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Physical conditions in molecular clouds

Recent developments have complicated the picture of the physical conditions in molecular clouds. The discoveries of widespread emission from high-J lines of CD and 12-micron IRAS emission have revealed the presence of considerably hotter gas and dust near the surfaces of molecular clouds. These components can complicate interpretation of the bulk of the cloud gas. Commonly assumed relations between column density or mean density and cloud size are called into question by conflicting results and by consideration of selection effects. Analysis of density and density structure through molecular excitation has shown that very high densities exist in star formation regions, but unresolved structure and possible chemical effects complicate the interpretation. High resolution far-IR and submillimeter observations offer a complementary approach and are beginning to test theoretical predictions of density gradients in clouds.

Evans, Neal J., II↗

Microstructure, compression properties, and oxidation behavior of Hf-25Ta-5Me alloys (Me is Mo, Nb, W, 0.5Mo + 0.5 W, Cr, or Zr)

Hf–Ta based alloys have recently been investigated as potential candidates for high-temperature structural applications. While most attentions have been given to the properties above ~1200 °C where the alloys are mainly single-phase BCC structures and have excellent oxidation performance due to formation of super-oxides, structural properties at lower temperatures are equally important for applications in which an alloy may experience a range of temperatures. In the present work, microstructure, phase composition, mechanical properties and oxidation behavior of six Hf-25Ta-5Me alloys (Me is Mo (HTM alloy), W (HTW), 0.5Mo + 0.5 W (HTMW), Cr (HTC) or Zr (HTZ), the compositions are in at.%) are reported at temperatures below the eutectoid transformation. The alloys were prepared by arc melting followed by hot isostatic pressing for 3 h at 1400 °C and 207 MPa. All the alloys display coarse grains of partially or fully transformed (by a eutectoid reaction) high-temperature BCC phase. The eutectoid regions consist of fine lamellae of Hf-rich HCP and Ta-rich BCC phases. The ternary alloys containing W or Cr also contained small amounts of a cubic Laves phase. At 25 °C, the HTW alloy was the strongest (yield stress σ y = 1966 MPa) but brittle and HTZ was the weakest (σ y = 1120 MPa) but ductile among the studied alloys. Other alloys showed intermediate behaviors. In general, the room temperature ductility of the alloys increased with decreasing σy. All alloys maintained high strength up to 800 °C, but displayed a noticeable strength decrease at 1000 °C. At 1000 °C, HTMW was the strongest alloy (σ y = 468 MPa) and HTC was the weakest alloy (σ y = 368 MPa). All alloys had excellent deformability at 1000 °C. Oxidation behavior of the alloys was studied at 800 °C and 1000 °C and compared with that of Hf–27Ta binary alloy. Although the ternary additions improved oxidation resistance, overall oxidation performance of the studied alloys at 800 °C and 1000 °C was poor.

36 MATERIALS SCIENCE↗

Energy densities and temperature associated with the diffuse X-ray background, galaxies and large scale structures

Model independent evidence indicating numerical coincidences between energy densities and temperatures which indicate possible connections between the diffuse X-ray background and the formation of galaxies and large scale structures is presented. A consideration of characteristic temperatures associated with galaxies, peculiar velocities of galaxies, and voids suggests characteristic energies of emission. Barring complications induced by magnetic fields, these temperatures may also be associated with components of the X-ray background. Thermal bremsstrahlung emmission associated with the formation of large scale structures may be the dominant contributor to the high energy X-ray background, 5 to 200 keV. Thermal bremsstrahlung emission produced by galaxies at the epoch of their formation may contribute significantly to the low energy X-ray background, 0.1 to 3 keV. It is concluded that an important, if not dominant fraction of the X-ray background, was probably emitted by hot gas associated with the formation of large scale structures and galaxies.

Daly, Ruth A.↗

Orbital resonances and planetary formation sites

A cascaded resonance structure where planetesimal growth was accelerated at 2:1 interior and 1:2 exterior resonances, with an early-formed Jupiter producing runaway growth of planetary embryos, is hypothesized in a solar system formation model. The planetary embryos produce their own resonances, and these in turn lead to additional embryos in a process that successively propagates inwardly and outwardly to generate a resonant configuration of embryos. The early presence of Jupiter would in this way have imposed a harmonic structure on the accumulating planetesimal swarm. The positions of the planetary embryos can be moved into a degree of agreement with most of the present planetary positions which is comparable to that given by the Titius-Bode law, for the case of an accretion disk whose surface density obeys a power law of index -1.2.

Torbett, M.↗

Williston Basin Resource Study for Commercial-Scale Subsurface Hydrogen Storage

The Energy & Environmental Research Center (EERC), in partnership with the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL), the EERC’s State Energy Research Center (SERC), MPLX Operations LLC, and TC Energy Development Holdings Inc. (a subsidiary of TC Energy Corporation), studied the potential for subsurface hydrogen storage and recovery in the Williston Basin of western North Dakota. The project’s goal was to evaluate the feasibility of large-scale, secure geologic H 2 storage to support future hydrogen generation, storage, and use. This work included laboratory testing, H 2 –rock–fluid exposure experiments, literature reviews on H 2 embrittlement, and reservoir modeling and simulations. The study included an assessment of storage potential across three types of storage reservoirs using both reservoir simulation and DOE’s web-based tool SHASTA-HELP (Subsurface Hydrogen Assessment, Storage, and Technology Acceleration – Hydrogen Estimator for Logistical Planning), as well as investigation of potential H 2 production and markets for commercial-scale deployment. Building on prior EERC gas storage research, three storage options were selected for detailed evaluation: the Broom Creek Formation (a clastic saline reservoir), the Dickinson Lodgepole Mounds (DLM) complex (carbonate mud mound structures) of the Lodgepole Formation (an active oil and gas producing reservoir), and the Dunham Salt Interval of the Piper Formation (to be used for engineered salt cavern development). These targets were prioritized based on prior EERC research using datasets related to seal capacity, reservoir quality, mechanical integrity, and injectivity. Exposure tests on Broom Creek and DLM samples showed mineral dissolution and precipitation that increased brine salinity and altered reservoir rock surfaces. Although these results provide useful insight, they are limited by small sample sizes and short-term (30-day) exposure, requiring further study to assess long-term storage integrity. Salt formations were not tested because of their known nonreactivity and established mechanical stability. Results of reservoir simulations performed for a single site demonstrated that the Broom Creek Formation may be capable of receiving up to 42,000 tonnes of injected H 2 over 7 months via one well. H 2 recovery took place over 5 months, resulting in approximately 26,000 tonnes (~62% without cushion gas [CG]). This work suggests water production may be important and subsequent cycles of injection and production may perform more efficiently; however, significant site-specific work in the future is needed to assess actual reservoir performance of injection and withdrawal of H 2 storage. For oil reservoir potential, a multiple-well model was used to simulate injection of approximately 32,000 tonnes of H 2 into a single wellbore while simultaneously producing in place reservoir fluids from four offset wells to maintain reservoir pressure. The simulation results suggested a high recovery (~98%); in addition, cost advantages through existing infrastructure could be realized. Challenges in this reservoir include vi managing gas purity and leakage risks. In both scenarios, production of H 2 takes place in a single-well scenario with 10 cycles (7 months of injection and 5 months of production) over 10 years. Finally, the use of engineered caverns in the Dunhan Salt was evaluated, and the results suggest that while they have a smaller capacity (<1000 tonnes per cavern), they exhibit nearly complete gas recovery (>99%), fast response times, and low purity risk. While caverns in North Dakota may be smaller in capacity, fields can be developed in galleries to accommodate the volumetric needs and rapid turnaround times necessary to meet market demands. Geographic limitations and thin salt intervals in North Dakota may represent less total storage potential than salt domes elsewhere, but significant opportunities exist to expand this market for gas storage in North Dakota. A basinwide assessment was performed to estimate a first-of-its-kind value for H 2 storage on a large scale. DOE’s SHASTA-HELP, combined with EERC simulation work, was used to perform the assessment. Estimated H 2 storage potential varied widely for each formation type. The Broom Creek saline formation was estimated to have a storage potential of approximately 1.7–90.5 million tonnes (MMt). The DLM oil reservoirs were estimated to have 0.07–0.19 MMt of capacity. Notably, each of these estimates relies on significant assumptions regarding reservoir thickness, porosity, permeability, and CG needed for operation. Much research is needed to understand the true site-specific storage resource potential of each formation. Using the Dunham Salt Interval for cavern development may result in as much as 4.79 MMt (up to 2.87 MMt working gas) of H 2 storage potential. An important note for consideration is that the values presented here need significantly more geological characterization and engineering assessments prior to gaining confidence in performance. This will be a focal point for future research and development needs. The basinwide evaluation also indicated that North Dakota has significant H 2 generation potential, with estimates up to a possible 13 MMt annually, suggesting a substantial opportunity for H 2 market development and thus the need for commercial-scale H 2 storage to facilitate growth and resilience. Key Recommendations 1. Conduct detailed site characterization (3D seismic, well logs, core sampling) to reduce geologic uncertainty. 2. Perform techno-economic analyses incorporating market, regulatory, and incentive frameworks. 3. Investigate long-term interactions among H 2 , CGs, well materials, and formations to assess risks. 4. Develop pilot- and field-scale demonstrations to validate models and establish best practices.

03 NATURAL GAS↗

The structure and evolution of galacto-detonation waves - Some analytic results in sequential star formation models of spiral galaxies

Waves of star formation in a uniform, differentially rotating disk galaxy are treated analytically as a propagating detonation wave front. It is shown, that if single solitary waves could be excited, they would evolve asymptotically to one of two stable spiral forms, each of which rotates with a fixed pattern speed. Simple numerical solutions confirm these results. However, the pattern of waves that develop naturally from an initially localized disturbance is more complex and dies out within a few rotation periods. These results suggest a conclusive observational test for deciding whether sequential star formation is an important determinant of spiral structure in some class of galaxies.

Cowie, L. L.↗

RATFOR user's guide version 2.0

This document is a user's guide for RATFOR at Ames Research Center. The main part of the document is a general description of RATFOR, and the appendix is devoted to a machine specific implementation for the Cray X-MP. The general stylistic features of RATFOR are discussed, including the block structure, keywords, source code, format, and the notion of tokens. There is a section on the basic control structures (IF-ELSE, ELSE IF, WHILE, FOR, DO, REPEAT-UNTIL, BREAK, NEXT), and there is a section on the statements that extend FORTRAN's capabilities (DEFINE, MACRO, INCLUDE, STRING). THE appendix discusses everything needed to compile and run a basic job, the preprocessor options, the supported character sets, the generated listings, fatal errors, and program limitations and the differences from standard FORTRAN.

Helmle, L. C.↗

Optimization of Structurally Enhanced Solder Transient Liquid Phase Bonding

High temperature packaging technologies are a necessity for high temperature capable devices. SAC305 solder has an operational limit of 174°C imposed by creep effects which aligns well with current junction temperature limits of 175°C. Wide band gap semiconductor materials have the potential to reach junction temperatures of up to 800°C that are not currently attainable with significant reliability. Capitalizing on this potential will requires substrates and attachments that can operate well beyond the current 175°C standard. Silver sintering pastes have received widespread interest as a high temperature attachment alternative. However, the process requires high pressure bonding in an inert environment to achieve acceptable bond quality. Transient liquid phase (TLP) sintering is capable of good bond quality without pressure requirements but suffers from low thermal conductivity and only slightly reduced cost compared to silver sintering. SAC305 solder contains the same constituent materials for TLP as available copper-tin TLP sintering paste. By introducing engineered surface structures into the bond, intermetallic formation can be accelerated producing a bond similar to TLP sintering but in an ambient environment and for reduced cost. While this process has been demonstrated, it has not yet been optimized. Currently bonds are formed using a 75 μm stencil on substrate surface structures 24 μm tall, covering 19% of the bonding area. The process takes about 4 hours not including the formation of surface structures. Here, this study will center on the effects of stencil thickness and coating methods. Samples will be analyzed by scanning acoustic microscopy, die shear testing and cross sectional scanning acoustic microscopy.

42 ENGINEERING↗

Characterization of boundary precipitation in a heavy ion irradiated tungsten heavy alloy under the simulated fusion environment

In the concerted effort to identify materials capable of surviving the adverse environment of a fusion reactor interior, tungsten heavy alloys have been put forth as leading candidates. Experimental trials and behavioral studies have yielded positive results for their adoption by taking advantage of the alloy’s unique balance of inherently high fracture toughness and low sputter yields; yet due to their relative novelty in the fusion community, there remains a lack of understanding on the response of these materials to the extended high temperature irradiation environment of the reactor interior. Further, to alleviate this issue and provide the necessary data on the behavior of tungsten heavy alloys to the simulated fusion environment, a 90W-7Ni-3Fe alloy has been subjected to elevated temperature sequential Ni + and He + ion irradiations to mimic the expected displacement damage and gas production expected after five years of service as a plasma facing material component. Atomic-scale structural analyses and nanoscale chemical mapping have identified the formation of two distinct precipitation structures, a surface localized η-carbide and an a-W 2 C type tungsten carbide, both of which appear to originate at the bi-phase interface between W and the ductile phase. This irradiation assisted and induced precipitate formation respectively is anticipated to adversely affect these materials by selective embrittlement at bi-phase interfaces leading to a reduction in the material’s overall fracture toughness during prolonged high temperature irradiation. It is asserted that any potential exposure to C during fusion reactor operational service should be minimized as to prevent the formation of these phases.

36 MATERIALS SCIENCE↗

Constitutive Modeling of the Cross-Linked Polymers During the Trio-Aging Mechanism: Effects of Water, Oxygen, UV

Abstract The synergized effects of diverse environmental conditions such as humidity, temperature, UV, and oxygen, are considered through a generic model by combining the concepts of network alteration, hygrothermal, and Photo-thermo oxidation Models [1–4]. Hygrothermal and Photo-oxidation are considered dual aging mechanisms which are due to the synergized effects of moisture-oxygen, and UV-oxygen, respectively at elevated temperatures. Here Trio-aging is considered as the synergized effects of Hygrothermal, and Photo-oxidation which the main environmental elements involved in polymer degradation are oxygen, water, and UV radiation where each of which has a different micro-structural impact on the polymer matrix. While oxygen imposes chain scission and cross-link formation, water, and UV radiation mainly cause chain scission. Similar to our recent models, the dual network hypothesis of Topolosky is utilized and as a result, the strain energy of the polymer matrix is written in terms of two states namely unaged and infinity. The infinity state network, itself, is decomposed into three networks, namely brittle, flexible, and dead networks. While the brittle network models the cross-link formation as sub-structural phenomena, the flexible and dead networks are utilized to represent the cross-link reduction and chain scission. The contribution of these networks in the infinity state is based on the amount of relevant environmental elements. The model is developed for a domain with plenty of oxygen and holds true for a gradual aging process that happens in super-thin samples.

Bahrololoumi, Amir↗

Geological indicators for impact: The anomalous case of the Vredefort structure, South Africa

The Vredefort Dome is located within and almost central to the Witwatersrand basin in its presently known extent. It exposes a central Archean granite core which is surrounded by a collar of supracrustal rocks. These collar rocks outline a strong polygonal geometry. The Archean core is comprised of two concentric zones, the Outer Granite Gneiss (OGG), and the core central Inlandsee Leucogranofels (ILG). The rocks of the inner core display granulite facies metamorphism, while the OGG is in amphibolite facies. The inner core is believed from recent drill hole information to be underlain by mafic and ultramafic gneisses, the extent of which cannot be assessed at present. A fairly broad zone of charnockites separates the OGG and ILG domains. This zone is characterized by a high concentration of pseudotachylite and ductile shearing. Whereas a number of other domical structures are located within or surrounding the Witwatersrand basin, the Vredefort structure is anomalous, in that it has: a partly polygonal geometry; extensive alkali intrusives in the northwestern sector; granophyre dykes (ring-dykes peripheral to the contact collar-basement and NW-SE or NE-SW trending dykes within the Archean basement); contact metamorphism of the collar supracrustal rocks; the overturning of collar supracrustals in the northern sectors; deformation phenomena widely regarded as representing shock metamorphism (pseudotachylite, (sub)planar microdeformation features in quartz, shatter cones and occurrences of high-P quartz polymorphs); a positive 30 mgal gravity anomaly; and high amplitude magnetic anomalies. Recent geophysical, structural and petrological evidence pertinent for the identification of the processes that led to the formation of the Vredefort structure are summarized.

Antoine, L. A. G.↗

Crystallization pathways and interfacial drivers for the formation of hierarchical architectures

The development of structural hierarchy on various length scales during crystallization process is ubiquitous in biological systems and is also observed in synthetic nanomaterials. The driving forces for the formations of complex architectures range from local interfacial interactions, that modify interfacial speciation, local supersaturation, and nucleation barriers, to macroscopic interparticle forces. Although it is enticing to interpret the formation of hierarchical architectures as the assembly of independently nucleated building blocks, often crystallization pathways follow monomer-by-monomer addition with structural complexity arising from interfacial chemical coupling and strongly correlated fluctuation dynamics in the electric double layers. Here, the mechanism of the development of structural hierarchy through heterogeneous nucleation, coupled interfacial nucleation and assembly, and oriented attachment of independently nucleated particles is discussed. In this article, the emphasis is made on the discussion of the underlying interfacial forces and chemical coupling that drives crystallization pathways towards the formation of structural hierarchy.

36 MATERIALS SCIENCE↗

Detecting thermal crack growth on a large additive manufactured structure using acoustic emission

Large format additive manufacturing (LFAM) proved to have a great potential to become an adjacent technology to traditional manufacturing methods. One of the sectors LFAM is targeting is rapid tool/mold development for composites. This includes large mold structures used for high-temperature molding techniques (in-oven or autoclave). Although, these large printed structures (reaching hundreds of pounds) develop thermal-residual stress during cool-down and can eventually crack, turning the structure into waste. Acoustic emission (AE), a passive non-intrusive global nondestructive evaluation (NDE) technique, was used to monitor crack growth and can provide the right tools that can be used for feedback loop for corrective action. This research performs thermal testing on a large AM mold with preexisting cracks, in an attempt to monitor crack growth using AE. AE was able to detect, identify and locate the crack source by means of acoustic features, waveform characteristics, spectrum analysis, and difference in arrival times.

Spencer, Ryan↗

Photocatalytic Hydrogen Evolution Using Mesoporous Honeycomb Iron Titanate

Mesoporous honeycomb iron titanate using a sol-gel, evaporation-induced self-assembly method is synthesized. A triblock copolymer, F127, serves as a structure-directing agents, with iron chloride and titanium (IV) isopropoxide as inorganic precursors. The strong intermolecular force of attraction among urea, metal precursors, and polymer led to the formation of the mesoporous honeycomb structure. The study of physicochemical properties using different techniques reveals the formation of microstructures with a remarkable degree of porosity. The amorphous iron titanate outperforms the photochemical generation of H 2 due to its disorderly structural arrangement and incomplete crystal formation. The randomness on the structure provides more area for catalytic reaction by providing more contact with the reactant and superior light absorption capability. The high amount of hydrogen gas, 40.66 mmolg -1 h -1 , is observed in the investigation over 3 h of activity for the iron titanate honeycomb sample. This yield is a more significant amount compared to the obtained for the commercially available TiO 2 (23.78 mmolg -1 h -1 ). The iron titanate materials synthesized with low-cost materials and methods are very effective and have the potential for hydrogen generation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Redox-Induced Structural Reorganization Dictates Kinetics of Cobalt(III) Hydride Formation via Proton-Coupled Electron Transfer

Two-electron, one-proton reactions of a family of [CoCp(dxpe)(NCCH 3 )] 2+ complexes (Cp = cyclopentadienyl, dxpe = 1,2-bis(di(aryl/alkyl)phosphino)ethane) form the corresponding hydride species [HCoCp(dxpe)] + through a stepwise proton-coupled electron transfer process. For three [CoCp(dxpe)(NCCH 3 )] 2+ complexes (dxpe = dppe (1,2-bis(diphenylphosphino)ethane), depe (1,2-bis(diethylphosphino)ethane), and dcpe (1,2-bis(dicyclohexylphosphino)ethane)), peak shift analysis was employed to quantify apparent proton transfer rate constants from cyclic voltammograms recorded with acids ranging 22 pK a units. The apparent proton transfer rate constants correlate with the strength of the proton source for weak acids, but these apparent proton transfer rate constants curiously plateau (k pl ) as the reaction becomes increasingly exergonic. The absolute apparent proton transfer rate constants across both these regions correlate with the steric bulk of the chelating diphosphine ligand, with bulkier ligands leading to slower kinetics (k plateau,depe = 3.5 x 10 7 M -1 s -1 , k plateau,dppe = 1.7 x 10 7 M -1 s -1 , k plateau,dcpe = 7.1 x 10 4 M -1 s -1 ). Mechanistic studies were conducted to identify the cause of the aberrant $k_PT^{app}$–ΔpK a trends. When the deuterated acids are employed, deuterium incorporation in the Cp ring is observed, indicating protonation of the CoCp(dxpe) species to form the corresponding hydride proceeds via initial ligand protonation. Digital simulations of cyclic voltammograms show ligand loss accompanying initial reduction gates subsequent PCET activity at higher driving forces. Together, these experiments reveal the details of the reaction mechanism: reduction of the Co(III) species is followed by dissociation of the bound acetonitrile ligand, subsequent reduction of the unligated Co(II) species to form a Co(I) species is followed by protonation, which occurs at the Cp ring, followed by tautomerization to generate the stable Co(III)-hydride product [HCoCp(dxpe)] + . Analysis as a function of chelating disphosphine ligand, solvent, and acid strength reveals that the ligand dissociation equilibrium is directly influenced by the steric bulk of the phosphine ligands and gates protonation, giving rise to the plateau of apparent proton transfer rate constant with strong acids. The complexity of the reaction mechanism underpinning hydride formation, encompassing dynamic behavior of the entire ligand set, highlights the critical need to understand elementary reaction steps in proton-coupled electron transfer reactions.

14 SOLAR ENERGY↗