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At least 145 records · Page 8

Monte Carlo simulation of a near-continuum shock-shock interaction problem

A complex shock interaction is calculated with direct simulation Monte Carlo (DSMC). The calculation is performed for the near-continuum flow produced when an incident shock impinges on the bow shock of a 0.1 in. radius cowl lip for freestream conditions of approximately Mach 15 and 35 km altitude. Solutions are presented both for a full finite-rate chemistry calculation and for a case with chemical reactions suppressed. In each case, both the undisturbed flow about the cowl lip and the full shock interaction flowfields are calculated. Good agreement has been obtained between the no-chemistry simulation of the undisturbed flow and a perfect gas solution obtained with the viscous shock-layer method. Large differences in calculated surface properties when different chemical models are used demonstrate the necessity of adequately representing the chemistry when making surface property predictions. Preliminary grid refinement studies make it possible to estimate the accuracy of the solutions.

Carlson, Ann B.↗

Gravitational Effects on the Morphology and Kinetics of Photodeposition of Polydiacetylene Thin Films From Monomer Solutions

The goal of this proposed work is to study gravitational effects on the photodeposition of polydiacetylene thin films from monomer solutions onto transparent substrates. Polydiacetylenes have been an extensively studied class of organic polymers because they exhibit many unusual and interesting properties, including electrical conductivity and optical nonlinearity. Their long polymeric chains render polydiacetylenes readily conducive to thin film formation, which is necessary for many applications. These applications require thin polydiacetylene films possessing uniform thicknesses, high purity, minimal inhomogeneities and defects (such as scattering centers), etc. Also, understanding and controlling the microstructure and morphology of the films is important for optimizing their electronic and optical properties. The lack of techniques for processing polydiacetylenes into such films has been the primary limitation to their commercial use. We have recently discovered a novel method for the formation of polydiacetylene thin films using photo-deposition from monomer solutions onto transparent substrates with UV light. This technique is very simple to carry out, and can yield films with superior quality to those produced by conventional methods. Furthermore, these films exhibit good third-order properties and are capable of waveguiding. We have been actively studying the chemistry of diacetylene polymerization in solution and the photo-deposition of polydiacetylene thin films from solution. It is well-known that gravitational factors such as buoyancy-driven convection and sedimentation can affect chemical and mass transport processes in solution. One important aspect of polydiacetylene thin film photodeposition in solution, relevant to microgravity science, is that heat generated by absorption of UV radiation induces thermal density gradients that under the influence of gravity, can cause fluid flows (buoyancy-driven convection). Additionally, changes in the chemical composition of the solution during polymerization may cause solutal convection. These fluid flows affect transport of material to and from the film surface and thereby affect the kinetics of the growth process. This manifests itself in the morphology of the resulting films; films grown under the influence of convection tend to have less uniform thicknesses, and can possess greater inhomogeneities and defects. Specifically, polydiacetylene films photodeposited from solution, when viewed under a microscope, exhibit very small particles of solid polymer which get transported by convection from the bulk solution to the surface of the growing film and become embedded. Even when carried out under conditions designed to minimize unstable density gradients (i.e., irradiating the solution from the top), some fluid flow still takes place (particles remain present in the films). It is also possible that defect nucleation may be occurring within the films or on the surface of the substrate; this, too, can be affected by convection (as is the case with crystal growth). Hence films grown in 1-g will, at best, still possess some defects. The objective of this proposal is to investigate, both in 1-g and in low-g, the effects of gravitational factors (primarily convection) on the dynamics of these processes, and on the quality, morphology, and properties of the films obtained.

Paley, Mark S.↗

Lower mass limit of an evolving interstellar cloud and chemistry in an evolving oscillatory cloud

Simultaneous solution of the equation of motion, equation of state and energy equation including heating and cooling processes for interstellar medium gives for a collapsing cloud a lower mass limit which is significantly smaller than the Jeans mass for the same initial density. The clouds with higher mass than this limiting mass collapse whereas clouds with smaller than critical mass pass through a maximum central density giving apparently similar clouds (i.e., same Av, size and central density) at two different phases of its evolution (i.e., with different life time). Preliminary results of chemistry in such an evolving oscillatory cloud show significant difference in abundances of some of the molecules in two physically similar clouds with different life times. The problems of depletion and short life time of evolving clouds appear to be less severe in such an oscillatory cloud.

Tarafdar, S. P.↗

Zwitterion Moieties in Polypeptides Synergistically Enhance the Release of Cellulose and Amorphous Polysaccharides from Plant Cell Walls

This study demonstrated that covalently localized zwitterionic moieties in zwitterionic polypeptides (ZIPs) effectively disrupt hydrogen bonds in cellulosic substrates, including filter paper and plant cell wall materials, without significant cytotoxicity. ZIPs with varying densities of zwitterionic side chains were synthesized via the postpolymerization modification of histidinecontaining oligopeptides. The newly developed ZIPs predominantly comprised repeating units with zwitterionically converted side chains. Such ZIPs can cleave multiple hydrogen bonds by anchoring the zwitterionic structure at specific sites, thereby partially dissociating the polysaccharide chains in the cell wall. They are especially effective in dissolving amorphous cellulose, even at low concentrations in aqueous solutions. Importantly, this effect was achieved with minimal cellular toxicity, harnessing the advantages of ionic liquid-like properties while mitigating their high-toxicity limitations. This biofriendly approach to cell wall denaturation highlights a novel method for controlling hydrogen bond networks in polysaccharides and cell walls. These findings indicate a new approach for reducing biomass recalcitrance and developing next-generation biobased materials and fuels derived from plant cell walls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructural Topology as a Prescriptor for Quantum Coherence: Towards A Unified Framework for Decoherence in Superconducting Qubits

In superconducting quantum circuits, decoherence improvements are frequently obtained through process interventions that simultaneously modify surface chemistry, microstructural topology, and device geometry, leaving mechanistic attribution structurally underdetermined. Predictive materials engineering requires measurable structural statistics to be separated from geometry-dependent coupling coefficients into independently testable factors. We introduce the concept of classical and quantum microstructure. In that context, we formulate a channel-wise separable framework for decoherence in superconducting transmon qubits in which each loss channel is described by a reduced prescriptor. Here, a channel-specific microstructural state variable is determined independently of device geometry, and a geometry-dependent coupling functional is computable from field solutions without reference to surface chemistry. We derive this product form from a spatially resolved kernel representation and establish a perturbative separability criterion that defines the regime where independent variation of the variables is valid. The framework specifies five prescriptor classes for dominant loss pathways in transmon-class devices. Falsifiability is operationalized through a pre-committed 2x2 experimental protocol in which the variables must satisfy independent ratio checks within propagated uncertainty. A Minimum-Dataset Specification standardizes reporting for cross-laboratory inference. Part I establishes the conceptual and mathematical architecture; coordinated experimental validation is reserved for Part II.

Dravid, Vinayak P. [Northwestern U.]↗

Spectroscopic Properties of Americium(III) in Mineral Acid Media

We report the preparation and optical characterization of three solutions of Am(III) in common aqueous (aq.) mineral acids (HCl, HNO 3 and HBr), including absorption, emission, and Raman vibrational analyses. To our knowledge, this study provides the first detailed absorption spectra of Am(III) spanning the entire UV/Vis/NIR region in these mineral acids reported since the 1960s. Here, using this high-resolution absorption data, provided in an open access format for the broader field, we build on prior work by Carnall and others to provide detailed optical analysis including all transition assignments. This work also includes the first reported absorption spectrum of Am(III) in aq. HBr. Characteristic Am(III) luminescence could be detected from all three samples. These are the first reports of emission from Am(III) in these acid systems, which build on prior emission reports collected from aq. HClO 4 solutions. The acquired emission spectra display anion-dependent shifting of the visible-region transitions by up to 21 nm from their predicted positions, akin to the nephelauxetic effect. The shift magnitude trends linearly according to the acid p K a and more generally according to the transition metal spectrochemical series. These ligand field effects, coupled with luminescence lifetime experiments, indicate that weak Am-X interactions persist in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A similarity solution of the Navier-Stokes equations with wall catalysis and slip for hypersonic, low Reynolds number flow over spheres

The slip conditions for a multicomponent mixture with diffusion, wall-catalyzed atom recombination and thermal radiation are derived. The more realistic multicomponent species slip conditions are shown to be necessary for accurate merged shock layer solutions on a sphere. These slip conditions are used in a first-order similarity solution of the Navier-Stokes equations with nonequilibrium chemistry for the merged shock layer. Results of this quick numerical solution are compared with a time dependent solution around the sphere and with measured arc jet results at low Reynolds numbers. The similarity solution, unlike the time dependent solution, shows smooth radial profiles of the pressure and smooth variations of velocity slip, skin friction, temperature slip and heat transfer around the body. The present first-order similarity solution is valid up to 25 deg from the stagnation point and takes less than 1% of the computer time to run a time dependent scheme. The smaller stand-off distance obtained from the similarity solution is supported by experimental data. The measured heat flux is closer to the similarity solution than the time dependent method at the stagnation point and shows the proper variation with circumferential angle up to at least 40 deg.

Hendricks, W. L.↗

Synthesis, Crystal Structure, and Optical Properties of the Barium meta -Pertechnetate Ba[TcO 4 ] 2

High-quality single crystals of the colorless title compound Ba[ 99 TcO 4 ] 2 were prepared from radioactive, isotope-pure 99 TcO 2 by oxidation with H 2 O 2 in an aqueous ammonia solution and subsequent cation metathesis using an ion-exchange column. Single-crystal X-ray diffraction revealed Ba[TcO 4 ] 2 to crystallize isotopically to Ba[MnO 4 ] 2 in the orthorhombic space group Fddd with the lattice parameters a = 747.34(5) pm, b = 1244.08(7) pm, and c = 1511.23(9) pm for Z = 8. Its crystal structure features [BaO 12 ] 22- icosahedra surrounded by ten [TcO 4 ] - tetrahedra connected via two edges and eight corners. The optical properties of Ba[TcO 4 ] 2 investigated by UV-vis spectroscopy show the broad O 2- → Tc 7+ ligand-to-metal charge transfer (2p → 4d) process within these discrete [TcO 4 ]- anions at an absorption maximum of around 350 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating Np(v) disproportionation: effect of Np concentration

The role of Np(V) concentration as a potential chemical driver of Np(V) disproportionation was investigated by probing Np redox chemistry in two different acid media using visible-near-infrared absorbance spectroscopy. In situ spectroscopy of chemically and electrochemically manipulated Np oxidation states at molar concentrations of Np underscores the difficulty in stabilizing pure Np(V), even in dilute acid. A Np(VI) component coexisting with the majority Np(V) component was observed in both HNO 3 and HCl. Electrochemical tuning and subsequent spectroscopic analysis of the Np(VI/V) ratio revealed neptunyl self-complexation as a key mechanism occurring in both acid media. Chemical reduction of the Np(VI) component and stabilization of a minor Np(IV) component in HNO 3 were observed; however, spectral data indicated that these two oxidation states were not observed to coexist, and pure Np(V) was stabilized only briefly. These findings demonstrate that high Np concentrations significantly affect the redox chemistry of Np in acidic solutions. Finally, the occurrence of Np(V) disproportionation could not be definitely determined by spectral data, but other mechanisms such as self-complexation and radiolysis, which potentially compete with disproportionation, must be considered.

Gilson, Sara E. [Oak Ridge National Laboratory (OR↗

Computations of Axisymmetric Flows in Hypersonic Shock Tubes

A time-accurate two-dimensional fluid code is used to compute test times in shock tubes operated at supersonic speeds. Unlike previous studies, this investigation resolves the finer temporal details of the shock-tube flow by making use of modern supercomputers and state-of-the-art computational fluid dynamic solution techniques. The code, besides solving the time-dependent fluid equations, also accounts for the finite rate chemistry in the hypersonic environment. The flowfield solutions are used to estimate relevant shock-tube parameters for laminar flow, such as test times, and to predict density and velocity profiles. Boundary-layer parameters such as bar-delta(sub u), bar-delta(sup *), and bar-tau(sub w), and test time parameters such as bar-tau and particle time of flight t(sub f), are computed and compared with those evaluated by using Mirels' correlations. This article then discusses in detail the effects of flow nonuniformities on particle time-of-flight behind the normal shock and, consequently, on the interpretation of shock-tube data. This article concludes that for accurate interpretation of shock-tube data, a detailed analysis of flowfield parameters, using a computer code such as used in this study, must be performed.

Sharma, Surendra P.↗

Field-Driven Simulations to Probe the Impact of Ionic Correlations on Solution Transport Coefficients in Binary, Ternary, and Reciprocal Quaternary Aqueous Electrolytes

Ionic correlations play a critical role in governing transport properties of mixed-salt aqueous electrolyte solutions, yet their quantitative characterization remains challenging, particularly for multicomponent aqueous systems. Here, we develop a general nonequilibrium molecular dynamics framework to efficiently compute Onsager transport coefficients and ionic correlations in mixed-salt aqueous solutions. Using field-driven simulations, we obtain accurate Onsager matrices for LiCl/ KCl, KCl/KBr, and LiBr/KCl electrolyte solutions with significantly reduced computational cost relative to equilibrium Green−Kubo methods. The framework enables direct assessment of how attractive cation−anion and repulsive like-ion interactions contribute to conductivity and salt diffusivity across compositions. While static ion pairing exhibits strong composition dependence, dynamic ion correlations remain nearly invariant, leading to constant deviations from Nernst−Einstein predictions. These results highlight the disconnect between static ion association and dynamic transport correlations, and they establish a transferable approach for analyzing ion transport in complex electrolyte environments relevant to separation processes and electrochemical systems.

36 MATERIALS SCIENCE↗

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

In this article, the structural dynamics, chemical reactivity, anisotropy, diffusivity, viscosity, and density were measured for concentrated lithium salt solutions, including lithium chloride (LiCl), lithium bromide (LiBr), lithium nitrite (LiNO 2 ), and lithium nitrate (LiNO 3 ), with methyl thiocyanate as an infrared vibrational probe molecule, using two-dimensional infrared spectroscopy (2D IR), nuclear magnetic resonance (NMR) spectroscopy, and viscometry. 2D IR, NMR, and viscosity results show that LiNO 2 exhibits longer correlation times, lower diffusivity, and nearly four times greater viscosity when compared to the other lithium salt solutions of the same concentration, suggesting that nitrite anions may strongly facilitate structure formation via strengthening water-ion interactions, directly impacting bulk solution properties at sufficiently high concentrations. Additionally, the LiNO 2 and LiNO 3 solutions show significantly reduced chemical reactivity with respect to lithium cations coordinating with the methyl thiocyanate when compared to the lithium halide salts.

2D IR↗

Decadal-Scale Hydrothermal Alteration of Basalt: Implications for Long-Term Reactivity in Subsurface Technologies

Global demands to secure critical mineral supply chains and managing water resources require innovative resource management strategies. Subsurface basalt reservoirs offer a dual-purpose application, where CO2 enhanced critical metal recovery can be coupled with water remediation strategies for the extraction of economically important and environmentally relevant elements. This study utilizes static batch experiments conducted on Columbia River Basalt Group samples to evaluate long-term fluid–rock interactions relevant to coupled subsurface applications. Samples were reacted under elevated temperature and pressure conditions, for 296 and 4,061 days, providing a unique dataset to assess geochemical evolution, element partitioning, and aqueous chemistry over decadal timescales. The alteration was dominated by silicate, aluminosilicate, and oxide phases. Progressive hydrothermal alteration increased the cation exchange capacity through the formation of secondary minerals (e.g. clays and zeolites), influencing solute retention, ion exchange behavior, and aqueous chemistry. Grain-scale and bulk analyses revealed selective cation release and retention patterns, establishing a mechanistic baseline for predicting element mobility. These geochemical constraints inform the prospective use of CO2-enhanced metal recovery for critical resources (e.g. Co, Ni, Mn, Mg, Ti, Fe) and associated water-quality impacts, providing a foundation for the design and management of engineered fluid–rock systems in basalt reservoirs.

Gibson, Marie N.↗

Analysis of the physical state of one Arctic polar stratospheric cloud based on observations

During the Arctic Airborne Stratospheric Expedition (AASE) simultaneous measurements of aerosol size distribution and NO(y)(HN03 + NO + NO2 + 2(N205)) were made along ER-2 flight paths. The flow characteristics of the NO(y) instrument allow us to derive the condensed NO(y) amount (assumed to be HN03) present during polar stratospheric cloud (PSC) events. Analysis of the January 24th flight indicates that this condensed HN03 amount does not agree well with the aerosol volume if the observed PSCs are composed of solid nitric acid trihydrate (NAT), as is generally assumed. However, the composition agrees well with that predicted for liquid H2S04/HN03/H20 solution droplets using a new Aerosol Physical Chemistry Model (APCM). The agreement corresponds in detail to variations in temperature and humidity. The weight percentages of H2SO4, HN03, and H2O derived from the measurements all correspond to those predicted for ternary, liquid solutions.

Drdla, K.↗

Assessment of Pioneer Venus Entry Heating with Coupled Radiation and Ablation

The objective of this work is to reconstruct thermocouple temperature measurements taken at the stagnation point of the Pioneer Venus large probe using uncoupled and coupled ablation calculations. The time history of the large probe forebody entry heating was obtained from a trajectory-based analysis that employed a material response solver to model equilibrium and nonequilibrium ablation chemistry at the surface. In the uncoupled approach, equilibrium ablation chemistry was assumed in the material response calculations, but the material response outputs were not returned to the flowfield solver. Therefore, the effects of char and pyrolysis gas injection into the boundary layer due to ablation (e.g., convective blockage and radiative energy absorption) did not influence the flowfield solutions. In the coupled approach, nonequilibrium ablation chemistry was performed and the material response outputs were returned to the flowfield solver. Therefore, the effects of char and pyrolysis gas injection into the boundary layer were accounted for in the flowfield solutions. Both uncoupled and coupled approaches produced reconstructed temperatures that were within 10% of the flight measurements through the entry heat pulse, with the coupled results comparing more favorably with the measurements. Overall, the reconstructed thermocouple temperatures in this work significantly improved on the results of previous reconstructions for the large probe.

Jannuel V V Cabrera↗

A hybrid multigrid technique for computing steady-state solutions to supersonic flows

Recently, Li and Sanders have introduced a class of finite difference schemes to approximate generally discontinuous solutions to hyperbolic systems of conservation laws. These equations have the form together with relevant boundary conditions. When modelling hypersonic spacecraft reentry, the differential equations above are frequently given by the compressible Euler equations coupled with a nonequilibrium chemistry model. For these applications, steady state solutions are often sought. Many tens (to hundreds) of super computer hours can be devoted to a single three space dimensional simulation. The primary difficulty is the inability to rapidly and reliably capture the steady state. In these notes, we demonstrate that a particular variant from the schemes presented can be combined with a particular multigrid approach to capture steady state solutions to the compressible Euler equations in one space dimension. We show that the rate of convergence to steady state coming from this multigrid implementation is vastly superior to the traditional approach of artificial time relaxation. Moreover, we demonstrate virtual grid independence. That is, the rate of convergence does not depend on the degree of spatial grid refinement.

Sanders, Richard↗

Finite-Difference Solution for Laminar or Turbulent Boundary Layer Flow over Axisymmetric Bodies with Ideal Gas, CF4, or Equilibrium Air Chemistry

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Hamilton, H. Harris, II↗