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At least 109 records · Page 6

Investigating the Effect of Water on the Mechanical Properties of Cellulose from Multiscale Molecular Dynamics Simulations

Classical molecular dynamics (MD) simulations provide insight into the structure and physicochemical properties of materials with atomic resolution. However, the length and time scales accessible to atomistic MD are orders of magnitude smaller than many relevant processes such as the response of a bulk material to experimentally accessible strain rates, which presents challenges when comparing models to experimental measurements. Bottom-up coarse-graining provides a means for systematically mapping atomistic information to lower resolution models to increase the length and time scales achievable by simulation. Cellulose is an abundant carbohydrate biopolymer with applications to many fields of research, such as materials science and renewable energy, due to its desirable mechanical properties and viability for conversion into biofuel. The effect of moisture content on the Young's modulus of cellulose is of special interest due to its native environment often being in the hydrated secondary plant cell wall and the grinding energy requirements for biomass feedstock preprocessing. The current work investigates the effects of water solvent on the Young's modulus of cellulose calculated from coarse-grained MD mechanical stress simulations. The coarse-grained model was parametrized from atomistic MD calculations of cellulose-cellulose potentials of mean force using umbrella sampling techniques under vacuum and solvated conditions. The Young's moduli of the coarse-grained cellulose assemblies parametrized from cellulose in vacuum or solvated in water were computed via mechanical stress simulations to highlight the importance of capturing solvent interactions for modeling the mechanical behavior of cellulose.

BASIC BIOLOGICAL SCIENCES,RADIATION PROTECTION AND↗

Axial and torsional fatigue behavior of Waspaloy

The cyclic flow response and crack growth behavior of Waspaloy at room temperature and 650 C under tensile loading and torsional loading was studied, for two conditions of Waspaloy: fine grain, large gamma prime size; coarse grain, small gamma prime size. The fine grain material showed 5 to 10 percent hardening after about 10 percent of life, with sequent softening to failure at both themperature levels. The coarse grain material showed either stable response or monotonic softening to failure. Early crack initiation was observed on planes of maximum shear, with eventual branching to principle planes under torsional loading; cracks were always normal to load axis under tensile loading. Also, crack paths were intergranular at 650 C, mostly transgranular at room temperature.

Zamrik, S.↗

Microstructure refinement of hot deformed Dy-free NdFeB magnets through a novel cold sintering approach by pressure-assisted spark plasma sintering

Anisotropic fine-grained Dy-free NdFeB high-performance magnets were produced using a novel cold sintering approach by pressure-assisted spark plasma sintering (SPS). The NdFeB nanocrystalline ribbon powders were subjected to cold sintering below 450 °C using pressure-assisted SPS, followed by hot deformation at 710 °C and 810 °C via SPS. Results indicate that cold sintering below 450 °C effectively restricts grain growth in the NdFeB magnets, yielding sub-100 nm scale grains across both fine-grained regions and most coarse-grained regions. The refined grain structure achieved through cold sintering allows for a lower hot deformation temperature as compared with the magnet by conventional sintering, as finer grains allow easier deformation and grain sliding/rotation. This process produces a highly fine-grained and anisotropic microstructure to achieve high magnetic performance (i.e., high intrinsic coercivity, remanence, and maximum energy product) in the magnets. The cold sintering (at 350 °C) and lower hot deformation temperatures required (e.g., 710 °C) help control grain coarsening and limit grain size that is commensurate with the size of a single magnetic domain of the Nd 2 Fe 14 B magnetic matrix phase, resulting in high intrinsic coercivity (H ci =11.4 kOe). Furthermore, the reduced hot deformation temperature mitigates the formation of coarse grain bands, leading to improved magnetic properties, specifically an increased remanence (B r = 14.3 kGs) and a high maximum energy product ((BH) max = 48 MGOe). In conclusion, cold sintered hot deformed NdFeB magnet also shows good thermal stability with reversible temperature coefficient α(B r )= -0.097 %/K and α(H ci )= -0.616 %/K at elevated temperatures up to 400 K.

Cold Sintering↗

The isotopic composition of uranium and lead in Allende inclusions and meteoritic phosphates

The isotopic compositions of uranium and lead in Ca-Al-rich inclusions from the Allende chondrite and in whitlockite from the St. Severin chondrite and the Angra dos Reis achondrite are reported. Isoptopic analysis of acid soluble fractions of the Allende inclusions and the meteoritic whitlockite, which show isotopic anomalies in other elements, reveals U-235/U-238 ratios from 1/137.6 to 1/138.3, within 20 per mil of normal terrestrial U abundances. The Pb isotopic compositions of five coarse-grained Allende inclusions give a mean Pb-207/Pb-206 model age of 4.559 + or - 0.015 AE, in agreement with the U results. Pb isotope ratios of two fine-grained inclusions and a coarse-grained inclusion with strong mass fractionation and some nonlinear isotopic anomalies indicate that the U-Pb systems of these inclusions have evolved differently from the rest of Allende. Th/U abundance ratios in the Allende inclusions and meteoritic phosphate are found to range from 3.8 to 96, presumably indicating an optimal case for Cm/U fractionation, although the normal U concentrations do not support claims of abundant live Cm-247 or Cm-247/U-238 fractionation at the time of meteorite formation, in contrast to previous results. A limiting Cm-247/U-235 ratio of 0.004 at the time of meteorite formation is calculated which implies that the last major r process contribution at the protosolar nebula was approximately 100 million years prior to Al-26 formation and injection.

Chen, J. H.↗

Opaque-rich lithology in the Divnoe achondrite: Petrology and origin

An opaque-rich lithology (ORL) makes up to approximately 9 vol. percent of the Divnoe achondrite. It is characterized by enrichment of troilite and pyroxene, compared to the bulk Divnoe, and by the presence of tiny remnants of olivine in low-CA pyroxene and low minor element concentrations in pyroxene. The ORL was formed by local reaction between gaseous sulfur and olivine in the Divnoe. The Divnoe meteorite is an olivine-rich achondrite with subchondritic chemistry and mineralogy. It has a granoblastic coarse-grained olivine groundmass (CGL: coarse-grained lithology) with relatively large (2-10 mm) poikilitic patches (PP) of pyroxene and, rarely, plagioclase. The groundmass also contains an opaque-rich fine-grained lithology (ORL) which comprises approximately 9 vol. percent of the meteorite, displays reaction boundaries with the groundmass, and differs in mineral chemistry from it. Numerous micron- to mm-thick veins of troilite and, rarely, metal cross all the lithologies found in the meteorite. The Divnoe itself appears to represent a sample of an igneous source region.

Petaev, M. I.↗

The Divnoe meteorite: Petrology, chemistry, oxygen isotopes and origin

The Divnoe meteorite is an olivine-rich primitive achondrite with subchondritic chemistry and mineralogy. It has a granoblastic, coarse-grained, olivine groundmass (CGL: coarse-grained lithology) with relatively large pyroxene-plagioclase poiklitic patches (PP) and small fine-grained domains of an opaque-rich lithology (ORL). Both PP and ORL are inhomogeneously distributed and display reaction boundaries with the groundmass. Major silicates, olivine Fa(20-28) and orthopyroxyene Fs(20-28 Wo(0.5-2.5), display systematic differences in composition between CGL and ORL as well as a complicated pattern of variations within CGL. Accessory plagioclase has low K content and displays regular igneous zoning with core compositions An(40-45) and rims An(32-37). The bulk chemical composition of Divnoe is similar to that of olivine-rich primitive achondrites, except for a depletion of incompatible elements and minor enrichment of refractory siderophiles. Oxygen isotope compositions for whole-rock and separated minerals from Divnoe fall in a narrow range, with mean delta O-18 = +4.91, delta O-17 = +2.24, and Delta O-17 = -0.26 +/- 0.11. The isotopic composition is not within the range of any previously recognized group but is very close to that of the brachinites. To understand the origin of Divnoe lithologies, partial melting and crystallization were modelled using starting compositions equal to that of Divnoe and some chondritic meteorites. It was found that the Divnoe composition could be derived from a chondritic source region by approximately 20 wt% partial melting at Ta approximately 1300 C and log(fO2) = IW-1.8, followed by approximtely 60 wt% crystallization of the partial melt formed, and removal of the still-liquid portion of the partial melt. Removal of the last partial melt resulted in depletion of the Divnoe plagioclase in Na and K. In this scenario, CGL represents the residue of partial melting, and PP is a portion of the partial melt that crystallized in situ. The ORL was formed during the final stages of partial melting by reaction between gaseous sulfur and residual olivine in the source region. A prominent feature of Divnoe is fine micron-scale chemical variations within olivine grains, related to lamellar structures the olivines display. The origin of these structures is not known.

Petaev, M. I.↗

High Temperature Fatigue Crack Growth Behavior of Alloy 10

Methods to improve the high temperature, dwell crack growth resistance of Alloy 10, a high strength, nickel-base disk alloy, were studied. Two approaches, heat treat variations and composition modifications, were investigated. Under the heat treat approach, solution temperature, cooling rates, and stabilization, were studied. It was found that higher solution temperatures, which promote coarser grain sizes, coupled with a 1550 F stabilization treatment were found to significantly reduce dwell crack growth rates at 1300 F Changes in the niobium and tantalum content were found to have a much smaller impact on crack growth behavior. Lowering the niobium:tantalum ratio did improve crack growth resistance and this effect was most pronounced for coarse grain microstructures. Based on these findings, a coarse grain microstructure for Alloy 10 appears to be the best option for improving dwell crack growth resistance, especially in the rim of a disk where temperatures can reach or exceed 1300 T. Further, the use of advanced processing technologies, which can produce a coarse grain rim and fine grain bore, would be the preferred option for Alloy 10 to obtain the optimal balance between tensile, creep, and crack growth requirements for small gas turbine engines.

Gayda, John↗

A study of fatigue damage mechanisms in Waspaloy from 25 to 800 C

The objective of the study was to examine the effect of various microstructures on the fatigue and damage accumulation behavior of Waspaloy, a nickel-base alloy commonly used in aircraft engines. Shearing was the dominant deformation mode in specimens with coarse grains and small (50-80 A) gamma prime particles, whereas Orowan looping was dominant in fine-grained specimens with large (about 900 A) gamma prime particles. At temperatures up to 500 C, cracks initiated transgranularly, while at 800 C the failure process was intergranular for both coarse-grained and fine-grained specimens. At temperatures above 500 C, a significant decrease in the fatigue life was observed for both coarse-grained and fine-grained material.

Lerch, B. A.↗

Alteration and formation of rims on the CM parent body

All types of coarse-grained components in CM chondrites are surrounded by fine-grained dust coatings, but the origin of these rims is not yet clear. Although a strictly nebular origin seems likely for rims in the relatively unaltered type 3 chondrites, the rims in CM chondrites are dominated by secondary alteration phases. It has been argued that either the coarse-grained cores accreted altered rim materials while still in the nebula or that alteration of primary rim phases occurred on the CM parent body. To constrain the origin of alteration phases in rim material, we have analyzed the textures and mineral associations from 10 CM chondritic falls by optical and scanning electron microscopy. Our results indicate that the secondary phases in CM chondritic rims were produced by parent body fluid-rock interactions which redefined some primary rim textures and may have produced, in some cases, both coarse-grained components and the rims that surround them. Textural features demonstrate the interactive exchange of alteration fluids between rims, matrix, and chondrules on the CM parent body. For example, most matrix-rim contacts are gradational, suggesting the synchronous alteration of both components. Several observations suggest the possibility of in situ rim production. For example, tochilinite and phyllosilicates commonly form rims around matrix carbonates, which are generally believed to have precipitated from alteration fluids on the CM parent body. This suggests that the rims surrounding matrix carbonates may also have been produced by alteration processes. Partially replaced chondrule olivines bear a striking resemblance to many rimmed olivines in the matrix which suggests, by analogy, that site-specific precipitation of S-bearing phases may also be responsible for the occurrence of many tochilinite-rich rims around isolated matrix olivines. Non-silicate rims precipitate around olivines of any composition, but the process is most effective for fayalitic olivines. Most of the remaining olivines in CM chondrites are relatively Mg-rich, which suggests that the precipitation of S-bearing rims on olivines may not have been an important process in the aqueous alteration of CM chondrites. We conclude that: (1) precursor rim materials in CM chondrites were subjected to pervasive aqueous alteration on the CM parent body; and (2) textures and mineral associations observed in CM chondrites also suggest the possibility of in situ rim production.

Browning, Lauren B.↗

Superalloy Disk With Dual-Grain Structure Spin Tested

Advanced nickel-base disk alloys for future gas turbine engines will require greater temperature capability than current alloys, but they must also continue to deliver safe, reliable operation. An advanced, nickel-base disk alloy, designated Alloy 10, was selected for evaluation in NASA s Ultra Safe Propulsion Project. Early studies on small test specimens showed that heat treatments that produced a fine grain microstructure promoted high strength and long fatigue life in the bore of a disk, whereas heat treatments that produced a coarse grain microstructure promoted optimal creep and crack growth resistance in the rim of a disk. On the basis of these results, the optimal combination of performance and safety might be achieved by utilizing a heat-treatment technology that could produce a fine grain bore and coarse grain rim in a nickel-base disk. Alloy 10 disks that were given a dual microstructure heat treatment (DMHT) were obtained from NASA s Ultra-Efficient Engine Technology (UEET) Program for preliminary evaluation. Data on small test specimens machined from a DMHT disk were encouraging. However, the benefit of the dual grain structure on the performance and reliability of the entire disk still needed to be demonstrated. For this reason, a high temperature spin test of a DMHT disk was run at 20 000 rpm and 1500 F at the Balancing Company of Dayton, Ohio, under the direction of NASA Glenn Research Center personnel. The results of that test showed that the DMHT disk exhibited significantly lower crack growth than a disk with a fine grain microstructure. In addition, the results of these tests could be accurately predicted using a two-dimensional, axisymmetric finite element analysis of the DMHT disk. Although the first spin test demonstrated a significant performance advantage associated with the DMHT technology, a second spin test on the DMHT disk was run to determine burst margin. The disk burst in the web at a very high speed, over 39 000 rpm, in line with the predicted location and speed. Furthermore, significant growth of the disk was observed before failure, in line with predictions, clearly demonstrating the reliability and safety of the DMHT technology. Although successful spin testing in Ultra Safe's Nickel Disk Program represents a significant milestone for DMHT technology, realistic engine operation will require repeated loading of a DMHT nickel disk. For this reason, a cyclic spin test study of DMHT nickel disk technology has been proposed to start in fiscal year 2003 under NASA's Aviation Safety Program. The goal of this program will be to determine the fatigue failure mechanism in DMHT nickel disks, thereby demonstrating the reliability and safety of DMHT technology under repetitive loading conditions encountered in realistic engine operation.

Gayda, John↗

The chaotic solar nebula - Evidence for episodic condensation in several distinct zones

Abundances of rare earth elements in Allende inclusions are considered along with the rim sequence on coarse-grained chondrules. It is found that in at least several zones the nebula went through episodes of condensation and gas/grain separation. Four separate zones are required to make the two types of fine-grained aggregates and the two types of coarse-grained chondrules. Other types of inclusions in Allende, such as the olivine aggregates, may well require additional condensation zones. All of these conclusions are based on data from one meteorite. Although the details of the gas/grain separation mechanism in these zones is not well understood, it is clear that a single monotonic-cooling condensation sequence followed by isolation of grains from gas cannot account for the observations.

Boynton, W. V.↗

Ar-39/Ar-40 systematics of Allende inclusions

A laser microprobe was used to measure the Ar isotopic contents of individual mineral grains in four neutron-irradiated Allende samples: two coarse-grained Ca-Al-rich inclusions; one fine-grained Ca-Al-rich inclusion; and one sample with matrix and miscellaneous chondrules. The following K-Ar ages (G.y.) were obtained after degassing low Ar retentive sites by preheating the samples for one hour at 675 C: matrix, 3.5 + or - 0.2; three miscellaneous chondrules, 4.4 + or - 0.1, 4.0 + or - 0.1, and 4.4 + or - 0.1; and the fine-grained inclusion, 4.5 + or - 0.2. The minerals in the coarse-grained Ca-Al-rich inclusions have ubiquitous chlorine, less than 10 ppm K and apparent ages ranging upwards from 4.6 G.y. to well over 10 G.y. Possible explanations for these apparent ages are atmospheric contamination, the decay of K-40 prior to the formation of the solar system, and the trapping of radiogenic Ar-40 lost by the matrix.

Herzog, G. F.↗

In-Situ Geochronology as a Mission-Enabling Technology

Although there are excellent estimates of ages of terrains on Mars from crater counting, even a few absolute ages would serve to validate the calibration. Results with uncertainties, although much larger than those that could be achieved in labs on Earth, would be extremely valuable. While there are other possibilities for in-situ geochronology instruments, we describe here to alternative technologies, being developed in JPL. There are two common features of both. The first is analysis by means of miniature mass spectrometer. The second is use of laser sampling to reduce or avoid sample handling, preparation and pre-treatment and equally importantly, to allow analysis of individual, textually resolved minerals in coarse-grained rocks. This textural resolved minerals in coarse-grained rocks. This textural resolution will aid in selection of grains more or less enriched in the relevant elements and allow construction of isochrons for more precise dating. Either of these instruments could enable missions to Mars and other planetary bodies.

geochronology↗

Understanding the Influence of Chain Architecture on the Transport Quantities of Polymer Electrolytes with Covalently Bonded Anions

Here, we use a combination of experiments and coarse-grained molecular dynamics simulations to elucidate the structure–property relationships in polymer electrolytes obtained by the copolymerization of poly(vinyl ethylene carbonate─lithium styrene bis(trifluoromethanesulfonyl)imide) or p(VEC-LiSTFSI). Experiments show that the conductivity reduces with increasing anion (i.e., STFSI) fraction on the chain, and the cation transference number (t + ) is found to be dependent on the anion fraction. Furthermore, a significant fraction of unpolymerized VEC monomers are observed. Since it is inherently difficult to experimentally control the chain architecture and the amount of unpolymerized VEC in these systems, we perform coarse-grained molecular dynamics simulations on model polymer systems with different chain architectures to mimic the plausible experimental systems. Specifically, we look at the differences in transference numbers arising from (i) a random copolymer of VEC and STFSI monomers; (ii) a blend of VEC-STFSI copolymer with VEC monomers; and (iii) a ternary blend of the VEC homopolymer, STFSI homopolymers, and VEC monomers. The ternary blend model demonstrates the closest resemblance with the experimental transference numbers and diffusivities. The lithium diffusivity obtained from the coarse-grained models with VEC monomers (plasticizers) is about 1.5 times that of the model without VEC monomers, showing that the plasticizing effect of VEC monomers is modest. We rationalize the experimental observations based on aggregate and cluster analyses obtained from molecular simulations. This work reveals that polymer electrolyte chain architecture and plasticizers can critically influence the transport properties, and these parameters should be considered when designing single ion conducting polymeric electrolytes.

cluster distribution↗

Grain size and the evolution of Luna 24 soils

The grain size distribution of six Luna 24 samples has been determined. These samples are characterized by a bimodal distribution which is indicative of soils formed primarily by mixing rather than by reworking. Although agglutinate content decreases with depth, it is not likely that the Luna 24 soils have undergone appreciable in situ reworking. Particle types and abundances in each of four size fractions have been determined petrographically. Mineral fragments are very abundant in all analyzed size fractions. Pyroxene and plagioclase increase slightly in abundance at finer grain sizes, but olivine decreases significantly. Compared with typical mare soils, the Luna 24 trends are anomalous. They are compatible with the hypothesis than many, if not most, of the mineral grains in the 20-250-micron fractions come from coarse-grain rocks having average mineral grain sizes greater than 250 microns. The mineralogy and chemistry of the coarse-grained rocks has not been well characterized, but there is evidence that at least some of them are higher in MgO than the analyzed finer-grained basalts.

Mckay, D. S.↗

VOTCA: multiscale frameworks for quantum and classical simulations in soft matter

Many physical phenomena in liquids and soft matter are multiscale by nature and can involve processes with quantum and classical degrees of freedom occurring over a vast range of length- and timescales. Examples range from structure formation processes of complex polymers or even polymer blends (Svaneborg & Everaers, 2023) on the classical side to charge and energy transport and conversion processes (Lee et al., 2019) involving explicit electronic and, therefore, quantum information. The Versatile Object-oriented Toolkit for Coarse-graining Applications (VOTCA) provides multiscale frameworks built on a comprehensive set of methods for the development of classical coarse-grained potentials (VOTCA-CSG) as well as state-of-the art excited state electronic structure methods based on density-functional and many-body Green’s function theories, coupled in mixed quantum-classical models and used in kinetic network models (VOTCA-XTP).

97 MATHEMATICS AND COMPUTING↗

The Pasamonte unequilibrated eucrite: Pyroxene REE systematic and major-, minor-, and trace-element zoning

We are evaluating the trace-element concentrations in the pyroxenes of Pasamonte. Pasamonte is a characteristic member of the main group eucrites, and has recently been redescribed as a polymict eucrite. Our Pasamonte sample contained eucritic clasts with textures ranging from subophitic to moderately coarse-grained. This study concentrates on pyroxenes from an unequilibrated, coarse-grained eucrite clast. Major-, minor-, and trace-element analyses were measured for zoned pyroxenes in the eucritic clast of Pasamonte. The major- and minor-element zoning traverses were measured using the JEOL 733 electron probe with an Oxford-Link imaging/analysis system. Complemenatry trace elements were then measured for the core and rim of each of the grains by SIMS. The trace elements analyzed consisted of eight REE, Sr, Y, and Zr. These analyses were performed on a Cameca 4f ion probe. The results of the CI chondrite normalized (average CI trace-element analyses for several grains and the major- and minor-element zoning patterns from a single pyroxene grain are given. The Eu abundance in the cores of the pyroxenes represents the detection limit and therefore the (-Eu) anomaly is a minimum. Major- and minor-element patterns are typical for igneous zoning. Pyroxene cores are Mg enriched, whereas the rims are enriched in Fe and Ca. Also, Ti and Mn are found to increase, while Cr and Al generally decrease in core-to-rim traverses. The cores of the pyroxenes are more depleted in the Rare Earth Elements (REE) than the rims. Using the minor- and trace-element concentrations of bulk Pasamonte and the minor- and trace-element concentrations from the cores of the pyroxenes in Pasamonte measured in this study, we calculated partition coefficients between pyroxene and melt. This calculation assumes that bulk Pasamonte is representative of a melt composition.

Pun, A.↗

Asia from Space: New Ideas for Exploration

Megafans, also known (incorrectly) as inland deltas, are partial cones of fluvial sediment with radii >~100 km. Each is generated by a formative river avulsing across a lowland. The alluvial tract (channel, levee, overbank, etc.) is the building block for megafans. Planform and sectional analyses, based on SRTM data, reveal their conical, low-angle morphology. Megafans are not geologically rare as often assumed but a normal feature in the hierarchy of fluvial features that is slowly beginning to be understood. Our global survey contains a total of >150 examples worldwide, in all tectonic basin types, with a majority of smaller, more easily distinguished megafans occupying classic foreland basins (54%) which may explain the general view that megafans only form in Himalaya-like foreland basins, especially since the Kosi Megafan in the Indogangetic Plain is one of the best known in the geological literature. Recent research has shown that all actively alluviating basins are occupied by fanlike sediment masses, from the well known smaller and steeper alluvial fan (level 8 in Miall s hierarchy of fluvial forms), to the much larger megafan feature (level 9). A close relationship exists between upland basin size and fan size and slope. Larger upland drainage basins give rise to low-slope megafan sedimentation, which can cover very large areas where the receptacle basin exists individual megafan areas are 10(sup 3-5) square kilometers, and collectively cover 1.2 million square kilometers in South America, for example. The habitat of megafans is now sufficiently well understood that prediction of some modern cryptic megafan locations has been successfully achieved. Underground prediction therefore seems possible, where sufficient data exists. It seems necessary to distinguish megafans from (i) steep, coarse-grained mountain-front alluvial fans which are overwhelmingly coarse-grained, (ii) deltas, since megafans lack distal shoreline processes), and (iii) confined floodplains which lack radial drainage. Numerous other differences can be identified. As a normal component of the modern fluvial environment, megafans must exist in the subsurface. Megafan size, predictable channel patterns of the formative river, and the gradation from coarser to finer sediments from apex to toe of megafans are characteristics that ought to assist in understanding subsurface patterns of hydrocarbon host rocks, and possibly source rocks as well. We show examples from various producing basins. A roughness map of Asia, based on an algorithm developed for Mars, shows megafan landscapes to be dominated by short baseline roughness and low slopes, consistent with megafan-dominated plains worldwide. Interestingly, this a unique signature for a larger continental landform.

Wilkinson, M. Justin↗