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At least 1,783 records · Page 99

Bubble Combustion

A method of energy production that is capable of low pollutant emissions is fundamental to one of the four pillars of NASA s Aeronautics Blueprint: Revolutionary Vehicles. Bubble combustion, a new engine technology currently being developed at Glenn Research Center promises to provide low emissions combustion in support of NASA s vision under the Emissions Element because it generates power, while minimizing the production of carbon dioxide (CO2) and nitrous oxides (NOx), both known to be Greenhouse gases. and allows the use of alternative fuels such as corn oil, low-grade fuels, and even used motor oil. Bubble combustion is analogous to the inverse of spray combustion: the difference between bubble and spray combustion is that spray combustion is spraying a liquid in to a gas to form droplets, whereas bubble combustion involves injecting a gas into a liquid to form gaseous bubbles. In bubble combustion, the process for the ignition of the bubbles takes place on a time scale of less than a nanosecond and begins with acoustic waves perturbing each bubble. This perturbation causes the local pressure to drop below the vapor pressure of the liquid thus producing cavitation in which the bubble diameter grows, and upon reversal of the oscillating pressure field, the bubble then collapses rapidly with the aid of the high surface tension forces acting on the wall of the bubble. The rapid and violent collapse causes the temperatures inside the bubbles to soar as a result of adiabatic heating. As the temperatures rise, the gaseous contents of the bubble ignite with the bubble itself serving as its own combustion chamber. After ignition, this is the time in the bubble s life cycle where power is generated, and CO2, and NOx among other species, are produced. However, the pollutants CO2 and NOx are absorbed into the surrounding liquid. The importance of bubble combustion is that it generates power using a simple and compact device. We conducted a parametric study using CAVCHEM, a computational model developed at Glenn, that simulates the cavitational collapse of a single bubble in a liquid (water) and the subsequent combustion of the gaseous contents inside the bubble. The model solves the time-dependent, compressible Navier-Stokes equations in one-dimension with finite-rate chemical kinetics using the CHEMKIN package. Specifically, parameters such as frequency, pressure, bubble radius, and the equivalence ratio were varied while examining their effect on the maximum temperature, radius, and chemical species. These studies indicate that the radius of the bubble is perhaps the most critical parameter governing bubble combustion dynamics and its efficiency. Based on the results of the parametric studies, we plan on conducting experiments to study the effect of ultrasonic perturbations on the bubble generation process with respect to the bubble radius and size distribution.

Corrigan, Jackie↗

Computational Investigation of the Chemical Bond between An(III) Ions and Soft-Donor Ligands

The chemical bonding of actinide ions with arene and borohydride ligands is explored via quantum chemical methods to understand how the transuranium elements interact with softdonor ligands. Specifically, the [An(C 6 Me 6 )(BH 4 ) 3 ] complexes (An = U, Np, and Pu) and their reduced congeners are studied. Density functional theory (DFT) shows that the metal–ligand interactions in the neutral complexes are governed by electrostatic interactions. Both DFT and complete active space (CASSCF) results show that as one moves from U to Pu, the 5f-orbitals are stabilized leading to a poorer energy match with the ligand orbitals. This contributes to progressively weaker metal-arene and metal-borohydride interactions across the series due to a decrease in energy-driven covalency. A reduction in orbital contributions to bonding is obtained for the transuranium-arene interactions as well. Upon reduction, the arene is reduced, forming a δ-bond. This causes the An–arene distances to contract by 0.1–0.2 Å compared to the neutral complexes. The ground state is assigned as the intermediate-spin state where the arene radical is antiferromagnetically coupled to the metal-centered f-electrons in Np and Pu. On the other hand, the ferromagnetically and antiferromagnetically coupled states are close in energy in the uranium complex, but do not mix when spin– orbit coupling is included using a state-interaction approach (SO-CASPT2). The population of the CASSCF δ*-antibonding natural orbital increases from U to Pu consistent with the increased An–arene distances, weaker interactions, and decreasing covalency across the series. Although the An–B distance increases by ca. 0.06 Å upon reduction, both the neutral and reduced species involve an An(III)–borohydride bond and as such are qualitatively similar. The Np complexes can be assigned to have slightly weaker bonding than the uranium analogs but are overall “uranium-like”. The Pu complexes are predicted to have less covalent contributions to bonding in both the Pu–arene and Pu–borohydride interactions; however, the Pu–arene interaction is predicted to be particularly weak.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural Aspects of Neutron Survival Probabilities

The neutron survival probability (and related quantities including probabilities of extinction and initiation) is a central element of the broader stochastic theory of neutron populations and finds application in fields including reactor start-up, analysis of reactor power bursts and criticality accidents, and safeguards. In a full neutron transport formulation, the equation governing the single-neutron survival probability is a backward or adjoint-like integro-partial differential equation with the added complexity of being highly nonlinear. Analogous formulations of this equation exist in the context of many approximate theories of neutron transport, with the point kinetics formulation having received significant theoretical attention since the 1940s. This work continues this tradition by providing a novel analysis of the single-neutron survival probability equation using the tools of boundary layer theory. The analysis reveals that the “fully dynamic” solution of the single-neutron survival probability equation—and some key probability distributions derived from it—may be cast as a singular perturbation around the underlying quasi-static single-neutron probability of initiation. In this perturbation solution, the expansion parameter is the ratio of the neutron generation time to a macroscopic time scale characterizing the overall system evolution; this interpretation illuminates some of the fundamental structural aspects of neutron survival phenomena.

97 MATHEMATICS AND COMPUTING↗

SIM Planetquest Science and Technology: A Status Report

Optical interferometry will open new vistas for astronomy over the next decade. The Space Interferometry Mission (SIM-PlanetQuest), operating unfettered by the Earth's atmosphere, will offer unprecedented astrometric precision that promises the discovery of Earth-analog extra-solar planets as well as a wealth of important astrophysics. Results from SIM will permit the determination of stellar masses to accuracies of 2% or better for objects ranging from brown dwarfs through main sequence stars to evolved white dwarfs, neutron stars, and black holes. Studies of star clusters will yield age determinations and internal dynamics. Microlensing measurements will present the mass spectrum of the Milky Way internal to the Sun while proper motion surveys will show the Sun's orbital radius and speed. Studies of the Galaxy's halo component and companion dwarf galaxies permit the determination of the Milky Way's mass distribution, including its Dark Matter component and the mass distribution and Dark Matter component of the Local Group. Cosmology benefits from precision (1-2%) determination of distances to Cepheid and RR Lyrae standard candles. The emission mechanism of supermassive black holes will be investigated. Finally, radio and optical celestial reference frames will be tied together by an improvement of two orders of magnitude. Optical interferometers present severe technological challenges. The Jet Propulsion Laboratory, with the support of Lockheed Martin Advanced Technology Center (LM ATC) and Northrop Grumman Space Technology (NGST), has addressed these challenges with a technology development program that is now complete. The requirements for SIM have been satisfied, based on outside peer review, using a series of laboratory tests and appropriate computer simulations: laser metrology systems perform with 10 picometer precision; mechanical vibrations have been controlled to nanometers, demonstrating orders of magnitude disturbance rejection; and knowledge of component positions throughout the whole test assembly has been demonstrated to the required picometer level. Technology transfer to the SIM flight team is now well along.

astrometry↗

Asymptotic-preserving gyrokinetic implicit particle-orbit integrator for arbitrary electromagnetic fields

We extend the asymptotic preserving and energy conserving time integrator for charged-particle motion developed in Ricketson and Chacón (2020) to include finite Larmor-radius (FLR) effects in the presence of electric-field length-scales comparable to the particle gyro-radius (the gyro-kinetic limit). We introduce two modifications to the earlier scheme. The first is the explicit gyro-averaging of the electric field at the half time-step, along with an analogous modification to the current deposition, which we show preserves total energy conservation in implicit PIC schemes. The number of gyrophase samples is chosen adaptively, ensuring proper averaging for large timesteps and the recovery of full-orbit dynamics in the small time-step limit. The second modification is an alternating large and small time-step strategy that ensures the particle trajectory samples gyrophases evenly. We show that this strategy relaxes the time-step restrictions on the scheme, allowing even larger speed-ups than previously achievable. We demonstrate the new method with several single-particle motion tests in a variety of electromagnetic field configurations featuring gyro-scale variation in the electric field. Finally, the results demonstrate the advertised ability to capture FLR effects accurately even when significantly stepping over the gyration time-scale.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Chiral population analysis: a real space visualization of X-ray circular dichroism

The microscopic understanding of probing and controlling molecular chirality is of considerable interest. Numerous spectroscopic techniques are capable of monitoring molecular asymmetry and its consequences, ranging from the infrared to the X-ray regime. Resonant X-rays have long been used to investigate local atomic sites within molecules thanks to the localized nature of core electronic transitions. These techniques can be used to determine the extent to which chirality is a local versus a delocalized property. However, how to systematically partition dichroic contributions from the point of view of electronic structure simulations remains an open question. Here, we introduce the concept of chiral population analysis that connects chirality to the atomic orbital picture. In analogy with Mulliken population analysis, which assigns charges to atomic orbitals, chiral populations allow the dichroic response to be distributed among the participating atomic orbitals. This decomposition can be further visualized in real space by representing it in terms of isosurface plots, providing an intuitive way to connect the dichroic response to its origins. Thus chiral population analysis can be particularly useful to assess the extent to which a given electronic transition is sensitive to chirality as a local or global feature of the molecular geometry.

36 MATERIALS SCIENCE↗

A New "Cloud Mode" for the AERONET

A key to predicting climate change is to observe an understand the global distribution of clouds and their physical properties such as optical thickness and droplet size. Since clouds change rapidly over short time and space intervals, they are difficult to simulate in computer models. But it is essential that global climate models predict realistic spatial and temporal distribution of cloud optical depth. The best way to verify these distributions is to infer optical depth from global coverage satellite data. However, satellite methods have many sources of uncertainty; thus, independent and reliable ground-based estimates are essential for validation. For aerosol, there is the AERONET - a ground based monitoring network that consists of identical multi-channel radiometers for assessing aerosol optical properties and validating their satellite retrievals. In addition to AEROSOL, we want the network monitoring CLOUD optical properties. It will use AERONET "time" (inappropriate for aerosol studies) to make basic new measurements related to cloud physics. In the presentation we will report on a new technique that retrieves cloud optical thickness for even broken clouds above green vegetation from surface measurements of zenith radiance in the visible (VIS) and near-IR (NIR) spectral regions. The idea of the method is simple: since green vegetation reflects 40-50% of incoming radiation in the NIR and only 5-10% in the VIS region, ground measurements under thin clouds have little spectral contrast between VIS and NIR, while thick clouds reflect much more of the surface-reflected radiation in the NIR than in VIS. Based on this idea, we use a combination of measurements (spectral indices) in VIS and NIR to estimate cloud optical thickness. By analogy with NDVI, the simplest index that can be defined is the Normalized Difference Cloud Index (NDCI) which is a ratio between the difference and the sum of two radiances measured for two narrow spectral bands in VIS and NIR.

Marshak, Alexander↗

Advanced Reactor Safeguards & Security Program: Cybersecurity Scenarios

The use of digital control systems and automation in advanced nuclear power systems introduces different types of vulnerabilities compared to legacy (i.e. analog) control systems that cyber adversaries can exploit. These vulnerabilities pose a challenge to reactor operators and cyber operations staff due to the dynamic nature of the event in which a human response or a lack of response can potentially evolve into a worsening plant condition. Using the Department of Homeland Security Cyber and Infrastructure Security Agency’s (CISA) critical infrastructure exercise framework, this document presents several cyber security scenarios typical of digital control systems that could be used in advanced reactor designs. These scenarios can be used in tabletop exercises to evaluate cyber security posture or conduct training on different aspects of cyber security, including detection, threat hunting using indicators of compromise, evaluating incident response, risk mitigation, incident reporting, information sharing and recovery.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Virtual Instrumentation for a Fiber-Optics-Based Artificial Nerve

A LabView-based computer interface for fiber-optic artificial nerves has been devised as a Masters thesis project. This project involves the use of outputs from wavelength multiplexed optical fiber sensors (artificial nerves), which are capable of producing dense optical data outputs for physical measurements. The potential advantages of using optical fiber sensors for sensory function restoration is the fact that well defined WDM-modulated signals can be transmitted to and from the sensing region allowing networked units to replace low-level nerve functions for persons desirous of "intelligent artificial limbs." Various FO sensors can be designed with high sensitivity and the ability to be interfaced with a wide range of devices including miniature shielded electrical conversion units. Our Virtual Instrument (VI) interface software package was developed using LabView's "Laboratory Virtual Instrument Engineering Workbench" package. The virtual instrument has been configured to arrange and encode the data to develop an intelligent response in the form of encoded digitized signal outputs. The architectural layout of our nervous system is such that different touch stimuli from different artificial fiber-optic nerve points correspond to gratings of a distinct resonant wavelength and physical location along the optical fiber. Thus, when an automated, tunable diode laser sends scans, the wavelength spectrum of the artificial nerve, it triggers responses that are encoded with different touch stimuli by way wavelength shifts in the reflected Bragg resonances. The reflected light is detected and a resulting analog signal is fed into ADC1 board and DAQ card. Finally, the software has been written such that the experimenter is able to set the response range during data acquisition.

Lyons, Donald R.↗

Generalized Jeans' Escape of Pick-Up Ions in Quasi-Linear Relaxation

Jeans escape is a well-validated formulation of upper atmospheric escape that we have generalized to estimate plasma escape from ionospheres. It involves the computation of the parts of particle velocity space that are unbound by the gravitational potential at the exobase, followed by a calculation of the flux carried by such unbound particles as they escape from the potential well. To generalize this approach for ions, we superposed an electrostatic ambipolar potential and a centrifugal potential, for motions across and along a divergent magnetic field. We then considered how the presence of superthermal electrons, produced by precipitating auroral primary electrons, controls the ambipolar potential. We also showed that the centrifugal potential plays a small role in controlling the mass escape flux from the terrestrial ionosphere. We then applied the transverse ion velocity distribution produced when ions, picked up by supersonic (i.e., auroral) ionospheric convection, relax via quasi-linear diffusion, as estimated for cometary comas [1]. The results provide a theoretical basis for observed ion escape response to electromagnetic and kinetic energy sources. They also suggest that super-sonic but sub-Alfvenic flow, with ion pick-up, is a unique and important regime of ion-neutral coupling, in which plasma wave-particle interactions are driven by ion-neutral collisions at densities for which the collision frequency falls near or below the gyro-frequency. As another possible illustration of this process, the heliopause ribbon discovered by the IBEX mission involves interactions between the solar wind ions and the interstellar neutral gas, in a regime that may be analogous [2].

Moore, T. E.↗

Biosensors for EVA: Improved Instrumentation for Ground-based Studies

During lunar excursions in the EVA suit, real-time measurement of metabolic rate is required to manage consumables and guide activities to ensure safe return to the base. Metabolic rate, or oxygen consumption (VO2), is normally measured from pulmonary parameters but cannot be determined with standard techniques in the oxygen-rich environment of a spacesuit. Our group has developed novel near infrared spectroscopic (NIRS) methods to calculate muscle oxygen saturation (SmO 2), hematocrit, and pH, and we recently demonstrated that we can use our NIRS sensor to measure VO 2 on the leg during cycling. Our NSBRI project has 4 objectives: (1) increase the accuracy of the metabolic rate calculation through improved prediction of stroke volume; (2) investigate the relative contributions of calf and thigh oxygen consumption to metabolic rate calculation for walking and running; (3) demonstrate that the NIRS-based noninvasive metabolic rate methodology is sensitive enough to detect decrement in VO 2 in a space analog; and (4) improve instrumentation to allow testing within a spacesuit. Over the past year we have made progress on all four objectives, but the most significant progress was made in improving the instrumentation. The NIRS system currently in use at JSC is based on fiber optics technology. Optical fiber bundles are used to deliver light from a light source in the monitor to the patient, and light reflected back from the patient s muscle to the monitor for spectroscopic analysis. The fiber optic cables are large and fragile, and there is no way to get them in and out of the test spacesuit used for ground-based studies. With complimentary funding from the US Army, we undertook a complete redesign of the sensor and control electronics to build a novel system small enough to be used within the spacesuit and portable enough to be used by a combat medic. In the new system the filament lamp used in the fiber optic system was replaced with a novel broadband near infrared LED light source. The compact grating spectrometer was replaced with a chip-scale spectrometer. With this new design, the sensor is 4 in 2 in 0.5 in, weighs 60 g, and no fiber optic cables are needed. The sensor, which contains the light source and the spectrometer, is adhered directly to the skin with medical grade adhesive. The sensor can be powered via the USB port of the laptop computer that controls the sensor operation. Alternatively, for studies in the spacesuit, the sensor can be powered by a small battery pack and operated by an ultra-portable hand-held computer. Both the handheld computer and battery pack will easily fit within the PLSS of the test spacesuit. System automation was significantly improved, to add features suggested by our colleagues in the Cardiovascular Laboratory and the NASA JSC Exercise Physiology and Countermeasures Project. The functionality and portability of this system were demonstrated in our UMass laboratory.

Soller, B.↗

Importance of Dispersion in the Molecular Geometries of Mn(III) Spin-Crossover Complexes

The computational investigation of the molecular geometries of a pair of manganese(III) spin-crossover complexes is reported. For the geometry of the quintet high-spin state, density functionals significantly overestimate Mn–Namine bond distances, although the geometry for the triplet intermediate-spin state is well described. Here, comparisons with several wave function-based methods demonstrate that this error is due to the limited ability of commonly used density functionals to recover dispersion beyond a certain extent. Among the methods employed for geometry optimization, restricted open-shell Møller–Plesset perturbation theory (MP2) appropriately describes the high-spin geometry but results in a slightly shorter Mn–O distance in both spin states. On the other hand, extended multistate complete active space second-order perturbation theory (XMS-CASPT2) provides a good description of the geometry for the intermediate-spin state but also sufficiently recovers dispersion, performing well for the high-spin state. Despite the fact that the electronic structure of both spin states is dominated by one-electron configuration, XMS-CASPT2 offers a balanced approach, leading to molecular geometries with much better agreement with experiment than MP2 and DFT. A scan along the Mn–N amine bond demonstrates that for these complexes coupled cluster methods (i.e., DLPNO-CCSD(T)) also yield bond distances in agreement with experiment while multiconfiguration pair density functional theory (MC-PDFT) is unable to recover dispersion well enough, analogous to single-reference DFT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ocean Turbulence, III: New GISS Vertical Mixing Scheme

We have found a new way to express the solutions of the RSM (Reynolds Stress Model) equations that allows us to present the turbulent diffusivities for heat, salt and momentum in a way that is considerably simpler and thus easier to implement than in previous work. The RSM provides the dimensionless mixing efficiencies Gamma-alpha (alpha stands for heat, salt and momentum). However, to compute the diffusivities, one needs additional information, specifically, the dissipation Epsilon. Since a dynamic equation for the latter that includes the physical processes relevant to the ocean is still not available, one must resort to different sources of information outside the RSM to obtain a complete Mixing Scheme usable in OGCMs. As for the RSM results, we show that the Gamma-alpha s are functions of both Ri and Rq (Richardson number and density ratio representing double diffusion, DD); the Gamma-alpha are different for heat, salt and momentum; in the case of heat, the traditional value Gamma-h = 0.2 is valid only in the presence of strong shear (when DD is inoperative) while when shear subsides, NATRE data show that Gamma-h can be three times as large, a result that we reproduce. The salt Gamma-s is given in terms of Gamma-h. The momentum Gamma-m has thus far been guessed with different prescriptions while the RSM provides a well defined expression for Gamma-m(Ri,R-rho). Having tested Gamma-h, we then test the momentum Gamma-m by showing that the turbulent Prandtl number Gamma-m/Gamma-h vs. Ri reproduces the available data quite well. As for the dissipation epsilon, we use different representations, one for the mixed layer (ML), one for the thermocline and one for the ocean;s bottom. For the ML, we adopt a procedure analogous to the one successfully used in PB (planetary boundary layer) studies; for the thermocline, we employ an expression for the variable epsilon/N(exp 2) from studies of the internal gravity waves spectra which includes a latitude dependence; for the ocean bottom, we adopt the enhanced bottom diffusivity expression used by previous authors but with a state of the art internal tidal energy formulation and replace the fixed Gamma-alpha = 0.2 with the RSM result that brings into the problem the Ri, R-rho dependence of the Gamma-alpha; the unresolved bottom drag, which has thus far been either ignored or modeled with heuristic relations, is modeled using a formalism we previously developed and tested in PBL studies. We carried out several tests without an OGCM. Prandtl and flux Richardson numbers vs. Ri. The RSM model reproduces both types of data satisfactorily. DD and Mixing efficiency Gamma-h(Ri,Rq). The RSM model reproduces well the NATRE data. Bimodal epsilon-distribution. NATRE data show that epsilon (Ri < 1) approximately equals 10epsilon(Ri > 1), which our model reproduces. Heat to salt flux ratio. In the Ri much greater than 1 regime, the RSM predictions reproduce the data satisfactorily. NATRE mass diffusivity. The z-profile of the mass diffusivity reproduces well the measurements at NATRE. The local form of the mixing scheme is algebraic with one cubic equation to solve.

Canuto, V. M.↗

Low-order preconditioning of the Stokes equations

A well-known strategy for building effective preconditioners for higher-order discretizations of some PDEs, such as Poisson's equation, is to leverage effective preconditioners for their low-order analogs. In this work, we show that high-quality preconditioners can also be derived for the Taylor–Hood discretization of the Stokes equations in much the same manner. In particular, we investigate the use of geometric multigrid based on the Q 1 iso Q 2 /Q 1 discretization of the Stokes operator as a preconditioner for the Q 2 /Q 1 discretization of the Stokes system. We utilize local Fourier analysis to optimize the damping parameters for Vanka and Braess–Sarazin relaxation schemes and to achieve robust convergence. Furthermore, these results are then verified and compared against the measured multigrid performance. While geometric multigrid can be applied directly to the Q 2 /Q 1 system, our ultimate motivation is to apply algebraic multigrid within solvers for Q 2 /Q 1 systems via the Q 1 iso Q 2 /Q 1 discretization, which will be considered in a companion paper.

97 MATHEMATICS AND COMPUTING↗

Losses of CO and CO 2 upon collision-activated dissociation of substituted 2-methoxyphenoxides after methyl radical loss

Some deprotonated, substituted 2-methoxyphenols fragment by methyl radical loss followed by competing losses of CO and CO 2 upon collisional activation in linear quadrupole ion trap mass spectrometers. These reactions were examined experimentally and computationally in order to determine their mechanisms. For deprotonated vanillin, the CO loss was found to involve ring contraction, with the highest free energy barrier of 58.0 kcal mol -1 (for the syn rotamer; here, syn refers to the relationship between the aldehyde oxygen atom and the oxygen atom of the methoxy group) for the entire process. The atoms lost in this fragmentation are the oxygen atom that was bound to the first eliminated methyl group and the aromatic carbon atom bound to this oxygen. Examination of carbon-13 labeled vanillin supports these assignments. Examination of several model compounds revealed that this reaction requires the presence of an electron-withdrawing substituent in the para-position relative to the phenol moiety. In contrast, the CO 2 loss from deprotonated vanillin occurs via ring opening followed by re-cyclization and then ring contraction, leading to the loss of CO 2 in a process wherein the highest free energy barrier is 84.5 kcal mol -1 (for the syn isomer). The atoms lost in this fragmentation are the carbon and oxygen atoms from the phenoxide group and the oxygen atom that was bound to the first eliminated methyl group, which is supported by examination of carbon-13 labeled vanillin. Despite the higher total free energy requirement, the CO 2 loss is competitive with CO loss, possibly due to favorable entropy and low activation energy (free energy barrier of 48.9 kcal mol -1 ) for the first reaction step (the analogous value for CO loss is 58.0 kcal mol -1 ). The extent of CO 2 loss is strongly affected by substituents – it either is not observed or is very slow for the other compounds studied here. For example, it is substantially less favorable than CO loss (highest free energy barrier 60.9 kcal mol -1 ) for deprotonated acetovanillone for which the first reaction step for CO 2 loss has a substantially greater free energy barrier (60.6 kcal mol-1) than for vanillin.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Itinerant Magnetism in Hydride-Synthesized CaCo 12 B 6

A new compound in the underexplored Ca–Co–B phase space has been discovered, validating high-throughput computations from the Open Quantum Materials Database, which predicted thermodynamic stability for CaCo 12 B 6 in the SrNi 12 B 6 structure type. The synthetic effects of different boron precursors and the advantages of using CaH 2 instead of Ca metal were demonstrated by the short synthesis duration and high purity of CaCo 12 B 6 , in contrast with traditional synthesis routes. Powder X-ray diffraction (PXRD) confirmed that CaCo 12 B 6 shares the SrNi 12 B 6 structure ( R $\bar{3}$m (#166), a = 9.469(4) Å, c = 7.468(2) Å, Z = 3) and is water- and air-stable. High-temperature in situ PXRD indicates that CaCo 12 B 6 is stable below 1050 K under vacuum in a silica capillary. CaCo 12 B 6 decomposes between 693 and 773 K during spark-plasma sintering. Density functional theory calculations indicate that CaCo 12 B 6 is metallic with a ferromagnetic ground state. X-ray absorption near-edge spectroscopy and Bader charge analysis indicate that Co atoms in CaCo 12 B 6 lack ionic character. Magnetometry reveals room-temperature paramagnetism with μ eff = 1.7(1)μ B per Co atom and a Weiss constant of +190(10)K. Ferromagnetic ordering occurs below 172(1)K, resulting in a saturation moment of 0.46 μ B per Co atom. Our findings demonstrate that the hydride route is a viable strategy for discovery of new ternary alkaline-earth-transition metal borides analogous to rare-earth-containing counterparts.

diffraction↗

Symmetry structure of a Riccati equation appearing in penetration mechanics

In the design of projectile penetration experiments a matter of considerable interest is scaling: that is, the potential relevance of small-scale experiments to their full-scale counterparts, in a manner analogous to that most often encountered in the context of fluid mechanics. From the theoretical standpoint, phenomena associated with scaling and scalability can be assessed using the well-established tools of dimensional analysis and the Buckingham-Pi Theorem. However, the familiar precepts of dimensional analysis are themselves a specific manifestation of the broader group invariance properties or symmetries of a mathematical model. Here, this work explores these notions – that is, dimensional analysis, the conditions for realizing complete similarity, and any additional symmetry structures – in the context of a Riccati differential equation appearing in the context of penetration mechanics. The aim of the investigation is twofold: 1) to complement existing empirical considerations with a concrete theoretical basis, and 2) to provide a deeper theoretical understanding of the projectile penetration model and its many implications.

97 MATHEMATICS AND COMPUTING↗

Mica filled polyetherketoneketones for material extrusion 3D printing

Polyetherketoneketone (PEKK) has superior physical properties to most available thermoplastics compatible with material extrusion-based 3D printing, including analogs in the polyaryletherketone (PAEK) family. To date, the performance of fused filament fabrication (FFF) compatible PEKK has been detailed primarily as a function of varying the isomer ratios composing the co-polymer structure. The strategy to form blends or composites with PEKK for FFF is attractive for further tailoring of performance in application, yet has received limited attention. Here, we report the integration of three grades of mica platelets into PEKK at 10% and 30% mass loadings to generate an array of filament feedstocks that were then used to print objects with a simple FFF machine. The effects of mica coating chemistry and surface treatment on the compatibility with PEKK and resulting properties are described. Mica fillers at both loadings have only subtle influence on the FFF relevant melt rheological properties inherent to PEKK. Pigment micas at high loadings can lower the melting temperature of PEKK (up to 19 ºC) without shifting its glass transition temperature and inhibit much of the undesirable crystallization occurring during processing with unfilled PEKK. The printed composites were effectively cold crystallized post-printing, affording crystalline fractions up to 90% relative to unfilled PEKK with increased dimensional stabilities. All micas, when used as fillers in low and high relative PEKK crystallinities, significantly increased the tensile modulus (as high as 126% or to 7.31 GPa) of parts in correlation to the loading. Furthermore, the underlying microstructural features of a printed composite were compared to unfilled PEKK by use of a high-resolution helical micro-computed tomography instrument. Practically, pigment micas can confer a wide range of rich colors to 3D-printed PEKK.

36 MATERIALS SCIENCE↗