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At least 523 records · Page 29

Retaining Geochemical Signatures during Aragonite-Calcite Transformation at Hydrothermal Conditions

Transformation of aragonite, a mineral phase metastable at Earth’s surface, to calcite widely occurs in both sedimentary and metamorphic systems with the presence of an aqueous phase. The transformation process can affect geochemical signatures of aragonite (a protolith). This study focused on quantification of the retention of Mg/Ca and Sr/Ca ratios, and δ18O during the transformation process as well as evaluation of the transformation rate. To investigate the effect of transformation from aragonite to calcite on elemental and stable isotope ratios, we conducted a series of experiments in NaCl solutions at temperatures between 120 and 184 °C. Two additional experiments at 250 °C were conducted to estimate the transformation rate of aragonite to calcite. Protolith materials consist of (1) synthetic (Mg; Sr-bearing or non-Mg; Sr bearing) needle-shaped microcrystals of aragonite (<5 µm in size) and (2) larger chips (>100 µm in size) of natural aragonite. X-ray diffraction (XRD) showed that microcrystals successfully transformed to calcite within 30 h and scanning electron microscopy (SEM) yielded a change in the crystal size to >10 µm in rhombohedral shape. Electron backscatter diffraction (EBSD) of the larger aragonite chips showed that transformation to randomly oriented calcite occurred at the rims and along the cracks while the core retained an aragonite crystal structure. Isotope-ratio mass spectrometry (IRMS) analyses showed that calcite δ18O was controlled by temperature and δ18O of the solution. The obtained calibration curve of isotope fractionation factor versus temperature is consistent with other studies. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses showed that calcite partially or completely retained Mg/Ca and Sr/Ca ratios through the transformation.

58 GEOSCIENCES↗

Transient magnetic field diffusion considerations relevant to magnetically assisted indirect drive inertial confinement fusion

We report application of a magnetic field to an indirect drive inertial confinement fusion target requires diffusion of the field through the high-Z and electrically conducting Hohlraum. The onset of the external field generates eddy currents in the Hohlraum wall that result in (1) a reduction of the peak field at the capsule, (2) heating of the Hohlraum wall through Ohmic dissipation, and (3) wall movement due to the inward force from the eddy current interacting with the field. Heating of the wall causes an increase in blackbody radiation which can preheat the capsule and frozen deuterium–tritium fuel, while wall motion leads to potential misalignment of the lasers at the Hohlraum wall. Limiting these detrimental effects sets requirements on the tolerable magnitude of each effect. We present a nonlinear model for B-field diffusion through an infinitely long thin-walled cylinder with a temperature dependent resistivity, to show that a 15 μm thick wall of pure gold fails to meet these requirements. A new Hohlraum material made from an alloy of Au and Ta has a measured resistivity of ≥60 times that of Au and is shown with the nonlinear model to meet the requirements for magnetization. We compare the nonlinear model to simulations of the actual Hohlraum target using a finite element code which includes temperature-dependent Hohlraum resistivity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Epitaxial Regrowth and Hole Shape Engineering for Photonic Crystal Surface Emitting Lasers (PCSELs)

In the present research, epitaxial regrowth by molecular beam epitaxy (MBE) is investigated as a fabrication process for void-semiconductor photonic crystal (PhC) surface emitting lasers (PCSELs). The PhC is patterned by electron beam lithography (EBL) and inductively coupled plasma (ICP) etch and is subsequently regrown by molecular beam epitaxy to embed a series of voids in bulk semiconductor. Experiments are conducted to investigate the effects of regrowth on air-hole morphology. The resulting voids have a distinct teardrop shape with the radius and depth of the etched hole playing a very critical role in the final regrown void’s dimensions. We demonstrate that specific hole diameters can encourage deposition to the bottom of the voids or to their sidewalls, allowing us to engineer the shape of the void more precisely as is required by the PCSEL design. A 980 nm InGaAs quantum well laser structure is optimized for low threshold lasing at the design wavelength and full device structures are patterned and regrown. An optically pumped PCSEL is demonstrated from this process.

36 MATERIALS SCIENCE↗

Multiple‐Repeated Plasma Surface Treatments for Significantly Improving Bonding Performance of Metal‐Carbon‐Fiber‐Reinforced Thermoplastic Polymer Dissimilar Adhesive Joints

This work investigates how multiple‐repeated plasma surface treatments can significantly enhance adhesively bonded metal‐carbon‐fiber‐reinforced thermoplastic polymer (CFRTP) dissimilar joints, a topic that has been rarely investigated compared to other parameters during the plasma treatment process. By conducting double cantilever beam tests on adhesively bonded AA6061‐carbon‐fiber‐reinforced polyphthalamide (CFRPPA) dissimilar joints, it is shown that the average Mode I specific fracture energy after 20 repetitions of the same plasma treatment, using processing parameters without noticeably changing surface roughness, can be improved and saturated up to almost 2000% compared to non‐treated joints and almost 240% compared to a single plasma treatment commonly used in the literature. The improvement can be attributed to the enhanced chemical bonding at the CFRPPA‐adhesive interface. This study is important for achieving strong bonding performance of CFRTP‐related structural joints using multiple plasma treatments, a simple and effective method.

36 MATERIALS SCIENCE↗

Ultra-rapid, physics-based development pathway for reactor-relevant RF antenna materials

This paper presents a rapid, atomistically-informed, experimental development pathway for fusion reactor-relevant radio frequency (RF) antenna materials in the Cu-Cr-(Nb,Al,Zr) composition system, with the goal of improving upon GRCop-84. RF antennas in a tokamak fusion reactor will face a unique set of challenges as both structural and functional materials. The desired material must simultaneously achieve and maintain high electrical conductivity, high strength, high thermal conductivity, resist high temperatures, possess low nuclear activation, and incur low damage due to neutron bombardment. The GRCop-84 alloy serves as a starting point for iterative improvement, with the desire to reduce or eliminate Nb from the material to minimize nuclear activation. The rapid development pathway makes use of a multi-target combinatorial thick film sputtering process to produce full ternary phase diagrams on a Si wafer substrate. Transient grating spectroscopy (TGS), a laser-ultrasonic method, will determine spatially-varying thermo-elastic properties, while four terminal electrical conductivity measurements will map out the best per- forming regions of the sample for in-depth study at larger length scales. High energy proton and self-ion irradiation emulates the effects of neutron damage on the thermal/electric properties. With rapid turnaround time (∼days) in terms of mapping radiation damage-induced material property changes in the full ternary system, these techniques allow rapid iteration towards an optimal material, testing hundreds of nearby compositions in the time it took to test one. Focused testing of larger, single composition samples (produced in an arc furnace or by laser sintering) provides data on structural and high power RF properties, and validates our thick-film based workflow.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

One-step atmospheric microplasma synthesis of an NMC-type lithium-ion battery cathode

The manufacture of battery cathode materials is the most energy-intensive step in the production of commercial lithium-ion batteries; specifically, the synthesis of the widely used transition metal oxide cathodes can require tens of hours at temperatures exceeding 700 °C. Attempts to limit the reaction time and energy required to form crystalline cathode materials often still include a heating or calcination step. This communication aims to highlight a nascent yet novel synthesis route: a one-step atmospheric microplasma process for synthesizing cathode particles in less than one second. The hollow-tube reactor employed produces crystalline particles measuring 0.1–3 μm in diameter, displays narrow XRD peaks corresponding to the 003, 104, and 101 planes, and exhibits anodic redox behavior at 3.75 V vs. lithium—characteristic of transition-metal oxide cathode materials—all without requiring an additional calcination step.

25 ENERGY STORAGE↗

Integrated TBC/EBC for SiC Fiber Reinforced SiC Matrix Composites for Next Generation Gas Turbines (Final Report)

In this ambitious project, a significant challenge preventing widespread use of ceramic matrix composites in hot section components of gas power generating turbines was addressed. Hot section components made from SiC fiber reinforced SiC matrix composites (SiC/SiC composites), have the potential to achieve a combined cycle energy efficiency of above 65%. To achieve this efficiency, the temperature of the combustion gases on the turbine component surface is expected to reach as high as ~1700ºC (3100ºF). However, SiC/SiC composites suffer from volatilization at high temperature under high velocity steam environment – typical in a turbine hot chamber. This integrated collaborative project, between two research groups at Clemson University and a team of engineers and scientists at GE Gas Power, focused on design, fabrication and evaluation of a new graded environmental barrier coating. Using the excellent compositional tailorability of polymer derived ceramics (PDCs), we developed an integrated EBC/BC that smoothly transitions from bottom SiC/SiC bond interface to hermetic sesquioxide (Y 2 O 3 ) top surface. This smooth compositional transition avoided the sharp CTE mismatch at interfaces to greatly reduce the thermal stress. The developed EBC is compatible with and bonds well with the bond coat that GE uses. The top hermetic oxide surface ensures low oxygen transportation and volatilization rates under the high velocity steam environment. The graded microstructure with increasing sesquioxide concentration also decreases the amount of Si and C elements near the top hermetic sesquioxide layer. Coatings made using a process suitable for manufacturing – atmospheric plasma spraying was demonstrated. The microstructure of coatings made using this process were fully characterized. Finally, the performance of these coatings was investigated under the most demanding conditions for this application. Specifically, high temperature, high velocity steam exposure; thermal shock test; and thermal cycling tests. The graded coatings performed exceptionally well in all these tests. Specific suggestions for future development in this area have also been identified. In addition to the excellent technical progress, this project helped initiate a robust collaboration between the research groups at Clemson and GE Gas Power. It also provided a high-quality learning and mentoring opportunity for the three post-doctoral research associates and two UG students at Clemson University who worked on this project. All proposed tasks, sub-tasks were completed, and all milestones achieved.

03 NATURAL GAS↗

Thin Film Characterization on Cu/SnAg Solder Interface for 3D Packaging Technologies

Copper is a commonly used interconnect metal in microelectronic interconnects due to its exceptional electrical and thermal properties. Particularly in applications of the 2.5 and 3D integration, Cu is utilized in through-silicon-vias (TSVs) and flip chip interconnects between microelectronic chips for providing miniaturization, lower power and higher performance than current 2D packaging approaches. Furthermore, SnAg capped Cu pillars are a common high-density interconnect technology for flip chip bonding. For these interconnects, specific properties of the Cu surface, such as roughness and cleanliness, are an important factor in the process to ensure quality solder bumps. During electroplating, tight processing parameters must be met so that defects are avoided, and high bump uniformity is achieved. An understanding of the interactions at the solder and Cu pillar interface is needed, based on the electroplating parameters, to determine the best method for populating solder on the wafer surface. In this study, surface treatment techniques such as oxygen plasma cleaning were performed on the Cu surfaces and the SnAg plating chemistry for depositing the solder were evaluated through hull cell testing to qualitatively determine the range of current densities to investigate. It was observed that current density while plating played a large role in solder bump deposition morphology. At the higher current densities greater than 60 mA/cm 2 , bump height non-uniformity and dendritic growth are observed and at lower current densities, less than or equal to 60 mA/cm 2 , uniform, continuous bump height occurred.

36 MATERIALS SCIENCE↗

Large Single Crystals of V 1– x Mo x O 2 from a Two-Step Chemical Vapor Transport Synthesis

This article details the synthesis of single crystals with the chemical formulas V 1-x Mo x O 2 ( 0 ≤ x ≤ 0.6) using the chemical vapor transport method at high temperatures (850 to 950 °C). These compounds are of interest due to the special relationship between their structure and electronic properties. Understanding this relationship will help guide future efforts in designing energy-saving devices. While some of these compounds have been synthesized before, this is the first time their synthesis has been reported for such a wide range of compounds in the form of bulk single crystals. The single crystal form is required for detailed characterization of the compounds. The materials were characterized chemically and structurally in order to validate the precise chemical compositions that were reported. Characterization methods included x-ray diffraction, inductively-coupled plasma atomic emission spectroscopy, and electron dispersive spectroscopy. The synthesis method is tunable, and the introduction of multiple steps both overcome the previous chemical challenges precluding synthesis of high molybdenum content crystals and allow for the creation of larger single crystals that were otherwise possible. The crystals synthesized this way are suitable for specialized measurements for determining the precise physical properties and atomic structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Operando XPS in reactive plasmas: The importance of the wall reactions

In this article, advancements in differential pumping and electron optics over the past few decades have enabled x-ray photoelectron spectroscopy (XPS) measurements at (near-)ambient pressures, bridging the pressure gap for characterizing realistic sample chemistries. Recently, we have demonstrated the capabilities of an ambient pressure XPS setup for in situ plasma environment measurements, allowing plasma-surface interactions to be studied in operando rather than using the traditional before-and-after analysis approach. This new “plasma-XPS” technique facilitates the identification of reaction intermediates critical for understanding plasma-assisted surface processes relevant to semiconductor nanomanufacturing, such as physical vapor deposition, etching, atomic layer deposition, and many other plasma applications. In this paper, we apply the plasma-XPS approach to monitor real-time surface chemical changes on a model Ag(111) single crystal exposed to oxidizing and reducing plasmas. We correlate surface-sensitive data with concurrent gas-phase XPS measurements and residual gas mass-spectrum analysis of species generated during plasma exposure, highlighting the significant role of plasma-induced chamber wall reactions. Ultimately, we demonstrate that plasma-XPS provides comprehensive insights into both surface and gas-phase chemistry, establishing it as a versatile and dynamic characterization tool with broad applications in microelectronics research. Finally, we outline potential enhancements and future metrology directions to advance plasma-XPS investigations further.

36 MATERIALS SCIENCE↗

Property enhancement of CoCrNi medium-entropy alloy by introducing nano-scale features

CoCrNi -medium-entropy alloy (MEA) has been widely investigated due to its superior mechanical properties that overcome strength-ductility tradeoff. Here we show further property enhancement of CoCrNi MEA by introducing nano-scale features. Both CoCrNi and oxide dispersion strengthened (ODS) CoCrNi are fabricated by mechanical alloying and spark plasma sintering. Microstructural characterization and mechanical testing of these nanostructured MEAs revealed that the nano-scale features significantly improves the strength of the alloys. In ODS-CoCrNi MEA, Y 2 Ti 2 O 7 oxides with an average diameter of 7.3 ± 3.2 nm are incoherent with the matrix, and a specific orientation relationship exists between Y 2 Ti 2 O 7 and the matrix, which is [011] Y 2 Ti 2 O 7 //[011]Matrix, (400) Y 2 Ti 2 O 7 //(200)Matrix and ($22\bar2$) Y 2 Ti 2 O 7 //($11\bar1$)Matrix. The recrystallization and grain growth processes are effectively suppressed by the introduction of Y 2 Ti 2 O 7 nanoparticles. Strengthening mechanism analyses indicate that the strength improvement of ODS-CoCrNi is mainly ascribed to the precipitation strengthening of Y 2 Ti 2 O 7 .

36 MATERIALS SCIENCE↗

Electron generation and multiplication at the initial stage of nanosecond breakdown in water

Electrical breakdown of liquid dielectrics under nanosecond pulsed high voltage has been investigated extensively in the last decade. Prior studies have focused on either experimental characterization of the breakdown process and discharge plasma or formulation/verification of the electrostrictive cavitation mechanism of the breakdown initiation. There remain knowledge gaps toward a clear physical picture of how the first plasma is generated in a region saturated by nanoscale cavities created by electrostrictive forces in inhomogeneous fields at the nanosecond timescale. Initial plasma results from the multiplication of primary electrons that gain energy collisionlessly in the cavities to cause collisional ionization of water molecules on the cavity walls. This paper quantitatively discusses the possible sources of primary electrons that seed the plasma discharge. Electron detachment from hydroxide is shown to be the most probable and sustainable electron source. Using numerical modeling, this study demonstrates the plausibility of an electron multiplication mechanism involving two neighboring cavities. The drift of hydrated electrons from one cavity to the next is the rate-limiting step and sets the minimum electric field requirement. Furthermore, this work will inform subsequent experimental studies and have implications in various applications such as plasma sources in biomedical applications, cavitation study, and insulation of pulsed power equipment.

42 ENGINEERING↗

Development of Multi-Filament Textured-Powder Bi-2212/Ag Wire With Enhanced Local Area Ratio

The performance and cost of Bi-2212/Ag wire is limited by the large fraction of Ag matrix (~3:1) that is required in the oxide-powder-in-tube fabrication process. An alternative fabrication process is being developed in which fine-powder Bi-2212 is uniaxially compressed to form bars with a thin Ag foil sheath. The fine powder naturally textures (aligns the a-b planes perpendicular to the direction of compaction) with texture >80% using 200 MPa compression. A billet is formed by stacking trapezoidal- cross-section bars in a symmetric 8-12-16 pattern around an Ag rod and enclosed in an Ag-wall extrusion can. Here, the billet is extruded and drawn to fine wire. Results are presented on present status of the development and testing.

17 WIND ENERGY↗

Hot-tail electrons’ impact on assimilation and injection penetration of D2 shattered pellet injections

The assimilation and the penetration of injected materials play significant roles in the mitigation efficiency of shattered pellet injection (SPI) as a disruption mitigation system (DMS), hence an accurate description of the fragment ablation rate is desirable. Current mainstream 3D MHD codes modelling SPIs mostly assume instantaneous thermalization between the previously hot ambient electrons and the newly released cold electrons. This could result in underestimation of the ablation rate if the hot electron thermalization time is comparable or even longer than the fragment flying time across flux tubes, putting the validity of these 3D SPI simulations into question. To resolve this doubt, we, in this study, investigate the thermalization dynamics and the overall hot-electron impact. The finite-time collisional thermalization of hot-tail electrons in a rapidly cooling plasma, as well as the so-called ‘self-limiting’ effect are considered. The former effect tends to deplete the colder population within a hot-tail species, while the latter is found to preferentially deplete the higher energy population. The combined result is found to cause an almost self-similar decay of the hot electron distribution function, while its shape does not deviate much from that of Maxwellian distribution and the mean energy does not change much during the thermalization process. Based on this observation, axisymmetric JOREK D2 SPI simulations were carried out with additional hot-tail contribution to evaluate their overall impact onto the injection assimilation and penetration. It is found that the hot-tail effect indeed causes enhanced assimilation and shallower penetration, although the overall effect depends on the exact injection configuration, with the slow injection showing negligible hot-tail effect while the fast single non-shattered pellet case shows drastic hot-tail ablation enhancement. For ITER-like SPI parameters, there is no significant deviation in the total assimilation, but some deviation in the injection penetration is observed for the fast injection velocity cases.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Modeling ablator defects as a source of mix in high-performance implosions at the National Ignition Facility

Recent indirect drive inertial confinement fusion implosions on the National Ignition Facility (NIF) [Spaeth et al., Fusion Sci. Technol. 69, 25 (2016)] have crossed the threshold of ignition. However, performance has been variable due to several factors. One of the leading sources of variability is the quality of the high-density carbon (HDC) shells used as ablators in these experiments. In particular, these shells can have a number of defects that have been found to correlate with the appearance of ablator mix into the hot spot and a degradation in nuclear yield. These defects include pits on the ablator surface, voids in the ablator bulk, high-Z debris from the Hohlraum wall that adheres to the capsule surface, and finally the inherent granular micro-structure of the crystalline HDC itself. This paper summarizes high-resolution modeling of each of these mix sources in two recent high-performance NIF implosion experiments. The simulated impact from a range of individual capsule defects is found to be broadly consistent with the trends seen in experiment, lending credence to the modeling results and the details of the mixing process that they reveal. Interestingly, modeling of the micro-structure inherent to HDC shows that this perturbation source results in considerable mixing of the deuterium–tritium fuel with ablator material during the implosion. The reduction in fuel compression from this mix results in an approximately factor of two reduction in neutron yield in current implosions and emphasizes the importance of mitigating this significant performance degradation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Evidence of gas phase nucleation of nanodiamond in microwave plasma assisted chemical vapor deposition

The mechanism of ballas-like nanodiamond formation still remains elusive, and this work attempts to analyze its formation in the framework of activation energy (Ea) of nanodiamond films grown from a H2/CH4 plasma in a 2.45 GHz chemical vapor deposition system. The Ea was calculated from the Arrhenius equation corresponding to the thickness growth rate using substrate temperature (∼1000−1300 K) in all the calculations. While the calculated values matched with the Ea for nanodiamond formation throughout the literature, these values of ∼10 kcal/mol were lower compared to ∼15–25 kcal/mol for standard single crystal diamond (SCD) formation, concluding thus far that the energetics and processes involved were different. Further, the substrate preparation and sample collection method were modified while keeping the growth parameters constant. Unseeded Si substrate was physically separated from the plasma discharge by a molybdenum disk with a pinhole drilled in it. Small quantity of a sample substance was collected on the substrate. The sample was characterized by electron microscopy and Raman spectroscopy, confirming it to be nanodiamond, thus suggesting that nanodiamond self-nucleated in the plasma and flowed to the substrate that acted as a mere collection plate. It is hypothesized then, if nanodiamond nucleates in gas phase, gas temperature has to be used in the Arrhenius analysis. The Ea values for all the nanodiamond films were re-calculated using the simulated gas temperature (∼1500−2000 K) obtained from a simple H2/CH4 plasma model, giving new values within the range characteristic to SCD formation. Based on these findings, a unified growth mechanism for nanodiamond and SCD is proposed, concluding that the rate-limiting reactions for nanodiamond and SCD formation are the same.

Materials Science↗

Interface-sensitive microwave loss in superconducting tantalum films sputtered on c-plane sapphire

Quantum coherence in superconducting circuits has increased steadily over the last decades because of a growing understanding of the various loss mechanisms. Recently, tantalum (Ta) emerged as a promising material to address microscopic sources of loss found on niobium (Nb) or aluminum (Al) surfaces. However, the effects of film and interface microstructure on low-temperature microwave loss are still not well understood. Here, in this study, we present a systematic study of the structural and electrical properties of Ta and Nb films sputtered on c-plane sapphire at varying growth temperatures. As growth temperature was increased, our results show that the onset of epitaxial growth of α -phase Ta correlates with lower Ta surface roughness, higher critical temperature, and higher residual resistivity ratio, but surprisingly also correlates with a significant increase in loss at microwave frequency. Notably, this high level of loss is not observed in Nb films prepared in the same way and having very similar structure. By experimentally controlling the surface on which the Ta film is nucleated, we determine that the source of loss was only present in samples having an epitaxial Ta/sapphire interface and show that it was apparently mitigated by either growing a thin, epitaxial Nb interlayer between the Ta film and the substrate or by intentionally treating, and effectively damaging, the sapphire surface with an in situ argon plasma before Ta growth. In addition to elucidating this interfacial microwave loss, this work provides adequate process details to aid reproducible growth of low-loss Ta films across fabrication facilities.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Single particle trace element analysis of uranium oxide standards with laser-induced breakdown spectroscopy

Femtosecond Laser-Induced Breakdown Spectroscopy (LIBS) was used to analyze over 1000 individual particles of uranium oxide trace element standard CRM124. Intra-granular analysis showed elemental concentrations were consistent across different surface locations on each uranium grain. However, inter-granular comparison revealed large heterogeneity between different grains of the same sample. By comparing the distribution of elemental concentrations across the particle populations, we were able to correctly identify a manufacturing process involving wet chemistry, rather than a dry mixing of two powders to give an overall chemical average. In conclusion, this demonstrates the utility of LIBS as a large-scale single particle analysis tool for nuclear forensics.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗