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At least 73 records · Page 4

Sequence-selective dynamic covalent assembly of information-bearing oligomers

Relatively robust dynamic covalent interactions have been employed extensively to mediate molecular self-assembly reactions; however, these assembly processes often do not converge to a thermodynamic equilibrium, instead yielding mixtures of kinetically-trapped species. Here, we report a dynamic covalent self-assembly process that mitigates kinetic trapping such that multiple unique oligomers bearing covalently coreactive pendant groups are able to undergo simultaneous, sequence-selective hybridization with their complementary strands to afford biomimetic, in-registry molecular ladders with covalent rungs. Analogous to the thermal cycling commonly employed for nucleic acid melting and annealing, this is achieved by raising and lowering the concentration of a multi-role reagent to effect quantitative dissociation and subsequently catalyze covalent bond rearrangement, affording selective assembly of the oligomeric sequences. The hybridization specificity afforded by this process further enabled information encoded in oligomers to be retrieved through selective hybridization with complementary, mass-labeled sequences.

36 MATERIALS SCIENCE↗

Issues on Fabrication and Evaluation of SiC/SiC Tubes With Various Fiber Architectures

SiC/SiC engine components, high-modulus Sylramic-iBN SiC fiber tows were used to form nine different tubular architectural preforms with 13 mm (0.5 in.) inner diameter and lengths of approx. 75 and 230 mm (approx. 3 and approx, 9 in.). The thin-walled preforms were then coated with a BN interphase and densified with a hybrid SiC matrix using nearly the same process steps previously established for slurry-cast melt-infiltrated Sylramic-iBN/BN/SiC flat panels. The as-fabricated CMC tubes were microstructurally evaluated and tested for tensile hoop and flexural behavior, and some of the tubes were also tested in a low-pressure burner rig test with a high thru-thickness thermal gradient. To date, four general tube scale-up issues have been identified: greater CVI deposits on outer wall than inner wall; increased ply thickness and reduced fiber fraction; poor test standards for accurately determining the hoop strength of a small-diameter tube; and poor hoop strength for architectures with seams or ply ends. The underlying mechanisms and possible methods for their minimization are discussed.

Yun, H. M.↗

Microstructural evolution and intermetallic formation in Zn-3Mg (wt%) powder mixture processed by high-pressure torsion

Severe plastic deformation (SPD) techniques have been used extensively over the past 40 years for producing strong metals and alloys. High-pressure torsion (HPT) is one of the most promising SPD techniques for achieving high strength through nanoscale grain refinement and phase transformation. In this research, a mixture of pure zinc (Zn) and magnesium (Mg) powders, Zn-3Mg (wt%), was HPT-processed under a pressure of 6 GPa for 1, 5, 10, 20, and 30 turns at room temperature to achieve a high strength biodegradable material. In order to understand the effects of pre-consolidation on the resulting microstructure and hardness, HPT processing was performed on loose powders placed in the die and also on a pre-compacted powder mixture and the resulting HPT disks were characterized by X-ray diffraction, scanning electron microscopy, atom probe tomography, and Vickers microhardness. In both cases, the HPT disk microstructures contained nanoscale grains, and stable and metastable strain-induced intermetallics, but an unusual softening appeared at large shear strains. Grain size, grain morphology, and the formation of different intermetallics were analyzed to explain the unusual hardness distribution, and it was found that an inverse Hall-Petch relationship between hardness and grain size exists. It is suggested that thermally-activated phenomena such as grain boundary sliding contributed to the strain-induced softening of this nano-structured biomaterial due to its low melting point. Finally, the current results are compared with those for HPT-processed cast alloys and hybrids of the same composition.

36 MATERIALS SCIENCE↗

Experimental Constraints on the Origin of Lunar High-Ti Ultramafic Glasses

Phase equilibria and dissolution rate experiments are used to develop a petrogenetic model for the high-Ti lunar ultramafic glasses. Near-liquidus phase relations of the Apollo 14 black glass, the most Ti-rich lunar ultramafic glass, are determined to 2.2-GPa. The liquidus is saturated with Cr-spinel at 1-atm, olivine between approximately 0.5- and 1.5-GPa, and low-Ca pyroxene + Cr-spinel above 1.5-GPa. Ilmenite does not crystallize near the liquidus and implies that high-Ti ultramafic glasses are not produced by melting of an ilmenite-saturated source. We infer that high-Ti ultramafic magmas are derived from low-Ti ultramafic parent magmas by assimilation of ilmenite +/- clinopyroxene +/- urKREEP +/- pigeonite in the shallow lunar interior. Heat is provided by adiabatic ascent of the low-Ti ultramafic primary magmas from the deeper lunar interior and crystallization of olivine during assimilation. The assimilation reaction is modeled by mass balance and requires that ilmenite and high-Ca pyroxene are assimilated in a approximately 3:1 ratio, a much higher ratio than the proportion in which these minerals are thought to exist in the lunar interior. In an effort to understand the kinetic controls on this reaction, the dissolution of ilmenite is examined experimentally in both low- and high-Ti lunar magmas. We find that ilmenite dissolves incongruently to Cr-spinel and a high-Ti melt. The dissolution reaction proceeds by a diffusion-controlled mechanism. An assimilation model for the origin of high-Ti melts is developed that leaves the magma ocean cumulates in their initial stratigraphic positions and obviates source hybridization models that require lunar overturn.

Wagner, T. P.↗

Upcycling Polyethylene Waste Into Hybrid Graphitic Porous Carbon Materials Used in High-Performance Zinc-Ion Hybrid Capacitors

Polyethylene (PE) waste is a challenge to upcycle into useful materials because this plastic tends to decompose into volatile compounds when heated at relatively low temperatures. In this work, we report a chemical process that addresses this challenge by converting mixtures of linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and high-density polyethylene (HDPE) waste into a hybrid graphitic porous carbon (HGPC) that can be used as a zinc-ion hybrid capacitor cathode. The process uses a low temperature thermal oxidation pre-treatment step, with assistance of an inert solid additive (KCl) to increase the effective surface area of the PE melt, to functionalize, cross-link, and stabilize the PE waste followed by carbonization and catalytic graphitization steps at higher temperatures with a potassium carbonate (K2CO3) catalyst. The PE waste derived HPGC (PW-HPGC) has a hybrid structure composed of graphene-like carbon nanosheets grown on the surface of carbon particles, high porosity with the Brunauer–Emmett–Teller (BET) specific surface area up to 1,763 m2g-1, and good graphitic degree with average Raman I2D/IG ratios of 0.53. When used as a cathode material for zinc-ion hybrid capacitors, this PW-HGPC exhibits an excellent specific capacity up to 126.7 mAhg-1 at high mass loading of 10 mgcm-2. Moreover, PW-HGPC exhibits remarkable cycling stability with capacity retention of >94% after 10,000 cycles at a current density of 2.0 A g-1.

hybrid graphitic porous carbon↗

Development and Characterization of SiC)/ MoSi2-Si3N4(p) Hybrid Composites

Intermetallic compound MoSi2 has long been known as a high temperature material that has excellent oxidation resistance and electrical/thermal conductivity. Also its low cost, high melting point (2023 C), relatively low density (6.2 g/cu cm versus 9 g/cu cm for current engine materials), and ease of machining, make it an attractive structural material. However, the use of MoSi2 has been hindered due to its poor toughness at low temperatures, poor creep resistance at high temperatures, and accelerated oxidation (also known as 'pest' oxidation) at temperatures between approximately 450 and 550 C. Continuous fiber reinforcing is very effective means of improving both toughness and strength. Unfortunately, MoSi2 has a relatively high coefficient of thermal expansion (CTE) compared to potential reinforcing fibers such as SiC. The large CTE mismatch between the fiber and the matrix resulted in severe matrix cracking during thermal cycling. Addition of about 30 to 50 vol % of Si3N4 particulate to MoSi2 improved resistance to low temperature accelerated oxidation by forming a Si2ON2 protective scale and thereby eliminating catastrophic 'pest failure'. The Si3N4 addition also improved the high temperature creep strength by nearly five orders of magnitude, doubled the room temperature toughness and significantly lowered the CTE of the MoSi2 and eliminated matrix cracking in SCS-6 reinforced composites even after thermal cycling. The SCS-6 fiber reinforcement improved the room temperature fracture toughness by seven times and impact resistance by five times. The composite exhibited excellent strength and toughness improvement up to 1400 C. More recently, tape casting was adopted as the preferred processing of MoSi2-base composites for improved fiber spacing, ability to use small diameter fibers, and for lower cost. Good strength and toughness values were also obtained with fine diameter Hi-Nicalon tow fibers. This hybrid composite remains competitive with ceramic matrix composites as a replacement for Ni-base superalloys in aircraft engine applications.

Hebsur, Mohan G.↗

Thermodynamic controls on the synthesis, structure and reactivity of materials for energy (Final Report)

The major objectives have been: a) to advance and use unique calorimetric capabilities to determine the energetics of oxide and other materials having possible energy applications, with an emphasis on new materials for batteries, fuel cells and solar energy conversion, b) to understand, in terms of both macroscopic energetics and microscopic structure and bonding, the interplay of defect chemistry, oxidation-reduction, and size effects at the bulk and nanoscale in determining materials properties. This project emphasizes mixed ionic-electronic conduction materials containing transition metals of variable valence, especially perovskites and lithium containing phases, with M = Mn, Fe, Co, Ni. The thermochemistry of new families of complex halide, chalcogenide, nitride and hybrid (organic-inorganic) perovskite materials were explored. The major and unique technique employed is high temperature oxide melt solution calorimetry, with careful attention given to materials synthesis and characterization. The thermochemical studies will be coupled with structural studies, especially to characterize order-disorder phenomena by in situ high temperature diffraction techniques.

14 SOLAR ENERGY↗

Accessing Icy Worlds Using Lattice Confinement Fusion (LCF) Fast Fission

Exploring the oceans of icy moons and planets requires a robust robotic probe powered by an energy source that can operate under icy world ocean conditions and be self-contained. We propose a non-fissile, compact, scalable nuclear energy source to electrically power untethered, autonomous probes to melt or bore through icy world crusts. The probe can be used for planetary (i.e. Pluto, lunar (i.e., Europa), or asteroid exploration (i.e. Ceres) where ice caps are encountered. This new approach may yield a variable output fission power source with a higher performance than 238Pu and a non-fissile alternative to a highly enriched uranium (HEU) core. This approach saves uranium enrichment expense, and both HEU and 238Pu security and launch safety costs. The reactor will produce electrical power with thermal waste heat to melt through the ice crust with possible sonic assistance. This NIAC funded proposal and presentation will introduce the hybrid fusion-fission reactor concept applied to the Saturnian moon, Enceladus, explore the potential for and benefits of this new type of nuclear reactor, and discuss applying this new technology.

Icy Worlds↗

Influence of geometry on columnar to equiaxed transition during electron beam powder bed fusion of IN718

Correlation between spot-melt scan parameters (linear spot-density aka areal energy density), build geometry, and solidification microstructure evolution (columnar vs equiaxed) in a powder bed fusion technology is investigated. It is shown that to maintain the equiaxed solidification microstructure evolution in electron beam powder bed additive manufacturing (AM), the areal energy density per layer needs to be scaled with respect to the 2D cross-sectional area of the layer being melted. Samples with two different cross-sectional areas (40 × 40 mm and 20 × 20 mm) have been fabricated with varying areal energy densities. For a given square cross-section (20 × 20 mm), increasing the areal energy density (4.8 MJ/sq.m to 14.7 MJ/sq.m) transitioned the solidification microstructure from columnar to equiaxed. The observed microstructure data (Electron Back Scattered Diffraction - EBSD) is quantified by calculating the principal component (PC) score using a spatial statistics methodology. The sample with equiaxed grains is found to have a low PC score while the sample with columnar grain had a high PC score. A semi-analytical model is used to simulate the heat transfer and the local solidification conditions as a function of processing parameters (linear spot-density). The result from the heat transfer model is correlated with previously quantified microstructure data. Space-Time analysis of the melt pattern is done and correlated with the observed microstructure. In addition, from the findings, appropriate parameters have been used to additively manufacture a turbine blade with site-specific or hybrid solidification microstructure (traditional fabrication possible via a patented method of localized cold working and heat treatment).

36 MATERIALS SCIENCE↗

Creep and Cyclic Fatigue Durability of 3D Woven SiC/SiC Composites with (CVI+PIP) Hybrid Matrix

SiC-SiC composites are potential candidate materials for turbine components such as combustor liners, nozzle vanes and blades because of their low density, high temperature capability, and tailorable mechanical properties. The first generation of SiC-SiC composites fabricated by melt infiltration are being introduced in current engines. These materials are limited to 1315 degrees Centigrade applications because of the presence of residual silicon in the SiC matrix. Currently there is an increasing interest in developing SiC-SiC composites without silicon for structural aerospace applications above 1315 degrees Centigrade. The developmental 3D woven SiC-SiC composites with Chemical Vapor Infiltration plus Polymer Impregnation and Pyrolysis (CVI+PIP) hybrid matrix show potential for 1482 degrees Centigrade applications. In this study 3D woven SiC-SiC composite specimens were creep tested at 1482 degrees Centigrade at different stress levels until failure or for 1000 hours without failure. The failed specimens were analyzed for under a scanning electron microscope to assess the damage mechanisms. The creep data of 3D woven SiC-SiC composites with (CVI+PIP) hybrid matrix were compared with those of full CVI SiC-SiC composites and sintered SiC from the literature. The potential benefits limitations and durability of 3D woven SiC-SiC composites for turbine applications will be discussed.

creep durability↗

Decoding the Atomic Structure of Ga 2 Te 5 Pulsed Laser Deposition Films for Memory Applications Using Diffraction and First-Principles Simulations

Neuromorphic computing, reconfigurable optical metamaterials that are operational over a wide spectral range, holographic and nonvolatile displays of extremely high resolution, integrated smart photonics, and many other applications need next-generation phase-change materials (PCMs) with better energy efficiency and wider temperature and spectral ranges to increase reliability compared to current flagship PCMs, such as Ge 2 Sb 2 Te 5 or doped Sb 2 Te. Gallium tellurides are favorable compounds to achieve the necessary requirements because of their higher melting and crystallization temperatures, combined with low switching power and fast switching rate. Ga 2 Te 3 and non-stoichiometric alloys appear to be atypical PCMs; they are characterized by regular tetrahedral structures and the absence of metavalent bonding. The sp 3 gallium hybridization in cubic and amorphous Ga 2 Te 3 is also different from conventional p-bonding in flagship PCMs, raising questions about its phase-change mechanism. Furthermore, gallium tellurides exhibit a number of unexpected and highly unusual phenomena, such as nanotectonic compression and viscosity anomalies just above their melting points. Using high-energy X-ray diffraction, supported by first-principles simulations, we will elucidate the atomic structure of amorphous Ga 2 Te 5 PLD films, compare it with the crystal structure of tetragonal gallium pentatelluride, and investigate the electrical, optical, and thermal properties of these two materials to assess their potential for memory applications, among others.

36 MATERIALS SCIENCE↗

Lunar and Planetary Science XXXV: Viewing the Lunar Interior Through Titanium-Colored Glasses

The session"Viewing the Lunar Interior Through Titanium-Colored Glasses" included the following reports:Consequences of High Crystallinity for the Evolution of the Lunar Magma Ocean: Trapped Plagioclase; Low Abundances of Highly Siderophile Elements in the Lunar Mantle: Evidence for Prolonged Late Accretion; Fast Anorthite Dissolution Rates in Lunar Picritic Melts: Petrologic Implications; Searching the Moon for Aluminous Mare Basalts Using Compositional Remote-Sensing Constraints II: Detailed analysis of ROIs; Origin of Lunar High Titanium Ultramafic Glasses: A Hybridized Source?; Ilmenite Solubility in Lunar Basalts as a Function of Temperature and Pressure: Implications for Petrogenesis; Garnet in the Lunar Mantle: Further Evidence from Volcanic Glasses; Preliminary High Pressure Phase Relations of Apollo 15 Green C Glass: Assessment of the Role of Garnet; Oxygen Fugacity of Mare Basalts and the Lunar Mantle. Application of a New Microscale Oxybarometer Based on the Valence State of Vanadium; A Model for the Origin of the Dark Ring at Orientale Basin; Petrology and Geochemistry of LAP 02 205: A New Low-Ti Mare-Basalt Meteorite; Thorium and Samarium in Lunar Pyroclastic Glasses: Insights into the Composition of the Lunar Mantle and Basaltic Magmatism on the Moon; and Eu2+ and REE3+ Diffusion in Enstatite, Diopside, Anorthite, and a Silicate Melt: A Database for Understanding Kinetic Fractionation of REE in the Lunar Mantle and Crust.

Source record↗

Petrogenesis of lunar troctolites

Models of petrogenesis for lunar troctolites are severely constrained by the high Mg(*) (greater than 88) values of the most primitive members of the Mg-rich suite. Melts derived by partial melting of olivine cumulates to the lunar magma ocean have high Mg(*) but are strongly undersaturated with respect to plagioclase. Assimilation of lunar crust cannot bring these melts to the plagioclase liquious without unduly reducing the Mg(*) values of olivine. Partial melts derived by melting a lherzolite primitive interior have higher normative plagioclase contents but require sources with Mg(*) greater than 90. More terrestrial-like Mg(*) (approximately 88) values are permitted if rising thermal plumes are capable of entraining the most Mg-rich cumulates of the magma ocean. The Mg(*) values of lunar troctolites may, therfore, reflect a hybrid source composed of primitive mantle and Mr-rich cumulates of the magma ocean. Higher Mg(*) values may also arise from the reducction of small amounts of FeO to Fe. Alternatively, the parent magmas to lunar troctolites may be impact melts of the anorthositic crust and the Mg-rich dunites cumulates of the magma ocean; the latter were brought to the upper mantle during the overturn of the unstable cumulate pile of the magma ocean.

Hess, Paul C.↗

Solvothermal synthesis of metal alkanoate and metal oxide nanoparticles

A facile solvothermal method can be used to synthesize metal alkanoate nanoparticles using a metal nitrate precursor, alcohol/water, and alkanoic acid. The method can produce lanthanide (e.g., La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, or Yb) and transition metal (e.g., Ag, Co, Cu, or Pb) alkanoate nanoparticles (<100 nm) with spherical morphology. These hybrid nanomaterials adopt a lamellar structure consisting of inorganic metal cation layers separated by an alkanoate anion bilayer and exhibit liquid crystalline phases during melting. The metal alkanoate nanoparticles can be calcined to produce metal oxide nanoparticles.

Treadwell, LaRico Juan↗

Melting of spatially modulated phases at domain wall/surface junctions in antiferrodistortive multiferroics

A physical understanding of the nature of spatially modulated phases (SMPs) in rare-earth-doped antiferrodistortive (AFD) multiferroics and how they behave close to surfaces and interfaces is lacking. Here the emergence of the antiferroelectric (AFE), ferroelectric (FE), or ferrielectric (AFE-FE) spatial modulation in the vicinity of the morphotropic phase transition in La x Bi 1 – x Fe O 3 ( x ~ 0.2 ) is explored on the atomic level using high-resolution scanning transmission electron microscopy (HRSTEM). The suppression, or “melting,” of the AFE-type SMP in the vicinity of the AFD twin wall/surface junction is revealed by HRSTEM in La 0.22 Bi 0.78 Fe O 3 films and explained by the hybrid approach combining Landau-Ginzburg-Devonshire (LGD) phenomenology and the semimicroscopic four-sublattice model (FSM). The LGD-FSM approach reduces the problem of AFE (or AFE-FE) SMP emergence and stability to the thermodynamic analysis of the free-energy functional with AFE, FE, and AFD long-range order parameters and two master parameters: the FE-AFE coupling strength between four neighboring A sites and the nonstoichiometry factor, which are proportional to the variations of La concentration in La x Bi 1 – x Fe O 3 films. Finally, we establish that the surface-induced melting of SMPs and the associated broadening of AFE AFD domain walls minimize the film free energy under certain conditions imposed on the master parameters and gradient energy below the critical value. The observed behavior provides insight into the origin of SMPs in AFD multiferroics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Molten Salt Lattice Confinement Fusion (LCF) Fast Fission Reactor for Lunar and Planetary Surface Power

Molten salt fission reactors (MSR) have been suggested for lunar and planetary surface power systems. They have the advantage of operating at high temperature, for efficient thermal-electrical conversion, low pressure, long-lived with high nuclear fuel burnup. MSR are often designed to breed fissile 233U from natural 232Th by neutron capture and  decay via: 232Th(n,)233Th(,)233Pa(,)233U Unfortunately, this process requires 233Pa isotope separation and segregation to decay to 233U. This requirement prevents additional neutron capture that interferes with 233U breeding. Instead, Wooley’s sub-critical, fast fission, molten salt reactor would use externally generated tokamak fusion neutrons1,2 to fission all actinides.We propose a simpler fusion-fast-fission sub-critical reactor that generates fast neutrons in situ from lattice confinement fusion (LCF) to fission fertile and fissile actinides. This hybrid reactor doesn't require enriched 235U fissile pins to initiate fis-sion reactions, nor 233Pa separation and segregation during operation. Like Wooley’s, this hybrid reactor “burns” natural uranium (238U) or thorium (232Th) which avoids uranium enrichment and additional fissile material launch safety and security costs. The LCF neutron source is initiated by bremsstrahlung photoneutrons (Fig. 1)3 or isotopic neutron sources in electron-screened lattices (Fig. 2)4,5. Alternatively, the electrolytic Pd-deuterium co-deposition6protocol fast fissions7 both 232Th and 238U. However, an aqueous electrolyte-based system, without pressurization similar to conventional pressurized water fission reactors, is incapable of high temperatures due to the boiling point of the electrolyte slightly over 100 C. Molten salts can be used instead as was demonstrated at the University of Hawaii8 using a variety of Ni and Pd cathodes in lithiated, hydrided and deuterated salts. These salts have melting points often exceeding 500C making them suitable to efficiently produce electrical power9 through either Advanced Stirling Genera-tors (< 100 kWe) or closed-Brayton Cycle (> 100 kWe). This hybrid reactor could power a wide range of lunar or Martian applications from unmanned in-struments, to charging vehicles and entire facilities such as human habitats or in situ resource utilization. The power conversion cycles are Carnot Cycle limited, but generally 30% efficient at best. However, waste heat on the moon or Mars is important to surviving either two-week lunar nights or Martian nights as well as providing process heat for mineral extraction and “living off the land”

Lawrence Forsley↗