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At least 685 records · Page 38

Compositional zoning of the Otowi Member of the Bandelier Tuff, Valles caldera, New Mexico, USA

The Otowi Member of the Bandelier Tuff erupted at ca. 1.60 Ma from the Valles caldera (New Mexico, USA). It consists of as much as 400 km 3 (dense rock equivalent) of strongly differentiated high-silica rhyolite and shows systematic upward variations in crystallinity, mineral chemistry, and trace element concentrations through its thickness, but the major element composition is almost constant and is near the low-pressure granite minimum. Incompatible trace elements in whole pumice fragments and glasses show well-correlated linear covariations. Upward zoning to lower abundances of incompatible trace elements is accompanied by development of overgrowths on quartz and alkali feldspar, although earlier-formed interiors of quartz and feldspar have near-constant compositions throughout the tuff, modified by cation diffusion in the case of feldspar. Melt inclusions in remnant quartz cores show diverse Pb isotope ratios, pointing to a wide range of distinct protoliths that contributed rhyolitic melt to the Otowi magma. Mineral thermometers suggest a modest temperature gradient through the melt body, perhaps of 40 °C, at the time of eruption. Chemical, textural, and mineralogical variations and volume-composition relations through the tuff are consistent with an origin for zoning by melting of a high-crystallinity cumulate layer beneath cognate supernatant liquid to produce denser, remobilized liquid of accumulative composition (i.e., the “modified mush model”). Melting may have occurred in several episodes. The latest of these episodes, probably thousands of years prior to eruption, introduced new rhyolitic liquid into the system and was associated with a thermal excursion, recorded in core compositions of pyroxene, during which much of the earlier crystal mass was dissolved. This left inherited cores and interiors of accumulated quartz and feldspar mantled with new growth having less-evolved compositions (higher Ti, Sr, and Ba). Changing solubility of zircon during cumulate melting produced a reversal of Zr concentrations. There is no clear petrologic evidence of a recharge eruption trigger; nonetheless, compositional zoning resulted mainly from repeated recharge-induced remobilization of quartz-feldspar cumulate. The Otowi system was built, evolved, and modified by several events over the course of a few hundred thousand years.

Wolff, J. A.↗

Imaging transient solidification behavior

Solidification processing offers the first opportunity to control microstructure, properties, and performance in metallic alloy components. Until recently, microstructural evaluations were limited to post-solidification characterization by destructive methods. We review the development of time-resolved, in situimaging techniques capable of capturing solid-liquid interfacial evolution in metallic alloys with high spatial and temporal resolution underdiverse solidification conditions relevant for applications ranging from conventional directional solidification, crystal growth, and casting,to welding and additive manufacturing. These experiments enable direct visualization of transient behaviors that would otherwise remain unknown, uniquely providinginsights into the physics that impact microstructure and defect development and strategies for microstructuralcontrol and defect mitigation. Understanding microstructural evolution and the characteristics that form under various solidification conditions is essential for the development of multiscale, experimentallyinformed predictive modeling. This is highlightedby solidification simulations that utilize in situmeasurements of solidification dynamics from state-of-the-art experimental techniques.

36 MATERIALS SCIENCE↗

Properties of Arctic liquid and mixed-phase clouds from shipborne Cloudnet observations during ACSE 2014

This article presents Cloudnet retrievals of Arctic clouds from measurements conducted during a 3-month research expedition along the Siberian shelf during summer and autumn 2014. During autumn, we find a strong reduction in the occurrence of liquid clouds and an increase for both mixed-phase and ice clouds at low levels compared to summer. About 80 % of all liquid clouds observed during the research cruise show a liquid water path below the infrared black body limit of approximately 50 g m -2 . The majority of mixed-phase and ice clouds had an ice water path below 20 g m -2 . Cloud properties are analysed with respect to cloud-top temperature and boundary layer structure. Changes in these parameters have little effect on the geometric thickness of liquid clouds while mixed-phase clouds during warm-air advection events are generally thinner than when such events were absent. Cloud-top temperatures are very similar for all mixed-phase clouds. However, more cases of lower cloud-top temperature were observed in the absence of warm-air advection. Profiles of liquid and ice water content are normalized with respect to cloud base and height. For liquid water clouds, the liquid water content profile reveals a strong increase with height with a maximum within the upper quarter of the clouds followed by a sharp decrease towards cloud top. Liquid water content is lowest for clouds observed below an inversion during warm-air advection events. Most mixed-phase clouds show a liquid water content profile with a very similar shape to that of liquid clouds but with lower maximum values during events with warm air above the planetary boundary layer. The normalized ice water content profiles in mixed-phase clouds look different from those of liquid water content. They show a wider range in maximum values with the lowest ice water content for clouds below an inversion and the highest values for clouds above or extending through an inversion. The ice water content profile generally peaks at a height below the peak in the liquid water content profile – usually in the centre of the cloud, sometimes closer to cloud base, likely due to particle sublimation as the crystals fall through the cloud.

54 ENVIRONMENTAL SCIENCES↗

Nonclassical Crystallization Pathway in Biomolecular Self-assembly

Biomolecular self-assembly plays a vital role in synthetic and biological material systems and has therefore attracted tremendous interest due to its great potential for applications in biomedical and tissue engineering, biosensing, materials science, and nanotechnology. Although there have been numerous studies focusing on these systems’ designs, structures, and functions, little attention has been given to the mechanisms by which they nucleate. In this chapter, we review some recent advances in understanding the nucleation pathways of self-assembling biomolecular systems. We will mainly focus on crystallization via nonclassical nucleation mechanisms, which involve the addition of oligomers and more complex species or passage through transient metastable states, including dense liquids, amorphous clusters, and crystalline polymorphs. However, some cases that go through classical pathways are also introduced and discussed.

Chen, Jiajun↗

Spiral spin cluster in the hyperkagome antiferromagnet Mn 3 RhSi

Local spin correlation orders emerge in a paramagnetic state, with notable examples such as the partial order, cooperative paramagnetism, and soliton spin liquid. The noncentrosymmetric intermetallic antiferromagnet Mn 3 RhSi also exhibits the local spin correlation order in the paramagnetic state as magnetic short-range order in a wide temperature range. Here, we show that the local spin correlation order has a spiral structure by neutron scattering measurement of a Mn 3 RhSi single crystal. The possible origins of the magnetic cluster formation are discussed in terms of the Lifshitz invariant and the Griffiths phase, and compared with the room-temperature skyrmion phase of Co 7 Zn 7 Mn 6 and non-Fermi liquid behavior of β-Mn.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Fouling characterization and treatment of water reuse concentrate with membrane distillation: Do organics really matter

Membrane distillation (MD) for the treatment of concentrated brines has been limited in part by membrane fouling, resulting in subsequent flux decline and membrane wetting. This study provides new insight into the identification of fouling and scaling mechanisms and pretreatment strategies for mitigating flux decline with MD treatment of water reuse reverse osmosis concentrate (ROC). Bench-scale direct contact MD experiments were performed with untreated and pretreated ROC. Biological activated carbon (BAC), chemical water softening, or fluidized bed crystallization reactor coupled with ion exchange (FBCR-IX) were selected as pretreatment strategies to isolate the effects of organic fouling and calcium scaling. Organic and inorganic compounds were analyzed by high-performance liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP-MS). Calcium ions were found to be the major contributor to flux decline despite the high organic content in the ROC. Minimal organic fouling is likely because the organic matter in the ROC is hydrophilic, limiting hydrophobic-hydrophobic interactions between the organics and the membrane. Furthermore, the water flux declined by 63 % after removing organic compounds by BAC pretreatment, with 60 % of the calcium mass precipitating from the solution. Whereas, the water flux remained constant after removing multivalent ions with fluidized bed crystallization. Cleaning the membrane by acid washing and temperature reversal recovered 73 % and 12 % of the water flux, respectively. The analyses outlined in this study can assist in selecting appropriate fouling and scaling mitigation strategies for water reuse ROC and a wide range of feed solutions used in MD applications.

42 ENGINEERING↗

Re-investigation of high-temperature phase equilibria in Fe-rich Sm–Fe–Ti alloys

Recently renewed attempts to develop high-performance rare-earth-lean permanent magnets based on the Sm(Fe,Ti) 12 compound have drawn attention to the limited knowledge about the high-temperature phase equilibria in the Sm–Fe–Ti system. Experimental investigation of equilibrated alloys with electron probe microanalysis, X-ray diffraction and thermomagnetic analysis revealed several inaccuracies in the currently accepted phase relations at 1000°C and allowed for a revision of the Fe-rich corner of the Sm–Fe–Ti phase diagram. The Sm(Fe,Ti) 12 and Sm 3 (Fe,Ti) 29 phases were found to have more extended Ti ranges of 5.1–9.7 at% and 2.8–6.9 at%, respectively. With increasing of the Ti content, the Curie temperature of the Sm(Fe,Ti) 12 remains nearly constant at 306–312°C, whereas that of the Sm 3 (Fe,Ti) 29 increases from 188°C to 207°C. The low-titanium Sm 3 (Fe,Ti) 29 phase equilibrates not only with the Sm(Fe,Ti) 12 and Sm2(Fe,Ti) 17 phases, but also with (α-Fe) solid solution. Newly demonstrated equilibrium between Sm 2 (Fe,Ti) 17 and TiFe 2 phases makes impossible the earlier reported equilibrium between the Sm 3 (Fe,Ti) 29 and Sm(Fe,Ti) 11 phases. Because of an invariant reaction at 1000 °C, the revised phase diagram also features a class II four-phase equilibrium Sm 3 (Fe,Ti) 29 + TiFe 2 + Sm(Fe,Ti) 12 + Sm 2 (Fe,Ti) 17 . Peritectic decomposition of the Sm(Fe,Ti) 11 phase, which occurs either at 1075°C or at 1087°C, was found to have among its products the Sm(Fe,Ti) 12 phase. Although no such equilibration was attempted, it must be possible to obtain above 1087°C a two-phase state composed of the Sm(Fe,Ti) 12 phase and a liquid – which is important for manufacturing of the Sm(Fe,Ti) 12 - based permanent magnets via the liquid-phase sintering.

36 MATERIALS SCIENCE↗

Actinide complexes with Wells–Dawson polyoxometalates (part 2): californium

We report the first example of a polyoxometalate (POM) compound containing californium. Using a Wells–Dawson POM ligand, K 17 Cf(P 2 W 17 O 61 ) 2 ·2H 2 O was synthesized and characterized. Californium is the heaviest element ever crystalized with a POM. Significant solubility differences among the POM's f-element complexes were observed, enabling selective precipitation with separation factors rivaling liquid–liquid extraction.

and nuclear chemistry↗

Unraveling Anisotropic and Pulsating Etching of ZnO Nanorods in Hydrochloric Acid via Correlative Electron Microscopy

Despite much technical progress achieved so far, the exact surface and shape evolution during wet chemical etching is less unraveled, especially in ionically bonded ceramics. Herein, by using in situ liquid cell transmission electron microscopy, a repeated two-stage anisotropic and pulsating periodic etching dynamic is discovered during the pencil shape evolution of a single crystal ZnO nanorod in aqueous hydrochloric acid. Specifically, the nanopencil tip shrinks at a slower rate along [0001̅] than that along the $\langle$101̅0$\rangle$ directions, resulting in a sharper ZnO pencil tip. Afterward, rapid tip dissolution happens due to accelerated etching rates along various crystal directions. Concurrently, the vicinal base region of the original nanopencil tip emerges as a new tip followed by the repeated sequence of tip shrinking and removal. The high-index surfaces, such as {101̅m} (m = 0, 1, 2, or 3) and {21̅1̅n} (n = 0, 1, 2, or 3), are found to preferentially expose in different ratios. Our 3D electron tomography, convergent beam electron diffraction, middle-angle bright-field STEM, and XPS results indicate the dissociative Cl – species were bound to the Zn-terminated tip surfaces. Furthermore, DFT calculation suggests the preferential Cl – passivation over the {101̅1} and (0001) surfaces of lower energy than others, leading to preferential surface exposures and the oscillatory variation of different facet etching rates. The boosted reactivity due to high-index nanoscale surface exposures is confirmed by comparatively enhanced chemical sensing and CO 2 hydrogenation activity. In conclusion, these findings provide an in-depth understanding of anisotropic wet chemical etching of ionic nanocrystals and offer a design strategy for advanced functional materials.

36 MATERIALS SCIENCE↗

Understanding the mechanisms of anisotropic dissolution in metal oxides by applying radiolysis simulations to liquid-phase TEM

Iron-based redox-active minerals are ubiquitous in soils, sediments, and aquatic systems. Their dissolution is of great importance for microbial impacts on carbon cycling and the biogeochemistry of the lithosphere and hydrosphere. Despite its widespread significance and extensive prior study, the atomic-to-nanoscale mechanisms of dissolution remain poorly understood, particularly the interplay between acidic and reductive processes. Here, we use in situ liquid-phase-transmission electron microscopy (LP-TEM) and simulations of radiolysis to probe and control acidic versus reductive dissolution of akaganeite (β–FeOOH) nanorods. Informed by crystal structure and surface chemistry, the balance between acidic dissolution at rod tips and reductive dissolution at rod sides was systematically varied using pH buffers, background chloride anions, and electron beam dose. We find that buffers, such as bis-tris, effectively inhibited dissolution by consuming radiolytic acidic and reducing species such as superoxides and aqueous electrons. In contrast, chloride anions simultaneously suppressed dissolution at rod tips by stabilizing structural elements while promoting dissolution at rod sides through surface complexation. Dissolution behaviors were systematically varied by shifting the balance between acidic and reductive attacks. The findings show LP-TEM combined with simulations of radiolysis effects can provide a unique and versatile platform for quantitatively investigating dissolution mechanisms, with implications for understanding metal cycling in natural environments and the development of tailored nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Helical Covalent Polymers with Unidirectional Ion Channels as Single Lithium-Ion Conducting Electrolytes

Single-ion conducting polymer electrolytes have attracted great attention as safe alternatives to liquid electrolytes in high energy density lithium-ion batteries. Herein, we report the first example of a crystalline anionic helical polymer as a single lithium-ion conducting solid polymer electrolyte (SPE). Single-crystal X-ray analysis shows that the polymer folds into densely packed double helices, with bundles of unidirectional negatively charged channels formed that can facilitate lithium-ion transportation. Such a helical covalent polymer ( HCP) exhibits excellent room temperature lithium-ion conductivity (1.2 x 10 -3 S cm -1 ) in the absence of external lithium salts, a high transference number (0.84), low activation energy (0.14 eV), and a wide electrochemical stability window (0.2-5 V). We found that nonflammable, nonvolatile ionic liquid can serve as a solvating medium and excellent conductivity enhancer (>1000 times increase). These ion-conducting properties are comparable to the best polyethylene oxide-based polymer electrolytes mixed with lithium salts. Finally, we show that the solvated HCP SPE enables the reversible cycling of an all-solid-state cell prepared with a high-voltage NMC 811 cathode. Our study opens up new possibilities for developing next-generation high-performance solid-state electrolytes.

25 ENERGY STORAGE↗

Imaging a solvent-swollen polymer gel network by open liquid transmission electron microscopy

Visualizing the network of a solvent-swollen polymer gel remains problematic. To address this challenge, open transmission electron microscopy (TEM) was applied to thin gel films permeated by a nonvolatile ionic liquid. The targeted physical gels were prepared by cooling concentrated solutions of poly(ethylene glycol) in 1-ethyl-3-methyl imidazolium ethyl sulfate [EMIM][EtSO 4 ]. During the cooling, gelation occurred by a frustrated crystallization of the dissolved polymer, leading to a percolated, solvent-permeated semicrystalline network in which nanoscale polymer crystals acted as crosslinks. Crystalline features ranging from ~5 to ~200 nm were observed, with the visible network strands dominantly consisting of long curvilinear crystallites of ~15–20 nm diameter. Nascent spherulites irregularly decorated the network, creating a complex structural hierarchy that complicated analyses. Lacking diffraction contrast, TEM did not visualize the many disordered, fully solvated PEG chains present in the voids between crystals. Finally, recognizing that a network's three dimensionality is ambiguous when assessed through two-dimensional microscopy projections, a small gel region was studied by TEM tomography, revealing a nearly isotropic three-dimensional arrangement of the curvilinear crystallites, which displayed remarkably uniform cylindrical cross sections.

36 MATERIALS SCIENCE↗

Structural relaxation and crystallization in supercooled water from 170 to 260 K

The structural relaxation and crystallization of deeply supercooled water are investigated in transiently-heated nanoscale water films using infrared spectroscopy for temperatures between 170 and 260 K. For temperatures above ~230 K, the relaxation kinetics can be fit with a simple exponential decay which is characteristic of normal liquids. At lower temperatures, increasingly non-exponential decay is observed indicating the onset of heterogeneous dynamics. Water’s relaxation rate depends on its initial structure with hyper-quenched glassy water (HQW) typically relaxing more quickly than low-density amorphous solid water (LDA). At all temperatures, the relaxation time, trel is faster than the crystallization time, txtal. For HQW, the ratio, txtal/trel, goes through a minimum at ~198 K where it is about 60. The research was designed and supervised by GAK and BDK. LK and WAT conducted the experiments and analyzed the data. LK and GAK wrote the manuscript, with input from all authors.

Kringle, Loni M.↗

Recovery of Zr from ZrCl 4 by Electrolysis in Fused Salts and Ionic Liquids: Literature Review and Test Plan

This report reviewed the current status on the research and development of Zr electrodeposition in high temperature molten salts and room temperature ionic liquids from ZrCl 4 , which is the product of the chlorination process developed for recycling the Zr claddings of the spent nuclear fuels. Due to the pyrophoricity issue, the Zr metal product from the electrodeposition process is desired to be of coarse, dense crystalline or plates (instead of powder or loose, fine crystals) that are not to be easily oxidized. The findings based on the literature review are included in the report.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Exploring the composition, phase separation and structure of AgFe alloys for magneto-optical applications

Bimetallic alloys with large discrepancies in atomic radii and crystal structure typically yield systems that are highly immiscible, even at high temperatures. The Ag x Fe 1−x binary system has limited solid and liquid solubility and thus phase separated Ag + Fe alloys should result. Furthermore, Ag has interesting plasmonic properties and Fe is a strong ferromagnet, thus magneto-plasmonic nanoparticles/films should result due to their phase separation. We have leveraged a combinatorial sputter deposition to synthesize thin films with a large Ag x Fe 1−x (0.19 < x < 0.84) phase space to correlate the composition and structure to the optical and magnetic properties for both as-deposited and annealed compositions.

Bimetallic alloys↗

Hybrid machine learning/physics-based approach for predicting oxide glass-forming ability

Predicting the liquid compositions that will vitrify at experimentally accessible quench rates remains one of the grand challenges in the field of condensed matter physics. This glass-forming ability can be quantified as the critical quench rate needed to suppress crystallization. Knowledge of this critical quench rate also informs which glass composition could be used for new applications. There have been several physical and empirical models presented in the literature to predict the critical quench rate/glass forming ability. These models range from those theoretically derived to those quantified only through experimental characterization. In this work, we instead propose a new method to calculate the critical quench rate using the recently developed toy landscape model combined with machine learning. The toy landscape model accesses the underlying physics that control the vitrification behavior by directly simulating the liquid thermodynamics and kinetics. In conclusion, the results are discussed in terms of industrial impact, physical insights, and how the glass science community can develop improved predictions of glass-forming ability.

Crystallization↗

Strange Metals as Ersatz Fermi Liquids

Here, a long-standing mystery of fundamental importance in correlated electron physics is to understand strange non-Fermi liquid metals that are seen in diverse quantum materials. A striking experimental feature of these metals is a resistivity that is linear in temperature (T). In this Letter we ask what it takes to obtain such non-Fermi liquid physics down to zero temperature in a translation invariant metal. If in addition the full frequency (ω) dependent conductivity satisfies ω/T scaling, we argue that the T-linear resistivity must come from the intrinsic physics of the low energy fixed point. Combining with earlier arguments that compressible translation invariant metals are “ersatz Fermi liquids” with an infinite number of emergent conserved quantities, we obtain powerful and practical conclusions. We show that there is necessarily a diverging susceptibility for an operator that is odd under inversion and time reversal symmetries, and has zero crystal momentum. We discuss a few other experimental consequences of our arguments, as well as potential loopholes, which necessarily imply other exotic phenomena.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Sound velocities in shock-compressed soda lime glass: Melting and liquid-state response

Longitudinal sound velocities (and elastic moduli) were determined in soda lime glass (SLG) at peak shock stresses ranging between 40 and 90 GPa. Laser interferometry was used to obtain particle velocity histories and sound velocities by impacting SLG samples on lithium fluoride (LiF) optical windows. In all experiments, the SLG response consists of a sharp jump to a constant state followed by a release wave. The measured longitudinal sound velocities and moduli showed a marked decrease between 52 and 58 GPa, providing experimental evidence for the transformation from an amorphous solid to a liquid in shock-compressed SLG. Furthermore, the stress threshold (~55 GPa) for melting in SLG is considerably lower than the threshold reported in shock-compressed fused silica (~72 GPa), showing the effect of network-modifying cations on the onset of melting. The relative values of sound velocities, shock velocities, and the Hugoniot slopes—between 58 and 90 GPa—are fully consistent with the thermodynamic response of a shock-compressed liquid. Using the experimental results, the Grüneisen parameter (Γ) values were determined for liquid SLG to 90 GPa and then used to provide the Mie-Grüneisen equation of state for liquid SLG.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗