS solar wind: (a) the PCS solar wind could be non-pressure-balanced structures rather than magnetic holes, and the total pressure enhancement mainly results from the less reduced magnetic pressure; (b) some of the PCS solar wind is mirror-unstable; and (c) the PCS solar wind is dominated by very low helium abundance but varied alpha–proton differential speed. We suggest that the PCS solar wind could originate from coronal loops deep inside the streamer belt, and it is pristine solar wind that still actively interacts with ambient solar wind; thus, it is valuable for further investigations of the heating and acceleration of slow solar wind.

Slow solar wind↗
DOE OSTI2015

Unexpected Voltage Fade in LMR-NMC Oxides Cycled below the “Activation” Plateau

A common feature of lithium-excess layered oxides, nominally of composition xLi 2 MnO 3 •(1-x)LiMO 2 (M = transition metal) is a high-voltage plateau (~4.5 V vs. Li/Li + ) in their capacity-voltage profile during the first delithiation cycle. This plateau is believed to result from activation of the Li 2 MnO 3 component, which makes additional lithium available for electrochemical cycling. However, oxides cycled beyond this activation plateau are known to display voltage fade which is a continuous reduction in their equilibrium potential. In this article we show that these oxides display gradual voltage fade even on electrochemical cycling in voltage ranges well below the activation plateau. The average fade is ~0.08 mV-cycle-1 for Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 vs. Li cells after 20 cycles in the 2–4.1 V range at 55°C; a ~54 mV voltage hysteresis, expressed as the difference in average cell voltage between charge and discharge cycles, is also observed. The voltage fade results from a gradual accumulation of local spinel environments in the crystal structure. Some of these spinel sites result from lithium deficiencies during oxide synthesis and are likely to be at the particle surfaces; other sites result from the migration of transition metal atoms in the partially-delithiated LiMO 2 component into the lithium planes during electrochemical cycling. The observed rate of voltage fade depends on a combination of factors that includes the phase equilibrium between the layered and spinel components and the kinetics of transition metal migration.

Li, Yan↗
NASA NTRS1994

High dynamic range radio observations of PKS 1413+135: A BL Lacertae object with a parsec-scale counterjet

We report the results of three high dynamic range, high-resolution radio observations with the Very Large Array (VLA), US Very Long Base Interferometry (VLBI) Network, and partially completed Very Long Baseline Array (VLBA) on the peculiar BL Lacertae objects PKS 1413+135. The VLA observations (resolution approximately 1.5 sec) reveal that PKS 1413+135 has no kiloparsec-scale extended structure to a dynamic range limit of 10,000:1. However, its milliarcsecond-scale structure appears to be a triple (i.e., a core, jet plus 'counterjet') at both 3.6 and 18 cm, a unique structure among BL Lac objects but similar to a recently discovered class of VLBI 'mini-triples.' The presence of a counterjet at fluxes comparable to the main jet is incompatible with the standard relativistically beamed jet model for BL Lac objects and with the high value of core dominance exhibited by this source at arcsec resolution. This suggests a nonstandard interpretation in which the radio source lies far in the background of the spiral galaxy it is projected upon so that its VLBI structure may be affected by gravitational lensing. At 18 cm, the core is much weaker than at 3.6 cm suggesting free-free absorption by the high-column-density gas found along this sightline by previous infrared(IR)/optical, X-ray and redshifted H I 21 cm observations. We discuss the roles that free-free absorption and gravitational lensing may have for PKS 1413+135 and other GHz-peaked spectrum radio sources.

Perlman, Eric S.↗
NASA NTRS2003

A Solar System Survey of Forced Librations in Longitude

Physical librations in longitude are forced periodic variations of a body's rotation rate. If the torque producing the librations can be calculated, then observations of the phase and amplitude of librations can provide information on mass distribution, and effective strength of the body. In the near future prospects for observing physical librations look quite promising. Radio interferometric observations of Venus and Mercury may yield sufficiently accurate rotational observations that librations there may be visible. Range measurements from Earth to networks of landed instrument packages on Mars are likely to yield librational data there as well. We compute expected libration amplitudes from physical and orbital parameters of a set of planets and satellites partially motivated by a desire to identify candidates for future observations. Solar system bodies occupy one of three general rotation states: non-resonant states, resonant states, and the synchronous resonant state. Analytical treatments of forced librations were initially motivated by the Moon. Lunar librations were predicted by Newton, first detected telescopically by Bessel, and definitively resolved through lunar laser ranging which has led to quite thorough analysis of of librations for the synchronous case. The synchronous resonant state is commonly observed among satellites. The only known body to exist in a non-synchronous resonance is Mercury which exists in a 3:2 resonance, completing three rotations for every two revolutions about the sun. The analysis of Goldreich and Peale has lead to improved understanding of the general case of half integer resonance states. The dynamics of forced librations in non-resonant rotators has received less attention. While there are few cases in which non-resonant forced librations have been observed, Earth is an important exception, and current observing techniques may have the capacity to detect them on Venus. A comprehensive observing program spanning a range of solar system bodies can address an array of geophysical issues involving interior mass distribution of planets, satellites, and asteroids. Calculations of expected librations can supply amplitude estimates helpful in identifying the likelihood of detecting librations observationally. We present a survey of expected libration amplitudes for a subset of solar system bodies, identifying those bodies with amplitudes likely to be detectable, and commenting on spin state, and radial structure implications.

Comstock, R. L.↗
DOE OSTI2014

Electron distributions observed with Langmuir waves in the plasma sheet boundary layer

The present paper investigates the Langmuir turbulence driven by counter-streaming electron beams and its plausible association with observed features in the Earth's plasma sheet boundary layer region. A one-dimensional electrostatic particle-in-cell simulation code is employed in order to simulate broadband electrostatic waves with characteristic frequency in the vicinity of the electron plasma frequency ω/ω{sub pe}≃1.0. The present simulation confirms that the broadband electrostatic waves may indeed be generated by the counter-streaming electron beams. It is also found that the observed feature associated with low energy electrons, namely quasi-symmetric velocity space plateaus, are replicated according to the present simulation. However, the present investigation only partially succeeds in generating the suprathermal tails such that the origin of observed quasi power-law energetic population formation remains outstanding.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Socioeconomic and particulate air pollution correlates of heart disease risk

Highlights: • Heart disease risk varies with age, sex, smoking, income, education, and particulate (PM2.5) air pollution. • How these risk factors interact is unclear. • We examine correlates of self-reported heart disease risk in a large data set. • Income is negatively associated with both PM2.5 exposure and heart disease risk. • Income is an important confounder of air pollution-heart disease associations. • Nonparametric methods can quantify associations and suggest causal interpretations. How does risk of heart disease depend on age, sex, smoking, income, education, marital status, and outdoor concentrations of fine particulate matter (PM2.5)? We join data available from the Centers for Disease Control and Prevention (CDC) Behavioral Risk Factor Surveillance (BRFSS) System for years 2008–2012 to US Environmental Protection Agency (EPA) data on county-specific concentrations of fine particulate matter (PM2.5) to quantify associations among these variables and to explore possible causal interpretations. Low income is identified as a direct cause of increased heart disease risk in this data set. The effect depends on age and sex: it is most pronounced for men under age 70 and for women under age 80. Income is significantly associated with all of the other variables examined and confounds the association between PM2.5 and heart disease risk. This association is significant in regression models that exclude income, but not in regression models that include it, both in the data set as a whole and in the subset of observations with PM2.5 < 15 μg/m{sup 3}. Causal directed acyclic graph (DAG) models and non-parametric model ensemble partial dependence plots confirm that higher incomes reduce heart disease risk, consistent with previous observations of socioeconomic gradients in health risks. They support interpretation of this as a robust causal relation apparent in non-parametric analyses, and hence independent of any specific parametric modeling assumptions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Robust half-metallicity of hexagonal SrNiO{sub 3}

In the rich panorama of the electronic and magnetic properties of 3d transition metal oxides SrMO{sub 3} (M=Ti, V, Cr, Mn, Fe, Co, Ni, Cu), one member (SrNiO{sub 3}) is missing. In this paper we use GGA+U method based on density functional theory to examine its properties. It is found that SrNiO{sub 3} is a ferromagnetic half-metal. The charge density map shows a high degree of ionic bonding between Sr and other atoms. Meanwhile, a covalent-bonding Ni–O–Ni–O–Ni chain is observed. The spin density contour of SrNiO{sub 3} further indicates that the magnetic interaction between Ni atoms mediated by O is semicovalent exchange. The density of states are examined to explore the unusual indirect magnetic-exchange mechanism. Corresponding to the total energies results, a robust half-metallic character is observed, suggesting a promising giant magneto-optical Kerr property of the material. The partial density of states are further examined to explore the origin of ferromagnetic half-metallicity. The O atoms are observed to have larger contribution at fermi level than Ni atoms to the spin-polarized states, demonstrating that O atoms play a critical role in ferromagnetic half-metallicity of SrNiO{sub 3}. Hydrostatic pressure effect is examined to evaluate how robust the half-metallic ferromagnetism is. - Graphical abstract: (a) The total energy as a function of the lattice constant a for hexagonal SrNiO3 with various magnetic phases. (b) The total electronic density of states for hexagonal SrNiO{sub 3} with FM configuration from GGA+U calculations. (c) Total electron-density distribution in the (110) plane. The colors gradually change from cyan (through pink) to yellow corresponding to charge density value from 0 to 4.0. (d) The magnetization density map in the (110) plane. The colors range from blue (through green) to red corresponding to magnetization density value from −0.15 to 0.45. Black and white contours stand for positive and negative values, respectively. - Highlights: • Hexagonal SrNiO{sub 3} is studied using first-principles method for the first time. • It is predicted that SrNiO{sub 3} is a ferromagnetic half metal. • The half-metallic ferromagnetism survives upon a pressure up to 20 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Impact of mechanical tolerances on partial turn skipping in helical flux compression generator

Maintaining tight mechanical tolerances of the components used in helical flux compression generators is crucial for optimizing device performance. Moving beyond current literature, which provides various approximations for acceptable tolerances, a 3D simulation of the armature stator interaction during generator operation was developed, revealing that existing equations frequently misestimate the tolerance limits. Without restricting the generality of the presented approach, the focus was primarily on the armature’s concentricity and roundness, comparing the acceptable tolerance limits between generators of different sizes. An analytical approach for select geometries was developed, confirming the 3D results. Quantitative results reveal that a steeper Gurney angle and increased winding pitch allow for less restrictive tolerances for eccentricity and ellipticity. Even small deviations from the ideal armature positioning and shape will result in fluctuations of the output current time-derivative, observed experimentally and in simulation. Larger deviations then cause partial turn skipping, associated with loss of magnetic flux. The simulation elucidates the impact of tolerance deviations on generator performance by offering precise tolerance ranges for various generator sizes, thereby facilitating informed design decisions.

42 ENGINEERING↗
DOE OSTI2018

Unraveling the Stereodynamics of Cold Controlled HD - H 2 Collisions

Measuring inelastic rates with partial-wave resolution requires temperatures close to a Kelvin or below, even for the lightest molecule. In a recent experiment, Perreault, Mukherjee, and Zare [Nat. Chem. 10, 561 (2018).] studied collisional relaxation of excited HD molecules in the v=1, j=2 state by para- and ortho-H2 at a temperature of about 1 K, extracting the angular distribution of scattered HD in the v=1, j=0 state. By state preparation of the HD molecules, control of the angular distribution of scattered HD was demonstrated. Here, we report a first-principles simulation of that experiment which enables us to attribute the main features of the observed angular distribution to a single L=2 partial-wave shape resonance. Finallly, our results demonstrate important stereodynamical insights that can be gained when numerically exact quantum scattering calculations are combined with experimental results in the few-partial-wave regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

NRL tethered balloon measurements at San Nicolas Island during FIRE IFO 1987

An overview is given of the tethered balloon measurements made during the First ISCCP Regional Experiment (FIRE) marine stratocumulus intensive field observations (IFO) at San Nicolas Island in 1987. The instrument utilized on the balloon flights, the 17 flights over a 10 day period, the state of the data analysis, and some preliminary results are described. A goal of the measurements with the Naval Research Laboratory (NRL) balloon was to give a unique and greatly improved look at the microphysics of the clear and cloud-topped boundary layer. For this goal, collocated measurements were made of turbulence, aerosol, cloud particles, and meteorology. Two new instruments which were expected to make significant contributions to this effort were the saturation hygrometer, capable of measuring 95 percent less than RH 105 percent (with an accuracy of 0.05 percent near 100 percent) and used for the first time in clouds; and the forward scatter meter which gives in situ LWC measurements at more than 10 Hz. The data set, while unfortunately only partially simultaneous with the bulk of the FIRE stratocumulus observations, is unique and worthwhile in its own right. For the first time accurate RH measurements near 100 percent have been made in-cloud; although, the use of the saturation hygrometer reflected a learning experience which will result is substantially better performance the next time. These measurements were made in conjunction with other microphysical measurements such as aerosol and cloud droplet spectra, and perhaps most important of all, they were all collocated with bivane turbulence measurements thus permitting flux calculations. Thus the analysis of this data set, which consisted of about 50 percent stratocumulus cases including increasing and decreasing partial cloud cover, should lead to new insights on the physical mechanisms which drive the boundary-layer/cloud/turbulence system.

Gerber, Hermann↗
DOE OSTI2016

Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass

The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO 3 /TiO 2 and MoO 3 /ZrO 2 at 500 °C and H 2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO 3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO 3 mass ratio exposed to the catalytic bed. For biomass to MoO 3 mass ratios <1.5, predominantly olefinic and aromatic hydrocarbons are produced with no detectable oxygen-containing species. For ratios ≥ 1.5, partially deoxygenated species comprised of furans and phenols are observed, with a concomitant decrease of olefinic and aromatic hydrocarbons. For ratios ≥ 5, primary pyrolysis vapours break through the bed, indicating the onset of catalyst deactivation. Product quantification with a tandem micropyrolyzer-GCMS setup shows that fresh supported MoO 3 catalysts convert ca. 27 mol% of the original carbon into hydrocarbons comprised predominantly of aromatics (7 C%), olefins (18 C%) and paraffins (2 C%), comparable to the total hydrocarbon yield obtained with HZSM-5 operated under similar reaction conditions. In conclusion, post-reaction XPS analysis on supported MoO 3 /ZrO 2 and MoO 3 /TiO 2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo 5+ and Mo 3+ ), and that catalyst deactivation is likely associated to coking.

09 BIOMASS FUELS↗
NASA NTRS1993

Experimental segregation of iron-nickel metal, iron-sulfide, and olivine in a thermal gradient: Preliminary results

Speculation about the possible mechanisms for core formation in small asteroids raises more questions than answers. Petrologic evidence from iron meteorites, pallasites, and astronomical observations of M asteroids suggests that many small bodies were capable of core formation. Recent work by Taylor reviews the geochemical evidence and examines the possible physical/mechanical constraints on segregation processes. Taylor's evaluation suggests that extensive silicate partial melting (preferably 50 vol. percent or greater) is required before metal can segregate from the surrounding silicate and form a metal core. The arguments for large degrees of silicate partial melting are two-fold: (1) elemental trends in iron meteorites require that the metal was at is liquidus; and (2) experimental observations of metal/sulfide inclusions in partially molten silicate meteorites show that the metal/sulfide tends to form spherules in the liquid silicate due to surface tension effects. Taylor points out that for these metal spherules to sink through a silicate mush, high degrees of silicate partial melting are required to lower the silicate yield strength. Although some qualitative experimental data exists, little is actually known about the behavior of metals and liquid sulfides dispersed in silicate systems. In addition, we have been impressed with the ability of cumulative olivine to expel trapped liquid when placed in a thermal gradient. Consequently, we undertook to accomplish the following: (1) experimentally evaluate the potential for metal/sulfide/silicate segregation in a thermal gradient; and (2) obtain quantitative data of the wetting parameters of metal-sulfide melts among silicate grains.

Jurewicz, Stephen R.↗
DOE OSTI2017

An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z ' = 12

A structural study of the complex aminated stereotriads, [( tert -butyldimethylsilyl)oxy]-4-ethynyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (1) and its reduced analogue, [( tert -butyldimethylsilyl)oxy]-4-ethenyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (2), revealed a k 12-type second-order phase transition in 1 and phase stability of 2 over the temperature range 100–400 K. The observed phase change in 1 has been linked to the partial ordering of the extensive positional disorder of the high temperature phase upon cooling as revealed by single-crystal X-ray diffraction. The ordering breaks the translational symmetry, introduces differences in the molecular volumes of the packed species, and results in a low-temperature crystal structure with Z '=12. The in situ powder X-ray diffraction studies suggest that the transition occurs between 237 K and 180 K upon cooling, but complete amorphization in the range of 244–274 K during heating complicated the assignment of the transition temperature. Lastly, the observed loss of crystallinity has been linked to the phase transition and implies that the loss of long range order is due to the crystallites undergoing the transformation independently from one another.

36 MATERIALS SCIENCE↗