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NASA NTRS1992

Study of density distribution in a near-critical simple fluid (19-IML-1)

This experiment uses visual observation, interferometry, and light scattering techniques to observe and analyze the density distribution in SF6 above and below the critical temperature. Below the critical temperature, the fluid system is split up into two coexisting phases, liquid and vapor. The spatial separation of these phases on earth, liquid below and vapor above, is not an intrinsic property of the fluid system; it is merely an effect of the action of the gravity field. At a fixed temperature, the density of each of the coexisting phases is in principle fixed. However, near T sub c where the fluid is strongly compressible, gravity induced hydrostatic forces will result in a gradual decrease in density with increasing height in the sample container. This hydrostatic density profile is even more pronounced in the one phase fluid at temperatures slightly above T sub c. The experiment is set up to study the intrinsic density distributions and equilibration rates of a critical sample in a small container. Interferometry will be used to determine local density and thickness of surface and interface layers. The light scattering data will reveal the size of the density fluctuations on a microscopic scale.

Michels, Teun↗

NASA NTRS1992

Self-diffusion of magnesium in spinel and in equilibrium melts - Constraints on flash heating of silicates

An isotopic tracer is used to measure Mg self-diffusion in spinel and coexisting melt at bulk chemical equilibrium. The diffusion coefficients were calculated from the measured isotope profiles using a model that includes the complementary diffusion of Mg-24, Mg-25, and Mg-26 in both phases with the constraint that the Mg content of each phase is constant. The activation energy and preexponential factor for Mg self-diffusion in spinel are, respectively, 384 +/- 7 kJ and 74.6 +/- 1.1 sq cm/s. These data indicate Mg diffusion in spinel is much slower than previous estimates. The activation energy for Mg self-diffusion in coexisting melt is 343 +/- 25 kJ and the preexponential factor is 7791.9 +/- 1.3 sq cm/s. These results are used to evaluate cooling rates of plagioclase-olivine inclusions (POIs) in the Allende meteorite. Given a maximum melting temperature for POIs of about 1500 C, these results show that a 1-micron radius spinel would equilibrate isotopically with a melt within about 60 min.

Sheng, Y. J.↗

NASA NTRS1993

The stability of hibonite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions

Phase fields in which hibonite (Hib) and silicate melt coexist with spinel (Sp), CaAl4O7 (CA2), gehlenitic melilite (Mel), anorthite (An), or corundum (Cor) in the system CaO-MgO-Al203-SiO2-TiO2 (CMAST) were determined and activity models developed for Mel and Hib solid solutions. Experimentally determined partition coefficients for Ti between Hib and coexisting melt, D sub t, vary from 0.8 to 2.1 and generally decrease with increasing TiO2 content in the liquid (L). Based on Ti partioning between Hib and melt, bulk inclusion compositions and Hib-saturated liquid use phase diagrams, the Hib in Fluffy Type A inclusions (FTA's) from Allende and at least some of the Hib from Hib-rich inclusions is relict; much of the Hib from Hib-glass spherules probably crystallized from a melt under nonequilibrium conditions. Bulk compositions for all of these Ca-Al-rich inclusions (CAI's) are consistent with an origin as Mel + Hib + Sp + perovskite (Pv) proto-inclusions in which Mel was partially altered. In some cases, the proto-inclusion was partially or completely melted with vaporization occurring over a period of time sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. If equilibration temperatures based on Hib-bearing CAI's reflect condensation in a cooling gas of solar composition, then Hib + Cor condensed at approximately 1260 C (referenced to 10 exp -3 atm) and Hib + Sp + Mel at approximately 1215 +/- 10 C. Simple thermochemical models for the substitution of trace elements into the Ca-site of meteoritic Hib suggest that virtually all Eu is divalent in early condensate Hibs but that Eu(2+)/Eu(3+) decreases by a factor of 20 or more during the course of condensation, primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phases condense. The relative sizes of Eu and Yb anomalies in meteoritic Hibs and CAI's may be influenced by this effect.

Beckett, J. R.↗

NASA NTRS1993

Solubilities of carbon dioxide and water in rhyolitic melt at 850 C and 750 bars

Concentrations of carbon dioxide and water dissolved in glasses quenched from rhyolitic melts equilibrated with H2O-CO2 fluids at 850 C and 750 bar were measured using IR spectroscopy; concentrations of H2O and CO2 in the quenched fluids were measured manometrically. The mole fraction of CO2 in the quenched fluid ranged from 0.06 to 0.91. Concentrations of CO2 in the coexisting rhyolitic melt increased from 23(+/-6) ppm for the sample equilibrated with the most CO2-poor fluid to 515(+/-16) ppm for that equilibrated with the most CO2-rich fluid. The water content of the melt varied from 0.51(+/-0.06) to 3.34(+/-0.08) wt pct. Our results show that concentrations of molecular CO2 and H2O in the glasses obey Henry's Law; the mole fractions of molecular CO2 and molecular H2O in the quenched melts are proportional to their fugacities in the coexisting vapor. CO2 contents of vapor-saturated melts are not enhanced by addition of water to CO2-rich vapor, contrary to previous reports for silicate melts at higher pressures. The Henrian behavior of CO2 and H2O at low pressure considerably simplifies modeling of the degassing of silicic magmas.

Blank, J. G.↗

NASA NTRS1994

Phase E in a water-saturated peridotite system at 9.3 GPa

The stability of hydrous phases in a natural upper mantle system has been investigated at 9.3 GPa using a gel of KLB-1 peridotite composition with brucite which contains 14 wt. percent (30 atom. percent) water. No hydrous mineral was found at 950 (+150 -50) degree C. At 800 degree C, an assemblage of phase A, phase E, enstatite, clinohumite, and garnet is obtained. Although there is a significant thermal gradient over the sample, phase E is found to be surrounded by phase A in the lower temperature part. Electron probe analyses show that phase E has 35.5 SiO2, 4.4 Al2O3, 41.1 MgO and 8.5 wt. percent FeO* (Mg value is 90) with an oxide sum of 89.7 wt. percent, and possesses a stoichiometry similar to that proposed by Kanzaki. CaO and TiO2 are both less than 0.1 wt. percent. Coexisting phase A has 0.5 wt. percent CaO but only 0.4 wt. percent Al2O3 concentration. Phase A coexists with only enstatite in the water-saturated MgO-FeO-SiO2 system at 800 degree C and 9.3 GPa as well as the results in the water-saturated MgO-SiO2 system. Therefore it is suggested that the addition of Al2O3 expands the stability field of phase E to lower than 13 - 17 GPa in the water-saturated MgO-SiO2 system.

Kawamoto, Tatsuhiko↗

NASA NTRS1994

Volatiles in the deep Earth: An experimental study using the laser-heated diamond cell

Experiments with the laser-heated diamond cell show that H2O and CO2 can be stabilized within crystalline mineral structures of the lower-mantle, and hence can be present at relatively non-volatile components of the Earth's deep interior. Samples quenched from high pressures and temperatures document that the MgCO3-FeCO3 magnesite-siderite solid-solution is stable and coexists with (Mg,Fe)SiO3 perovskite at 30-40 GPa and approximately 1500-2000 K. In contrast, H2O combines with the silicate to form (Mg,Fe)SiH2O4 phase D, coexisting with (Mg,Fe)SiO3 perovskite at these conditions. If enough water is present, phase D can become the predominant phase in the MgSiO3-H2O system at lower-mantle conditions. Our work extends previous studies to Fe-bearing compositions and to the pressures of the mid-lower mantle. Thus, the results of high-pressure experiments suggest that both H2O and CO2 can be abundant in the Earth's lower mantle, being present in stable hydroxisilicate and carbonate phases.

Li, Xiaoyuan↗

NASA NTRS1995

Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

Wooldridge, Paul J.↗

NASA NTRS1994

The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical modes for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu(2+)/Eu(#+) decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phase condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect.

Beckett, J. R.↗

NASA NTRS1995

Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

Wooldridge, Paul J.↗

NASA NTRS2000

Understanding Microbial Contributions to Planetary Atmosphere

Should our search of distant, extrasolar planetary atmospheres encounter evidence of life, that evidence will most likely be the gaseous products of microorganisms. Our biosphere was exclusively microbial for over 80 percent of its history and, even today, microbes strongly influence atmospheric composition. Life's greatest environmental impact arises from its capacity for harvesting energy and creating organic matter. Microorganisms catalyze the equilibration of C, S and transition metal species at temperatures where such reactions can be very slow in the absence of life. Sunlight has been harvested through photosynthesis to create enormous energy reservoirs that exist in the form of coexisting reservoirs of reduced, organic C and S stored in Earth's crust, and highly oxidized species (oxygen, sulfate and ferric iron) stored in the crust, oceans and atmosphere. Our civilization taps that storehouse of energy by burning fossil fuels. As astrobiologists, we identify the chemical consequences of distant biospheres as expressed in the atmospheres of their planets. Our approach must recognize that planets, biospheres and atmospheres evolve and change. For example, a tectonically more active early Earth hosted a thermophilic, non-photosynthetic biosphere and a mildly reducing, carbon dioxide-rich and oxygen-poor atmosphere. Microorganisms acquired energy by consuming hydrogen and sulfide and producing a broad array of reduced C and S gases, most notably, methane. Later, diverse types of bacterial photosynthesis developed that enhanced productivity but were incapable of splitting water to produce oxygen. Later, but still prior to 2.6 billion years ago, oxygenic photosynthesis developed. We can expect to encounter distant biospheres that represent various stages of evolution and that coexist with atmospheres ranging from mildly reducing to oxidizing compositions. Accordinaly, we must be prepared to interpret a broad range of atmospheric compositions, all containing signatures of life. Remarkably little is known about the composition of our own earlier atmosphere, particularly prior to the rise of oxygen levels some 2.0 to 2.2 billion years ago. Thus, field and laboratory observations and theoretical simulations should be conducted to examine the relationships between the structure and function of microbial ecosystems and their gaseous products. Ecosystems that are analogs of our ancient biosphere (e.g., based upon chemosynthesis or non-oxygenic photosynthesis, thermophilic and subsurface communities, etc.) should be included. Because key environmental parameters such as temperature and levels of hydrogen, carbon dioxide and oxygen varied during planetary evolution, their consequences for microbial ecosystems should be explored.

DesMarais, David J.↗

NASA NTRS2002

Size distribution of retrovirally marked lineages matches prediction from population measurements of cell cycle behavior

Mechanisms that regulate neuron production in the developing mouse neocortex were examined by using a retroviral lineage marking method to determine the sizes of the lineages remaining in the proliferating population of the ventricular zone during the period of neuron production. The distribution of clade sizes obtained experimentally in four different injection-survival paradigms (E11-E13, E11-E14, E11-E15, and E12-E15) from a total of over 500 labeled lineages was compared with that obtained from three models in which the average behavior of the proliferating population [i.e., the proportion of cells remaining in the proliferative population (P) vs. that exiting the proliferative population (Q)] was quantitatively related to lineage size distribution. In model 1, different proportions of asymmetric, symmetric terminal, and symmetric nonterminal cell divisions coexisted during the entire developmental period. In model 2, the developmental period was divided into two epochs: During the first, asymmetric and symmetric nonterminal cell divisions occurred, but, during the second, asymmetric and symmetric terminal cell divisions occurred. In model 3, the shifts in P and Q are accounted for by changes in the proportions of the two types of symmetric cell divisions without the inclusion of any asymmetric cell divisions. The results obtained from the retroviral experiments were well accounted for by model 1 but not by model 2 or 3. These findings demonstrate that: 1) asymmetric and both types of symmetric cell divisions coexist during the entire period of neurogenesis in the mouse, 2) neuron production is regulated in the proliferative population by the independent decisions of the two daughter cells to reenter S phase, and 3) neurons are produced by both asymmetric and symmetric terminal cell divisions. In addition, the findings mean that cell death and/or tangential movements of cells in the proliferative population occur at only a low rate and that there are no proliferating lineages "reserved" to make particular laminae or cell types. Copyright 2002 Wiley-Liss, Inc.

NASA Discipline Developmental Biology↗

NASA NTRS2003

Progress in Developing a New Field-theoretical Crossover Equation-of-State

A new field-theoretical crossover equation-of-state model is being developed. This model of a liquid-gas critical point provides a bridge between the asymptotic equation-of-state behavior close to the transition, obtained by the Guida and Zinn-Justin parametric model [J. Phys. A: Math. Gen. 31, 8103 (1998)], and the expected mean field behavior farther away. The crossover is based on the beta function for the renormalized fourth-order coupling constant and incorporates the correct crossover exponents and critical amplitude ratios in both regimes. A crossover model is now being developed that is consistent with predictions along the critical isochore and along the coexistence curve of the minimal subtraction renormalization approach developed by Dohm and co-workers and recently applied to the O(1) universality class [Phys. Rev. E, 67, 021106 (2003)]. Experimental measurements of the heat capacity at constant volume, isothermal susceptibility, and coexistence curve near the He-3 critical point are being compared to the predictions of this model. The results of these comparisons will be presented.

Rudnick, Joseph↗

NASA NTRS2006

Mechanisms for Diurnal Variability of Global Tropical Rainfall Observed from TRMM

The behavior and various controls of diurnal variability in tropical-subtropical rainfall are investigated using Tropical Rainfall Measuring Mission (TRMM) precipitation measurements retrieved from the three level-2 TRMM standard profile algorithms for the 1998 annual cycle. Results show that diurnal variability characteristics of precipitation are consistent for all three algorithms, providing assurance that TRMM retrievals are producing consistent estimates of rainfall variability. As anticipated, most ocean areas exhibit more rainfall at night, while over most land areas, rainfall peaks during daytime; however, important exceptions are noted. The dominant feature of the oceanic diurnal cycle is a rainfall maximum in late-evening-early-morning (LE-EM) hours, while over land the dominant maximum occurs in the mid- to late afternoon (MLA). In conjunction with these maxima are pronounced seasonal variations of the diurnal amplitudes. Amplitude analysis shows that the diurnal pattern and its seasonal evolution are closely related to the rainfall accumulation pattern and its seasonal evolution. In addition, the horizontal distribution of diurnal variability indicates that for oceanic rainfall, there is a secondary MLA maximum coexisting with the LE-EM maximum at latitudes dominated by large-scale convergence and deep convection. Analogously, there is a preponderancy for an LE EM maximum over land coexisting with the stronger MLA maximum, although it is not evident that this secondary continental feature is closely associated with the large-scale circulation. Neither of the secondary maxima exhibit phase behavior that can be considered semidiurnal in nature. Diurnal rainfall variability over the ocean associated with large-scale convection is clearly an integral component of the general circulation. Phase analysis reveals differences in regional and seasonal features of the diurnal cycle, indicating that underlying forcing mechanisms differ from place to place. This is underscored by the appearance of secondary ocean maxima in the presence of large-scale convection, along with other important features. Among these, there are clear-cut differences between the diurnal variability of seasonal rainfall over the mid-Pacific and Indian Ocean Basins. The mid-Pacific exhibits double maxima in spring and winter but only LE-EM maxima in summer and autumn, while the Indian Ocean exhibits double maxima in spring and summer and only an LE-EM maximum in autumn and winter. There are also evident daytime maxima within the major large-scale marine stratocumulus regions off the west coasts of continents. The study concludes with a discussion concerning how the observational evidence either supports or repudiates possible forcing mechanisms that have been suggested to explain diurnal rainfall variability.

Yang, Song↗

NASA NTRSDate not supplied

Oxygen Isotopic Composition of Refractory Inclusions from the Miller Range (MIL) 090019 Carbonaceous Chondrite

Introduction: Primitive meteorites contain Calcium-Aluminum-rich Inclusions (CAIs)that preserve the records of the earliest times in the Solar System. CAIs record O isotopic variations with time and/or location from solar (16O-rich) to planetary (16O-poor) compositions [e.g., 1, 2].However, CAIs were also affected by parent body processing to varying degrees. The goal of this work was to identify the processes that resulted in the fine-scale spatial variations in oxygen isotopic compositions within the most ancient Solar System solids. We report oxygen isotopic composition of CAIs from MIL 090019 CO3.1 carbonaceous chondrite. MIL 090019 contains a high abundance of CAIs showing mineralogical as well as textural variations [3]. Methods: We analyzed 10 CAIs with different mineralogical assemblages, classified as corundum-bearing, grossite-bearing, hibonite-bearing, melilite-bearing, anorthite-bearing inclusions and amoeboid olivine aggregates(AOA’s). The mineralogical and petrological characterization of CAIs was performed using the JOEL Hyperprobe 8530 electron microprobe at NASA JSC. Oxygen isotopic imaging of the CAIs was done using the Cameca NanoSIMS 50L ion microprobe at NASA JSC. We followed the analytical protocol described in [4]. O-isotopic maps of the CAI were acquired by rastering a ~3 pA primary Cs+beam at 16 keVover an area of 20 ×20μm2over a period of ~7 hours. Negative secondary ions of 16O−, 17O−, 18O−, 28Si−, 24Mg16O−, 27Al16O−, and 40Ca16O−were simultaneously acquired using electron multiplier detectors at a mass resolving power sufficient to resolve the 16OH−interference from the 17O−peak, where the contribution of 16OH−was <0.1%.An electron flood gun was used to mitigate sample charging during the analyses. We used San Carlos olivine and Madagascar hibonite as isotopic standards to correct for the instrumental mass fractionation. The O-isotopic ratios were corrected for the quasi simultaneous arrival (QSA) effect and the detector dead time. All reported errors are 1 sigma. Results: The MIL 090019 carbonaceous chondrite hosts refractory inclusions varying in their mineralogies and textures[2, 3]. We found the oxygen isotopic compositions of mineral phases in MIL 090019 CAIs show large variations with Δ17O values varying from -27 to 0‰. A corundum-bearing inclusion records isotopic variations with corundum, melilite, perovskite, and anorthite showing Δ17Ovalues of -20 ±2.5, -10.2 ± 6.5, -10.7 ± 1.3,and -1.2 ± 3.2‰ respectively. A grossite-hibonite-bearing inclusion also records O-isotopic heterogeneity, where grossite, hibonite, Mg-rich spinel, and melilite show -3.7 ± 2.7, -22.9 ± 2.5, -21.4 ± 2.6, and -17.3 ± 2.8‰ respectively, whereas perovskite grains record a heterogenous isotopic composition ranging from -22.6 to -13.9‰. A hibonite-bearing inclusion shows average Δ17Ο values of -17.6 ± 5.3 ‰ and -15.1 ± 4.8 ‰ for hibonite and spinel respectively. The two perovskite grains also show relatively 16O-poor composition (Δ17Ο = -11.8 ± 6.4 ‰ and -8.6 ± 5.2 ‰). Anorthite has ~0.1 wt% Na2O and ~0.52 wt% FeO and a Δ17Ο value of -7.2 ± 5.0 ‰, whereas diopside records a Δ17Ο value of -3.5 ± 5.0 ‰. A hibonite-spinel-rich inclusion contains spinel and hibonite that are16O-rich (Δ17Οvalues -21.3 ± 2.8‰ and -19.4 ± 3.0‰, respectively). Melilite shows heterogenous oxygen isotopic composition, with an inner 16O-rich region and an outer 16O-poor region separated by a sharp boundary, with a bulk Δ17Ο= -16.2 ± 2.1‰, whereas two perovskite grains are relatively 16O-poor (Δ17Ο= -13.2 ± 3.7‰ and -7.1 ± 3.4‰).A spinel-rich inclusion contains perovskite grains with Δ17Οranging from -27.0 to -22.8 ‰and spinel with average Δ17Οvalue of -21.4 ± 2.8 ‰. In a melilite and spinel-rich CAI, perovskite, spinel, diopside, melilite, and Al-Ti-rich pyroxene record Δ17Ο values of-26.9 ± 4.6‰, -22.4 ± 4.3‰,-23.4 ± 4.9, -19.3 ± 3.4, and -19.0 ± 4.3 ‰ respectively. Olivine and spinel components of 2 AOA’s record a 16O-rich composition with Δ17O~-23‰. Discussion: The coexistence of 16O-rich and 16O-poor minerals within CAIs has been attributed to differing degrees of O isotopic exchange, reflecting a wide range of O diffusion rates[5]. However, the O isotopic heterogeneity observed in these CAIs cannot be explained by oxygen diffusion in nebular or parent body settings alone. The isotopic imaging of CAIs from the MIL 090019 meteorite shows variations in the O isotopic composition recorded in their mineral components, suggesting that these CAIs record the oxygen isotopic heterogeneity in the nebular gas from which they condensed. The coexistence of 16O-rich and 16O-poor mineral components in the CAI-forming region suggests that the gas in this region was not well-mixed and consisted of distinct 16O-rich and 16O-poor gaseous reservoirs.

P Mane↗

DOE OSTI2020

Hierarchical Membrane Dynamics in Phase-Separated Model Membranes

Lipid membranes, the primary matrix of cell membranes, exhibit a hierarchy of dynamics from molecular motions to collective undulations, which control spatiotemporal membrane phenomena and regulate various cellular functions. Thus, understanding how various dynamic modes influence membrane behavior is crucial to uncovering the design rules of cell membranes and implementing them in future technologies. Previous membrane dynamics studies using neutron spin-echo spectroscopy (NSE) have shed light on the dependence of collective membrane fluctuations on viscoelastic membrane properties, demonstrating that thickness fluctuation modes (100ns) are dictated by membrane viscosity, which directly governs fast (ps) molecular diffusive motions. Here, we focus on phase-separating lipid membranes, composed of DMPC:DSPC mixtures, to understand the effect of domain formation/growth on hierarchical matrix dynamics using selective lipid deuteration and different neutron spectroscopy techniques. NSE measurements on DMPC:DSPC-d83 (70:30 mol%) show that bending rigidity of the DMPC-rich matrix graduallyincreases with decreasing temperature - as the fully-fluid membrane approaches the upper phase transition (i.e. with the formation of transient DSPC clusters) - and increases further in the phase coexistence region with the growth of DSPC domains. Comparatively, NSE measurements on DMPC-d54:DSPC-d83 vesicles show pronounced matrix thickness fluctuations in the fully-fluid phase and drastic suppression of this fluctuation mode in the gel-fluid coexistence phase, even when the DMPC-rich matrix is still in its fluid phase. This suppression in fluctuations suggests an increase in the matrix viscosity with the growth of gel DSPC domains, which is further investigated by selectively measuring lipid diffusion in the DMPC-rich matrix using neutron backscattering spectroscopy. Comparisons of the experimental results with coarse-grained MD simulationsillustrate the underlying coupling mechanisms. Overall, these observations indicate a clear mechanical and viscoelastic coupling betweenlipid domains and their host matrix, suggesting that domain formation influences membrane properties beyond local effects.

Carrillo, Jan Michael↗

DOE OSTI2020

CP-DSSS: An OFDM Compatible Variable Rate Modulation for 5G and Beyond

Cyclic prefix direct sequence spread spectrum (CPDSSS) is a recently proposed waveform that has been designed for coexistence with OFDM (orthogonal frequency division multiplexing) in the same or a pair of parallel networks. The first contribution of this paper is to present equations that reveal similarities and differences of CP-DSSS and OFDM. Furthermore, we show that the channel model of CP-DSSS reduces to that of a cyclic prefixed block-wise single carrier modulation (CP-SCM). However, unlike CP-SCM whose symbol rate is always equal to the transmission bandwidth, CP-DSSS can be adopted to any symbol rate equal to or smaller than the transmission bandwidth. This reduction in symbol rate allows CP-DSSS power spectral density to drop to an arbitrarily low level, hence, facilitates it coexistence as a secondary waveform in a network of primary users. The peak-to-average power ratio (PAPR) of CP-DSSS is also explored and a method for reducing it is proposed.

5G↗

DOE OSTI2020

Influences of Mg Ions and Al Ions on Deposition Behavior of Supersaturated Silicic Acid - 20261

Silicic acid can change into various species such as deposit, colloidal, and soluble form under certain conditions: for example, gradual pH changes around geological disposal repositories. In particular, silicic acid deposits narrow groundwater flow paths, thereby restricting the flow of groundwater. Such effects may contribute to a delay in radionuclide migration. Previous studies have reported that silicic acid supersaturated in sodium and calcium ions can narrow the flow paths. This study examined the effect of magnesium (Mg) and aluminum (Al) ions on the deposition of supersaturated silicic acid on the solid phase. The deposition behavior of supersaturated silicic acid on the solid phase was investigated in a batch system while changing the initial supersaturation concentration, the coexisting ion concentration, and the amount of added solid phase. In the presence of Mg ions, silicic acid precipitation increased with increasing Mg ion concentration due to the influence of the electrolyte, and crosslinking reactions. The coexistence of Al ions significantly suppressed silicic acid deposition due to the formation of a covering on the solid surface during Al ion hydrolysis under conditions of high Al concentration (1.4 mM). On the basis of these experimental results, the apparent deposition rate constant of silicic acid was estimated to be in the range from 10{sup -11} to 10{sup -10} m/s. The Damkoehler number (the dimensionless number expressed by the ratio of the characteristic time of mass transfer and the chemical reaction constant) was sufficient to cause the clogging of the host rock by deposition. This suggests that supersaturated silicic acid deposition, regardless of the presence of Mg ions (and Al ions), contributes to improving barrier performance against radionuclide migration in the host rock. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Strain-relaxed tetragonal MAPbI 3 results in efficient mesoporous solar cells

In mesoporous organo-halide perovskite solar cells, the coexistence of tetragonal phase and cubic phase in the perovskite layer is found to result in strained crystal structure at the mesoporous TiO 2 (mp-TiO 2 )/perovskite heterointerface. This results in structural defects pinholes, grain boundaries, and interfacial porosity which is detrimental towards photovoltaic performance and device stability. The strain at the interface originates from the lattice mismatch between the mp-TiO 2 nanoparticles (NPs) and perovskite. Here, a transformative approach is demonstrated to realize relaxed and high purity tetragonal phase MAPbI 3 (RP) near the mp-TiO 2 interface region. This approach involves inserting a ~2 nm lattice matched buffer layer of cubic CsPbBr 3 between mp-TiO 2 NPs and MAPbI 3 , which serves as a template for epitaxial growth for top MAPbI 3 . As a result, the solar cell with relaxed MAPbI3 shows a power conversion efficiency (PCE) of 22.12% with significantly enhanced environmental, light, and thermal stability.

14 SOLAR ENERGY↗