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144 records · Page 8

Over What Length Scale Does an Inorganic Substrate Perturb the Structure of a Glassy Organic Semiconductor?

While the bulk structure of vapor-deposited glasses has been extensively studied, structure at buried interfaces has received little attention, despite being important for organic electronic applications. To learn about glass structure at buried interfaces, we study the structure of vapor-deposited glasses of the organic semiconductor DSA-Ph (1,4-di-[4-(N,N-diphenyl)amino]styrylbenzene) as a function of film thickness; the structure is probed with grazing incidence X-ray scattering. Here, we deposit on silicon and gold substrates and span a film thickness range of 10–600 nm. Our experiments demonstrate that interfacial molecular packing in vapor-deposited glasses of DSA-Ph is more disordered compared to the bulk. At a deposition temperature near room temperature, we estimate ~8 nm near the substrate can have modified molecular packing. Molecular dynamics simulations of a coarse-grained representation of DSA-Ph reveal a similar length scale. In both the simulations and the experiments, deposition temperature controls glass structure beyond this interfacial layer of a few nanometers.

36 MATERIALS SCIENCE↗

Development of test methodology for dynamic mechanical analysis instrumentation

Dynamic mechanical analysis instrumentation was used for the development of specific test methodology in the determination of engineering parameters of selected materials, esp. plastics and elastomers, over a broad range of temperature with selected environment. The methodology for routine procedures was established with specific attention given to sample geometry, sample size, and mounting techniques. The basic software of the duPont 1090 thermal analyzer was used for data reduction which simplify the theoretical interpretation. Clamps were developed which allowed 'relative' damping during the cure cycle to be measured for the fiber-glass supported resin. The correlation of fracture energy 'toughness' (or impact strength) with the low temperature (glassy) relaxation responses for a 'rubber-modified' epoxy system was negative in result because the low-temperature dispersion mode (-80 C) of the modifier coincided with that of the epoxy matrix, making quantitative comparison unrealistic.

Allen, V. R.↗

Theory-Guided Inelastic Neutron Scattering of Crystalline Alkaline Aluminate Salts Bearing Principal Motifs of Solution-State Species

Aluminate salts precipitated from caustic alkaline solutions exhibit a correlation between the anionic speciation and the identity of the alkali cation in the precipitate, with the aluminate ions occurring either in monomeric (Al(OH) 4 – ) or dimeric (Al 2 O(OH) 6 2– ) forms. The origin of this correlation is poorly understood as are the roles that oligomeric aluminate species play in determining the solution structure, prenucleation clusters, and precipitation pathways. Characterization of aluminate solution speciation with vibrational spectroscopy results in spectra that are difficult to interpret because the ions access a diverse and dynamic configurational space. To investigate the Al(OH) 4 – and Al 2 O(OH) 6 2– anions within a well-defined crystal lattice, inelastic neutron scattering (INS) and Raman spectroscopic data were collected and simulated by density functional theory for K 2 [Al 2 O(OH) 6 ], Rb 2 [Al 2 O(OH) 6 ], and Cs[Al(OH) 4 ]·2H 2 O. These structures capture archetypal solution aluminate species: the first two salts contain dimeric Al 2 O(OH) 6 2– anions, while the third contains the monomeric Al(OH) 4 – anion. Here, comparisons were made to the INS and Raman spectra of sodium aluminate solutions frozen in a glassy state. In contrast to solution systems, the crystal lattice of the salts results in well-defined vibrations and associated resolved bands in the INS spectra. The use of a theory-guided analysis of the INS of this solid alkaline aluminate series revealed that differences were related to the nature of the hydrogen-bonding network and showed that INS is a sensitive probe of the degree of completeness and strength of the bond network in hydrogen-bonded materials. Results suggest that the ionic size may explain cation-specific differences in crystallization pathways in alkaline aluminate salts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of Common Thermoplastic Polymers in High-Pressure Cycling Hydrogen Under Ambient and Cold Environments as Applicable to the Hydrogen Infrastructure

Thermoplastic polymers are required to perform unfailingly under stringent conditions of changing pressures (35 MPa to 70 MPa) and temperatures (-40°C to +85°C) in storage and fueling operations. Although diffusivity in glassy polymers appear to be an order of magnitude lower than elastomers, polymer microstructural attributes such as degree of crystallinity and presence of polar and non-polar groups on the main chain with and without branching can play a substantial role in influencing their behaviors in hydrogen environments. In the work described here, the effect of high-pressure hydrogen cycling on PEEK, PTFE, PA11, HDPE, POM (and different commercial grades of these polymers) under ambient and cold (-40°C) conditions is addressed. Ex-situ characterization for polymer changes included density measurements for impact of hydrogen retention, hardness changes using nanoindentation, storage modulus and glass transition changes using dynamic mechanical and thermal analysis (DMTA), degree of crystallization with Differential Scanning Calorimetry (DSC) and tensile testing following ASTM D412. In other evaluations, solid-state nuclear magnetic resonance (NMR), attenuated total reflectance Fourier transform infra-red spectroscopy (ATRFTIR), X-ray diffraction (XRD), and X-ray CT results are presented. The overall impact of these evaluations is to establish a technical basis for the behaviors of common thermoplastics in cycling hydrogen environments under ambient and cold temperatures while establishing the relationship between polymer structure-based properties and hydrogen transport effects.

Menon, Nalini C.↗

Computational investigation of water glasses using machine-learning potentials

The molecular origins of water’s anomalous properties have long been a subject of scientific inquiry. The liquid–liquid phase transition hypothesis, which posits the existence of distinct low-density and high-density liquid states separated by a first-order phase transition terminating at a critical point, has gained increasing experimental and computational support and offers a thermodynamically consistent framework for many of water’s anomalies. However, experimental challenges in avoiding crystallization near the postulated liquid–liquid critical point have focused attention to water’s canonical glassy states: low-density and high-density amorphous ice. Here, we use two Deep Potential machine-learning models, trained on the Strongly Constrained and Appropriately Normed density functional and the highly accurate Many-Body Polarizable potential, to conduct an investigation of water’s glassy phenomenology based on quantum mechanical calculations. Despite not being explicitly trained on amorphous ices, both models accurately capture the structure and transformation of the water glasses, including their interconversion along different thermodynamic paths. Isobaric quenching of liquid water at various pressures generates a continuum of intermediate amorphous ices and density fluctuations increase near the liquid–liquid critical pressure. The glass transition temperatures of the amorphous ices produced at different pressures exhibit two distinct branches, corresponding to low-density and high-density amorphous ice behaviors, consistent with experiment and the liquid–liquid transition hypothesis. Extrapolating transformation pressures from isothermal compressions to experimental compression rates brings our simulations into excellent agreement with data. Our findings demonstrate that machine-learning potentials trained on equilibrium phases can effectively model nonequilibrium glassy behavior and pave the way for studying long-timescale, out-of-equilibrium processes with quantum mechanical accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Liquid and Glass Phases of an Alkylguanidinium Sulfonate Hydrogen-Bonded Organic Framework

Glassy phases of framework materials feature unique and tunable properties that are advantageous for gas separation membranes, solid electrolytes, and phase-change memory applications. However, the structural and chemical diversity of porous frameworks that can be liquified and quenched into a glass has been limited by thermal decomposition at-or below-the high temperatures required to induce a melting transition. Utilizing a desymmetrization strategy, in this work we report a new guanidinium organosulfonate hydrogen-bonded organic framework (HOF) that melts and vitrifies below 100 °C. In this low-temperature regime, non-covalent interactions between guest molecules and the porous framework become a dominant contributor to the overall stability of the structure, resulting in unusual phase behavior such as guest dependent melting, glass, and recrystallization transitions. Through molecular dynamics simulations and pair distribution function analysis, we show that the local structure of the amorphous liquid and glass phase resembles that of the parent crystalline framework. Access to molten phases of framework materials at moderate temperatures should permit the use of more thermally sensitive functional groups and enhance the structural control and tunability that can be realized in network-forming glasses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Experimental Investigation of Low Cost, Low Thermal Conductivity Thermal Barrier Coating on HCCI Combustion, Efficiency, and Emissions

In-cylinder surface temperature is of heightened importance for Homogeneous Charge Compression Ignition (HCCI) combustion since the combustion mechanism is thermo-kinetically driven. Thermal Barrier Coatings (TBCs) selectively manipulate the in-cylinder surface temperature, providing an avenue for improving thermal and combustion efficiency. A surface temperature swing during combustion/expansion reduces heat transfer losses, leading to more complete combustion and reduced emissions. At the same time, achieving a highly dynamic response sidesteps preheating of charge during intake and eliminates the volumetric efficiency penalty. The magnitude and temporal profile of the dynamic surface temperature swing is affected by the TBC material properties, thickness, morphology, engine speed, and heat flux from the combustion process. This study follows prior work of authors with Yttria Stabilized Zirconia, which systematically engineered coatings for HCCI combustion. Herein, a modeling study was used to assess the impacts of various TBC material properties, e.g. density, thickness, and thermal conductivity on the temperature swing effect. Reducing conductivity emerged as a most promising avenue, rather than reducing both the density and effective conductivity by increasing porosity, the current work emphasizes a material with natively low conductivity. A novel TBC formulation was developed, leverages a class of materials that, to the author’s best knowledge, have not been used as a thermal barrier coating previously. Here, a systematic experimental investigation was carried out using single-cylinder research engine. Experimental engine studies utilizing the novel ‘glassy’ low-K coating exhibit advanced ignition phasing and reduced combustion duration relative to the baseline engine. Heat transfer measurements indicate a net reduction in heat flux over the entire cycle, although main effect is felt during expansion, and the reduced heat transfer losses manifest in higher gross indicated thermal efficiency by approximately 5-6% on a relative basis.

42 ENGINEERING↗

Calcium silicate hydrate colloid at different humidities: Microstructure, deformation mechanism, and mechanical properties

Calcium silicate hydrate (C-S-H) is the main hydration product of Portland cement, while fundamental questions persist regarding its colloidal structure and water content. In this work, we developed a full atomistic C-S-H colloid model and investigated the physical and mechanical properties at different gel water concentrations. Water confined in nanometer gel pores degrades the mechanical properties of C-S-H because of its hydrolysis effect. A “ductile to brittle” transition was observed in the C-S-H colloid model with increasing gel water contents, evolving from transgranular failure to intergranular fracture. The gel water confined in nanometer-sized pores displays glassy characteristics, and it acts as a lubricant and facilitates structure distortions during the deformation. We elucidated the topology effect of the hydrogen bond network on the evolution of the viscoelasticity of C-S-H at different humidities. In conclusion, this work sheds light on the role of water in C-S-H colloids from nanostructure perspectives.

36 MATERIALS SCIENCE↗

Medium-Range Ordering in the Ionic Glass Electrolytes LiPON and LiSiPON

In this work, we provide an in-depth structural characterization of the amorphous ionic glasses LiPON and LiSiPON with high Li content. Based on ab initio molecular dynamics simulations, the structure of these materials is an inverted structure with either isolated polyanion tetrahedra or polyanion dimers in a Li+ matrix. Based on neutron scattering data, this type of inverted structure leads to a significant amount of medium-range ordering in the structure, as demonstrated by two sharp diffraction peaks and a periodic structural oscillation in the density function G(r). While this medium-range ordering is commonly observed in liquids and metallic glasses, it has not previously been observed in oxides. On a local scale, adding N and Si increases the number of anion bridges and polyanion dimer structures, leading to higher ionic conductivity. In the medium-range ordering, the addition of Si leads to more disorder in the polyanion substructure but a significant increase in the ordering of the O substructure. Finally, we demonstrate that this inverted structure with medium-range ordering results in a glassy material that is both mechanically stiff and ductile on the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational and Experimental Study of Li-doped Ionic Liquids at Electrified Interfaces

We evaluate the influence of Li-salt doping on the dynamics, capacitance, and structure of three ionic liquid electrolytes, [pyr14][TFSI], [pyr13][FSI], and [EMIM][BF4], using molecular dynamics and polarizable force fields. In this respect, our focus is on the properties of the electric double layer (EDL) formed by the electrolytes at the electrode surface as a function of surface potential (Psi). The rates of EDL formation are found to be on the order of hundreds of picoseconds and only slightly influenced by the addition of Li-salt. The EDLs of three electrolytes are shown to have different energy storage capacities, which we relate to the EDL formation free energy. The differential capacitance obtained from our computations exhibits asymmetry about the potential of zero charge and is consistent with the camel-like profiles noted from mean field theories and experiments on metallic electrodes. The introduction of Li-salt reduces the noted asymmetry in the differential capacitance profile. Complementary experimental capacitance measurements have been made on our three electrolytes in their neat forms and with Li-salt. The measurements, performed on glassy carbon electrodes, produce U-like profiles, and Li-salt doping is shown to strongly affect capacitance at high magnitudes of Psi. Differences in the theoretical and experimental shapes and magnitudes of capacitance are rationalized in terms of the electrode surface and pseudocapacitive effects. In both neat and Li-doped liquids, the details of the computational capacitance profile are well described by Psi-induced changes in the density and molecular orientation of ions in the molecular layer closest to the electrode. Our results suggest that the addition of Li+ induces disorder in the EDL, which originates from the strong binding of anions to Li+. An in-depth analysis of the distribution of Li+ in the EDL reveals that it does not readily enter the molecular layer at the electrode surface, preferring instead to be localized farther away from the surface in the second molecular layer. This behavior is validated through an analysis of the free energy of Li+ solvation as a function of distance from the electrode. Free energy wells are found to coincide with localized concentrations of Li+, the depths of which increase with Psi and suggest a source of impedance for Li+ to reach the electrode.

Haskins, Justin B.↗

Predicting Char Yield of High-Temperature Resins

A simulation technique has been developed for predicting the char yield of organic resins during high-temperature processing. In silico methods can aid in the screening of new advanced materials for a number of important properties, but no chemistry-sensitive protocol currently exists for predicting the important experimental value of char yield. The proposed method utilizes a reactive force field (ReaxFF) to model the chemical transformation of precursor monomers into carbonized structures during three processing stages: ramp-up to pyrolysis temperatures (~3000 K), pyrolysis, and quenching. Achieving good agreement with experimental char yields requires continuous removal of small by-product molecules to mimic outgassing, and the application of high pressure to encourage the formation of a dense, glassy network. Six different resin chemistries were investigated: an ethynyl, a phenylethynyl, a cyanate ester, a phthalonitrile, acrylonitrile, and adamantane. These candidates represent a diverse group of precursors with respect to initial cyclic content, presence of heteroatoms, and types of reactive groups. The protocol developed accurately predicts the relative char yield between the investigated chemistries and provides quantitative agreement with experimental values, especially for high char yield resins. Several simulated properties of the carbonized structures are compared with experimental results, including outgassing products, morphology of the final chemical configurations, cyclic content, and mechanical properties.

polymer simulations, molecular dynamics↗

Structure and properties of densified silica glass: characterizing the order within disorder

The broken symmetry in the atomic-scale ordering of glassy versus crystalline solids leads to a daunting challenge to provide suitable metrics for describing the order within disorder, especially on length scales beyond the nearest neighbor that are characterized by rich structural complexity. Here, we address this challenge for silica, a canonical network-forming glass, by using hot versus cold compression to (i) systematically increase the structural ordering after densification and (ii) prepare two glasses with the same high-density but contrasting structures. The structure was measured by high-energy X-ray and neutron diffraction, and atomistic models were generated that reproduce the experimental results. The vibrational and thermodynamic properties of the glasses were probed by using inelastic neutron scattering and calorimetry, respectively. Traditional measures of amorphous structures show relatively subtle changes upon compacting the glass. The method of persistent homology identifies, however, distinct features in the network topology that change as the initially open structure of the glass is collapsed. The results for the same high-density glasses show that the nature of structural disorder does impact the heat capacity and boson peak in the low-frequency dynamical spectra. Densification is discussed in terms of the loss of locally favored tetrahedral structures comprising oxygen-decorated SiSi 4<:sub> tetrahedra.

36 MATERIALS SCIENCE↗

Exploring sodium dynamics in the dilute oxygen regime of mixed oxy-sulfide NaPSiSO glasses

All-solid-state‑sodium batteries have great potential to lower the cost of grid-scale energy storage systems. However, they require a low cost, high conductivity solid electrolyte to become a reality. The electrochemical properties of mixed oxy-sulfide glasses NaPSiSO exceed those of either the pure sulfide or the pure oxide glass alone. In this work, we have tested models of sodium ion dynamics in the NaPSiSO series: zNa 2 S+(1-z)[(1-y)[(1-x)SiS 2 + xPS 5/2 ] + yNaPO 3 ] where 0.57 ≤ z ≤ 0.588, 0 ≤ x ≤ 0.35, and 0.15 ≤ y ≤ 0.35 using 23 Na nuclear magnetic resonance to directly probe the local fields and their fluctuations at the nuclear sites. We determined the distribution of activation energies in these materials arising from distributions of local environments and provided quantitative information about the connectivity of the ionic pathways through which the sodium ions move. We found that the sodium ion conduction dynamics were described as an ionic percolation through a Gaussian distribution of energy barriers and that the composition dependence of the ionic conductivity in the dilute oxygen regime is well-described by the Nernst-Einstein relation modified for percolation.

25 ENERGY STORAGE↗

Noble Gases in Samples Returned From Asteroids Ryugu and Bennu

Introduction: The asteroid sample return missions, JAXA’s Hayabusa2 [1] and NASA’s OSIRIS-REx [2], fromC-rich asteroids Ryugu and Bennu offer unique opportunities to sample pristine early solar system material, unaffected by terrestrial weathering and contamination, and with a known geological context. The comparison with most primi-tive members of carbonaceous –and inner solar system ordinary and enstatite– chondrite classes allows us to (i) assess the variation (or the lack of thereof) of the distribution of the most volatile elements throughout the entire early solar system, (ii) determine the effects of parent body thermal and aqueous alteration, and (iii) learn about the dynamic evolution and history of the various parent bodies, as sampled by both return missions and meteorite delivery. Here we will present noble gas data obtained from newly received particles from Ryugu and Bennu. Samples & Analysis: We received nine particles allocated by JAXA, with masses of 0.5-1.7 mg mass: four col-lected during Hayabusa2’s first touchdown (chamber A) and five from a small artificial crater (chamber C). We received three particles from Bennu of 0.07, 0.89 and 0.94 mg mass (OREX-800032-102/3/4). All particles were processed, allocated, weighed, and transferred into our UHV sample chamber within pure N2, to prevent any contact with air. We examined all He-Xe isotopes with our custom-built mass spectrometer “Albatros” ([3,4]). Gases were extracted individually from each particle by melting induced by a 1064 μm Nd:YAG IR laser in 2–4 heating steps. Large amounts of water and other reactive volatiles were released, consistent with the presence of abundant volatiles from both Ryugu and Bennu. Residues of Ryugu particles remaining after lasering, subsequently exposed to air, were additionally extracted in a crucible to verify complete gas extraction. Only the particle that still showed a “crystalline” structure after lasering contained detectable Ryugu noble gases, whereas all other particles turned immediately into glassy spheres by laser heating and lacked any gas. Results & Discussion: Ryugu and Bennu matter contains noble gases similar to the most pristine, unheated aqueously altered meteorites, e.g., CM or CI chondrites [5,6]. Remarkably, all four chamber A samples that originated from Ryugu’s surface show solar wind (SW) Ne (trapped (20Ne/22Ne)tr ~12–13), whereas all five chamber C samples do not ((20Ne/22Ne)tr ~9.0–10.7 consistent with the presence of non-solar trapped Ne components such as Q and HL). This demonstrates that JAXA’s sampling strategy succeeded: Chamber C samples analyzed in this work originated from areas shielded from SW, slightly below the surface, that was sampled after the impactor excavated material. The three Bennu particles populate the same range as the Ryugu particles in Ne isotope space with one particle containing SW suggesting that it was part of the uppermost surface layer of Bennu during sampling, while Ne in the smallest sample can be explained best by mixing Ne from presolar diamonds and SiC or graphite, and that in the third one by mixing of, e.g., Q and HL. Using cosmic ray production rates given by [7] yields preliminary exposure ages for Ryugu particles in the same range as determined in [7]. There is, as expected, also no systematic difference between samples from chambers A and C because both sample sets were likely collected within the uppermost layer of Ryugu, which were not shielded from cosmic rays. The concentration of cosmogenic (cos) Ne in the Bennu particle, where Necos was resolvable, is in the same range as found for Ryugu, suggesting roughly similar exposure time to cosmic rays for 5–8 Ma for all particles examined here. The Xe isotopic compositions of all particles are consistent with those of phase Q, with small additions of Xe-HL from presolar diamonds and excess 129Xe* from short-lived 129I decay. The comparably high 129Xe*/129XeQ ratio is similar in all samples, suggesting similar initial I concentrations and closure to Xe loss –or the incorporation of a well-mixed Xe reservoir. The Bennu material was in brief contact with air in the capsule, after atmospheric entry and before storage in pure N2 in a clean room. Both, the –most diagnostic– Xe isotopes and the Ar/Xe vs. Kr/Xe systematics prove that the noble gases are not affected by terrestrial contamination, in contrast to many CI, CY, and CM chondrites found on Earth [5,6], illustrating the importance of sample return. He-Xe concentrations in all particles unaffected bySW are comparable to but at the upper end of ranges reported [5-7]. In accordance with the strong aqueous alteration experienced on the parent bodies of Ryugu and Bennu [1,2], all samples lack the Ar-rich and water-susceptible noble gas components found in less aqueously altered CMs or CRs [e.g., 5,8] and all COs.

Henner Busemann↗

Short- and medium-range orders in Al90Tb10 glass and their relation to the structures of competing crystalline phases

Molecular dynamics simulations using an interatomic potential developed by artificial neural network deep machine learning are performed to study the local structural order in Al90Tb10 metallic glass. We show that more than 80% of the Tb-centered clusters in Al90Tb10 glass have short-range order (SRO) with their 17 first coordination shell atoms stacked in a ‘3661’ or ‘15551’ sequence. Medium-range order (MRO) in Bergman-type packing extended out to the second and third coordination shells is also clearly observed. Analysis of the network formed by the ‘3661’ and ‘15551’ clusters show that ~82% of such SRO units share their faces or vertexes, while only ~6% of neighboring SRO pairs are interpenetrating. Such a network topology is consistent with the Bergman-type MRO around the Tb-centers. Moreover, crystal structure searches using genetic algorithm and the neural network interatomic potential reveal several low-energy metastable crystalline structures in the composition range close to Al 90 Tb 10 . Some of these crystalline structures have the ‘3661’ SRO while others have the ‘15551’ SRO. While the crystalline structures with the ‘3661’ SRO also exhibit the MRO very similar to that observed in the glass, the ones with the ‘15551’ SRO have very different atomic packing in the second and third shells around the Tb centers from that of the Bergman-type MRO observed in the glassy phase.

36 MATERIALS SCIENCE↗

Apollo Sample 64455: Petrologic and Geochemical Characterization of a Glass-Coated Impact Melt Rock

Introduction and Background: Impact melts are a key product of the impact cratering process. Impact melts can turbulently entrain pre-existing rock fragments, and melt part of those entrained materials until thermal equilibrium is achieved [1–3]. Lunar impact melt rocks are valuable for determining the precise ages of basin-forming and cratering events, which anchor the cratering chronology and dynamics of the entire solar system [4, and references therein]. Additionally, entrained clasts can inform on the petrology and age of crustal materials that predate the melt-forming impact. In lithologies where no pristine samples are available, entrained materials may hold the record of endogenous lunar volatiles, provided we can untangle their impact histories as high temperature impact melt can heat the clasts and may alter their native volatiles or isotopic signatures [5–6]. Here, we characterize an Apollo 16 sample, 64455,70B, in an effort to understand the physical, microstructural, and geochemical consequences of impact melt contact metamorphism. We acquired optical light and x-ray maps of the sample, as well as quantitative analyses via electron probe microanalysis (EPMA). These tasks allow us to better understand the interaction between impact melts and entrained clasts, ultimately closing knowledge gaps in high-temperature impact processing on planetary surfaces. Sample Description: Sample 64455 is an oblong crystalline rock encased in glass to form an egg-like shape [7–8]. The impact melt coating has altered the outer (1 to 2 mm) rind of the crystalline rock and has preserved schlieren. The interior crystalline rock is likely a crystalline impact melt rock based on its bulk Ir content of 2.25 parts per billion [9]. The composition of the impact melt glass rind cannot be solely derived from the crystalline interior, the glassy rind is more aluminous and less magnesian [10]. Neither the crystalline interior nor the glassy rind were radiometrically age dated, although several studies investigated its cosmogenic isotopes and exposure ages, which reveal the sample was exposed on the lunar surface for ~1–2 Ma [11–13]. Preliminary Results: The interior crystalline rock consists primarily of plagioclase with interstitial pyroxene and olivine. Plagioclase grains are zoned and compositions range from An97–89, while pyroxene compositions generally range from En68Fs19Wo13 to En82Fs15Wo3 and olivine are Fo77 to Fo85. Minor phases include Fe-Ni metal, Ca-phosphates, a K- and Si-rich phase, sulfides, and Fe-phosphides. The glass rind contains approximately 44 wt.% SiO2, 25 wt.% Al2O3, 6 wt.% FeO, 8 wt.% MgO, and 14 wt.% CaO, with other oxides at <1 wt.% each, although the composition of the glass becomes more variable closest to the crystalline rock. The rind consists of rounded plagioclase, pyroxene, and olivine crystals with interstitial melt. In some locations, the rounded crystals are surrounded by closely-packed, blade-like crystals, <5 µm in width. These results indicate that the crystalline interior has partially melted where in contact with the high-temperature impact melt and while further investigation is needed, pyroxene may have preferentially melted relative to olivine and plagioclase. Future Work: We plan to conduct electron backscatter diffraction (EBSD) mapping in order to determine crystallinity and crystal orientation. Next using transmission electron microscopy (TEM) data in conjunction with EBSD and EPMA information, we will model the diffusion of moderately volatile elements between the melt and remnant crystals.

A C Stadermann↗

Microscopic theory of onset of decaging and bond-breaking activated dynamics in ultradense fluids with strong short-range attractions

We theoretically study thermally activated “in cage” elementary dynamical processes that precede full structural relaxation in ultra-dense particle liquids interacting via strong short range attractive forces. The analysis is based on a microscopic theory formulated at the particle trajectory level built on the dynamic free energy concept and an explicit treatment of how attractive forces control the formation and lifetime of physical bonds. Mean time scales for bond breaking, the early stage of cage escape, and non-Fickian displacement by a fixed amount are analyzed in the repulsive glass, bonded repulsive (attractive) glass, fluid, and dense gel regimes. The theory predicts a strong length-scale-dependent growth of these time scales with attractive force strength at fixed packing fraction, a much weaker slowing down with density at fixed attraction strength, and a strong decoupling of the shorter bond breaking time with the other two time scales that are controlled mainly by perturbed steric caging. All results are in good accord with simulations, and additional testable predictions are made. In conclusion, the classic statistical mechanical projection approximation of replacing all bare attractive and repulsive forces with a single effective force determined by pair structure incurs major errors for describing processes associated with thermally activated escape from transiently localized states.

36 MATERIALS SCIENCE↗

Strong pinning and slow flux creep relaxation in Co-doped CaFe 2 As 2 single crystals

In this paper we report on measurements of critical current densities J c and flux creep rates S of freestanding Ca(Fe 1–x Co x ) 2 As 2 (x ≈ 0.033) single crystals with T c ≈ 15.7 K by performing magnetization measurements. The magnetic field dependences of J c at low temperature display features related to strong pinning. In addition, we find that the system displays small flux creep rates. The characteristic glassy exponent, μ, and the pinning energy, U 0 , display exceptional high values for pristine crystals. We find that for magnetic fields between 0.3 T and 1 T, μ decreases from ≈ 2.8 to ≈ 2 and U 0 remains ≈ 300 K. Analysis of the pinning force indicates that the mechanism is similar to the observed in polycrystalline systems in which grain boundaries and random disorder produce the vortex pinning. Considering the large U 0 observed in the single crystal, we attempt to improve the pinning by adding random point disorder by 3 MeV proton irradiation with a fluence of 2 × 10 16 proton/cm 2 . The results show that, unlike other iron-based superconductors, the superconducting fraction is sharply reduced by irradiation. This fact indicates that the superconductivity in the system is extremely fragile to an increment in the disorder. The superconducting volume fraction in the irradiated crystal systematically recovers after removal disorder by thermal annealing, which evidences as to the observation of critical state in curves of magnetization versus magnetic field. No features related to a reentrant antiferromagnetic transition are observed for the irradiated sample.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗