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At least 631 records · Page 35

Light element ($$Z=1,2$$) production from spontaneous ternary fission of $$^{252}$$Cf

Abstract The yields of light elements ( $$Z=1,2$$ Z = 1 , 2 ) obtained from spontaneous ternary fission of $$^{252}$$ 252 Cf are treated within a nonequilibrium approach, and the contribution of unstable nuclei and excited bound states is taken into account. These light cluster yields may be used to probe dense matter, and to infer in-medium corrections such as Pauli blocking which is determined by the nucleon density. Continuum correlations are calculated from scattering phase shifts using the Beth-Uhlenbeck formula, and the effect of medium modification is estimated. The relevant distribution is reconstructed from the measured yields of isotopes. This describes the state of the nucleon system at scission and cluster formation, using only three Lagrange parameters which are the nonequilibrium counterparts of the temperature and chemical potentials, as defined in thermodynamic equilibrium. We concluded that a simple nuclear statistical equilibrium model neglecting continuum correlations and medium effects is not able to describe the measured distribution of H and He isotopes. Moreover, the freeze-out concept may serve as an important ingredient to the nonequilibrium approach using the relevant statistical operator concept.

Röpke, G.↗

Numerical solution of stiff systems of ordinary differential equations with applications to electronic circuits

Systems of ordinary differential equations in which the magnitudes of the eigenvalues (or time constants) vary greatly are commonly called stiff. Such systems of equations arise in nuclear reactor kinetics, the flow of chemically reacting gas, dynamics, control theory, circuit analysis and other fields. The research reported develops an A-stable numerical integration technique for solving stiff systems of ordinary differential equations. The method, which is called the generalized trapezoidal rule, is a modification of the trapezoidal rule. However, the method is computationally more efficient than the trapezoidal rule when the solution of the almost-discontinuous segments is being calculated.

Rosenbaum, J. S.↗

Biological particle analysis by mass spectrometry

An instrument that analyzes the chemical composition of biological particles in aerosol or hydrosol form was developed. Efforts were directed toward the acquisition of mass spectra from aerosols of biomolecules and bacteria. The filament ion source was installed on the particle analysis by mass spectrometry system. Modifications of the vacuum system improved the sensitivity of the mass spectrometer. After the modifications were incorporated, detailed mass spectra of simple compounds from the three major classes of biomolecules, proteins, nucleic acids, and carbohydrates were obtained. A method of generating bacterial aerosols was developed. The aerosols generated were collected and examined in the scanning electron microscope to insure that the bacteria delivered to the mass spectrometer were intact and free from debris.

Vilker, V. L.↗

Chemical analyses of provided samples

Two batches of samples were received and chemical analysis was performed of the surface and near surface regions of the samples by the surface analysis by laser ionization (SALI) method. The samples included four one-inch optics and several paint samples. The analyses emphasized surface contamination or modification. In these studies, pulsed sputtering by 7 keV Ar+ and primarily single-photon ionization (SPI) by coherent 118 nm radiation (at approximately 5 x 10(exp 5) W/cm(sup 2) were used. For two of the samples, also multiphoton ionization (MPI) at 266 nm (approximately 5 x 10(exp 11) W/cm(sup 2) was used. Most notable among the results was the silicone contamination on Mg2 mirror 28-92, and that the Long Duration Exposure Facility (LDEF) paint sample had been enriched in K and Na and depleted in Zn, Si, B, and organic compounds relative to the control paint.

Becker, Christopher H.↗

A model for the evolution of CO2 on Mars

We have constructed a model that predicts the evolution of CO2 on Mars from the end of the heavy bombardment period to the present. The model draws on published estimates of the main processes believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures which we calculate using a modified version of the Gierasch and Toon energy balance model. The modifications account for the change in solar luminosity with time, the greenhouse effect, and a polar and equatorial energy budget. Using published estimates for the main parameters, we find no evolutionary scenario in which CO2 is capable of producing a warm (global mean temperatures greater than 250 K) and wet (surface pressures greater than 30 mbar) early climate, and then evolves to present conditions with approximately 7 mbar in the atmosphere, less than 300 mbar in the regolith, and less than 5 mbar in the caps. Such scenarios would only exist if the early sun were brighter than standard solar models suggest, if greenhouse gases other than CO2 were present in the early atmosphere, or if the polar albedo were significantly lower than 0.75. However, these scenarios generally require the storage of large amounts of CO2 (greater than 1 bar) in the carbonate reservoir. If the warm and wet early Mars constraint is relaxed, then we find best overall agreement with present day reservoirs for initial CO2 inventories of 0.5-1.0 bar. We also find that the polar caps can have a profound effect on how the system evolves. If the initial amount of CO2 is less than some critical value, then there is not enough heating of the poles to prevent permanent caps from forming. Once formed, these caps control how the system evolves, because they set the surface pressure and, hence, the thermal environment. If the initial amount of CO2 is greater than this critical value, then caps do not form initially, but can form later on, when weathering and escape lower the surface pressure to a point at which polar heating is no longer sufficient to prevent cap formation and the collapse of the climate system. Our modeling suggests this critical initial amount of CO2 is between 1 and 2 bar, but its true value will depend on all factors affecting the polar heat budget.

Haberle, Robert M.↗

Isolated Liquid Droplet Combustion: Inhibition and Extinction Studies

Introduction of fire suppressants to the ambient environment surrounding a heterogeneous diffusion flame may be an inefficient technique for fire safety in systems without buoyant flows. Carbon dioxide substitution for nitrogen diluent leads to significant modifications of the sphero-symmetric burning behavior of isolated n-heptane droplets, partly through increased heat capacity within the gaseous diffusion flame, but mostly because of modifications in spectral radiative coupling in the gas phase. Effects of longer time scale phenomena such as sooting and slow gas-phase/droplet convection remain to be determined. Similar methodologies can be applied to evaluate the effects and efficacy of chemical inhibitors in the liquid and gas phases.

Dryer, F. L.↗

Stratospheric photochemical studies using Nimbus 7 data. I - Ozone photochemistry. II - Development of inferred trace specie distributions

The present investigation has the objective to make use of the limb infrared monitor of the stratosphere (LIMS) data set in conducting stratospheric photochemical studies. A description of the data is provided. The data are utilized in a zero-dimensional model incorporating the relevant chemistry. The chemical reaction scheme considered is a subset of the scheme used in the Langley one-dimensional model discussed by Callis et al. (1983). Attention is given to a comparison of model results and data, a model uncertainty analysis, model response to modifications in rate data, the ozone-temperature relationship, and the diurnal variation in the upper stratospheric ozone.

Natarajan, M.↗

A computational study of the flowfield surrounding the Aeroassist Flight Experiment vehicle

A symmetric total variation diminishing (STVD) algorithm has been applied to the solution of the three-dimensional hypersonic flowfield surrounding the Aeroassist Flight Experiment (AFE) vehicle. Both perfect-gas and chemical nonequilibrium models have been used. The perfect-gas flows were computed at two different Reynolds numbers, including a flight trajectory point at maximum dynamic pressure, and on two different grids. Procedures for coupling the solution of the species continuity equations with the Navier-Stokes equations in the presence of chemical nonequilibrium are reviewed and tested on the forebody of the AFE and on the complete flowfield assuming noncatalytic wall and no species diffusion. Problems with the STVD algorithm unique to flows with variable thermodynamic properties (real gas) are identified and algorithm modifications are suggested. A potential heating problem caused by strong flow impingement on the nozzle lip in the near wake at 0-deg angle of attack has been identified.

Gnoffo, Peter A.↗

Regulation of Surface Defect Chemistry toward Stable Ni-Rich Cathodes

Surface reconstruction of Ni-rich layered oxides (NLO) degrades the cycling stability and safety of high-energy-density lithium-ion batteries (LIBs), which challenges typical surface-modification approaches to build a robust interface with electrochemical activity. Here, a strategy of leveraging the low-strain analogues of Li- and Mn-rich layered oxides (LMR) to reconstruct a stable surface on the Ni-rich layered cathodes is proposed. The new surface structure not only consists of a gradient chemical composition but also contains a defect-rich structure regarding the formation of oxygen vacancies and cationic ordering, which can simultaneously facilitate lithium diffusion and stabilize the crystal structure during the (de)lithiation. These features in the NLO lead to a dramatic improvement in electrochemical properties, especially the cyclability under high voltage cycling, exhibiting the 30% increase in capacity retention after 200 cycles at the current density of 1 C (3.0-4.6 V). We report the findings offer a facile and effective way to regulate defect chemistry and surface structure in parallel on Ni-rich layered structure cathodes to achieve high-energy density LIBs.

25 ENERGY STORAGE↗

Modification and Development of a Control Mechanism for the Scanning Microwave Limb Sounder

The scanning microwave limb sounder (SMLS) is the latest instrument to probe the Earth's atmosphere to come out of the Microwave Limb Sounder (MLS) team. Once deployed to the upper stratosphere, it will use microwave detection to measure geo-atmospheric variables such as temperature, pressure, and chemical composition. In addition to previous missions that used vertical limb scans to observe altitudinal variations, the SMLS will rotate laterally allowing it to establish two-dimensional variable dependencies with a single run. A program was originated by a previous intern that will automatically control the movement of the two rotational axes along with a switching mirror and chopper once the instrument is in flight. However, it lacked the code essential to control system's ability to function fully and reliably. By modifying and rewriting parts of the code I sought to have a finished ready-for-flight control system that would be easy to navigate. Three of the major alterations I made including instituting a gyroscope, implementing a restart button, and instigating the automatic creation of a file log with each run to record the position and orientation of the SMLS.

Scanning Microwave Limb Sounder (SMLS)↗

Tuning the Molecular Structure and Reaction Mechanism of Olefin Metathesis by Model Bilayered Supported MoO x /AlO x /SiO 2 Catalysts

The molecular structure and activity of supported MoO x olefin metathesis catalysts are heavily impacted by the choice of catalyst support. In this study, surface modification of the SiO 2 support with AlO x and selective anchoring of the MoO x on the surface AlO x sites were used to tune the structure, activation, and reactivity of the resulting surface MoO x sites. Extensive in situ molecular characterization, chemical probe studies, and density functional theory (DFT) calculations reveal that the enhanced activity of the supported MoO x /AlO x /SiO 2 catalyst over the MoO x / SiO 2 catalyst is associated with more favorable activation and kinetics of surface MoO x anchored at AlO x sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transmission of Images on High-Temperature Nuclear-Grade Metallic Pipe with Ultrasonic Elastic Waves

Transmission of information using elastic ultrasonic waves on existing metallic pipes provides an alternative communication option for a nuclear facility. The advantages of this approach consist of transmitting information through barriers, such as the containment building wall, with minimal modification of the existing hardware. Because bit rates on the order of kilobits per second are achievable, relatively large volumes of data, such as images, can be transmitted. A viable candidate for an ultrasonic communication channel is a stainless steel pipe of the chemical volume control system (CVCS) that penetrates through the reactor containment building wall through a sealed tunnel. To study ultrasonic communication under simulated nuclear facility conditions of high temperature, a test article was developed by installing heating tapes, temperature controllers, and thermal insulation on a laboratory CVCS-like stainless steel pipe. High temperature and radiation-resilient lithium niobate ultrasonic transducers were utilized for information transmission on the heated pipe. The amplitude shift keying (ASK) digital communication protocol was developed and implemented in a GNU Radio software-defined radio environment. A root-raised-cosine filter was introduced to suppress ultrasonic transducer ringing and thus reduce inter-symbol interference. This resulted in the enhancement of the data transmission bit rate compared to information encoding with square pulses. Demonstrations of communication at high temperature included transmission of a 90-KB image at the bit rate of 10 Kbps with a bit error rate of 10 -3 across a 6-ft-long straight pipe heated up to 230 degrees C. Additional preliminary studies were conducted to evaluate ultrasonic communication system resilience to environmental degradation and damage.

42 ENGINEERING↗

Effect of heat release on the stability of compressible reacting mixing layer

Reacting free shear layers are of fundamental importance in many industrial systems including gas turbine combustors and rockets. Efficient propulsion systems are essential for air breathing supersonic ramjets in the high Mach number range. A limiting factor in these engines is the time for fuel and oxidizer to mix in the combustion chamber; for fast mixing, the flow must be vigorously turbulent which requires the laminar flow to be unstable. Understanding the stability characteristics of compressible reacting free shear layers is, therefore, very important and may allow one to control the flow. Low speed shear layers are highly unstable but, as chemical reaction and compressibility effects tend to stabilize them, it is important to investigate the stability of high speed reacting mixing layers. The latter consists of two fluid streams containing fuel and oxidizer respectively, and the conclusions are expected to apply, with quantitative modifications, to other shear flows, e.g., jets. Since low speed reacting cases have been studied earlier, we concentrate on the effects of Mach number and heat release. We are primarily interested in solving the stability problem over a large range of Mach number and heat release. In order to understand the effect of the heat release on the stability of this flow, one must first study the characteristics of the non-reacting flow. Inviscid theory is a reliable guide for understanding stability of compressible shear flows at moderate and large Reynolds numbers and is the basis for this work.

Shin, Dong-Shin↗

Carbidic Mo is the sole kinetically-relevant active site for catalytic methane dehydroaromatization on Mo/H-ZSM-5

Systematic variation of Mo/Al = {0.10, 0.25, 0.35} in Mo/H-ZSM-5 catalysts effects ~20× change of Mo-to-H + ratio during methane dehydroaromatization (DHA) reactions at steady state and on deactivating catalysts. Mo and Brønsted-acid site count, respectively enumerated by ethane hydrogenolysis probe reaction and dimethyl ether chemical titration, evolve disparately during DHA catalysis, indicating the two sites reduce in number by distinct mechanisms. Here, the deactivation of Mo/H-ZSM-5 catalytic activity is uniquely attributed to the loss of active, or accessible, Mo sites, evinced by (i) the non-selective nature of deactivation (i.e. that deactivation occurs without modification of residual active sites), (ii) invariance in product distribution from Mo/H + = 0.10–2.1, and (iii) linear correspondence between Mo-catalyzed ethane hydrogenolysis rate and active site count during DHA on deactivating samples. DHA forward rate – the intrinsic kinetic descriptor of catalyst activity – normalizes by Mo content at steady state and on deactivating catalysts with Mo/Al = 0.10–0.35 for Mo-based contact times in the range τ Mo = 0.79–44 mol Mo s mol –1 C , unequivocally establishing Mo aggregates as the sole kinetically-relevant active site on Mo/H-ZSM-5. Brønsted-acid site content over a ~40× range in τ H+ = 1.4–54 mol H+ s mol –1 C has no discernable correlation with or effect on DHA rate, methane conversion, or product distribution – demonstrating H + does not catalyze any rate- or selectivity-determining steps in the benzene formation pathway and suggesting that the benefits of zeolitic acid sites are only to disperse Mo during catalyst synthesis and, conceivably, to catalyze equilibrated reaction steps.

02 PETROLEUM↗

Simplifying the Chemical Design of Nonfused-Ring Electron Acceptors─Lessons Learned from Thienothiophene and Benzodithiophene Cores

Nonfused-ring electron acceptors (NFREA)s have been proposed as alternatives to fused-ring acceptors in organic photovoltaics (OPV)s. The simpler molecular design of NFREAs results in a reduced synthetic complexity, potentially lowering manufacturing costs, and easier access to desired optoelectronic properties by structural modifications. However, they have not seen the same rise in popularity as fused nonfullerene acceptors (NFA)s due to their lower performances in devices. In this work, we explore structure–property relationships of three NFREA molecules based on thieno[3,2-b]thiophene (TT) and benzo[1,2-b:4,5-b′]dithiophene (BDT) cores and malononitrile functionalized-isatin end group acceptors. We describe their synthetic routes, computational analysis, and photophysical and electronic properties. Here, we investigated the effect of changing the core from TT to BDT on electronic properties of the molecules─a result of raising/lowering of the frontier molecular orbital (FMO) levels. We also explored the effect of branched vs nonbranched alkyl groups on the morphological and blend-capabilities in bulk heterojunction (BHJ) OPV devices. These effects were then reflected in the overall device performances, primarily due to favorable FMO energy alignment between the NFREA and polymer. To investigate the behavior of the excited states of the NFREAs within the active layer of the devices, we performed time-resolved microwave conductivity and transient absorption experiments, which confirmed that the TT molecules exhibited very low conductance while the BDT molecule showed moderate photoconductance. Our combined theoretical, synthetic, device, and charge carrier dynamics studies of these materials reveal the central role that structure–property relationships play in future molecular designs of NFREAs that can perform as well as their fused counterparts.

14 SOLAR ENERGY↗

Fracture Strength Determination Methods for Ceramic Materials Applied to Uranium Dioxide

The Advanced Fuels Campaign is currently focusing on development of accident-tolerant fuels that possess a range of property modifications intended to improve fuel performance during accident and transient conditions as well as extend license limits to burnups beyond 62 MWd/kgU. Both of these drivers have identified understanding and mitigating fuel cracking as a key performance criterion. Small-scale cantilever beam testing has been identified as a plausible method by which to collect fracture data for UO 2 as a function of chemical and structural evolutions introduced either during fabrication or irradiation. While this method has been found to be capable of providing data that are in reasonable agreement with literature for unirradiated UO 2 , the inherently small sample volumes that can be sampled limit its ability to capture the statistical nature of mechanisms that govern the fracture of brittle ceramics. A biaxial flexure strength test was developed to be used for unirradiated UO 2 . This method is standard in the community, but no systems presently in use at national laboratories, universities, or private companies are available to be used for nuclear fuel materials. This report describes the operation and benchmarking of this system, which has been validated for a number of common oxides. Future work will extend this system to characterization of both doped UO 2 and other relevant microstructural modifications that can also be measured using small-scale cantilever beam testing. Comparison of datasets collected using both methods will allow the overall applicability of small-scale techniques to be assessed and provide confidence or bounds on their use for irradiated fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Temporal Galactose‐Manganese Feeding in Fed‐Batch and Perfusion Bioreactors Modulates UDP‐Galactose Pools for Enhanced mAb Glycosylation Homogeneity

ABSTRACT Monoclonal antibodies (mAbs) represent a majority of biotherapeutics in the market today. These glycoproteins undergo posttranslational modifications, such as N‐linked glycosylation, that influence the structural & functional characteristics of the antibody. Glycosylation is a heterogenous posttranslational modification that may influence therapeutic glycoprotein stability and clinical efficacy, which is why it is often considered a critical quality attribute (CQA) of the mAb product. While much is known about the glycosylation pathways of Chinese Hamster Ovary (CHO) cells and how cell culture chemical modifiers may influence the N‐glycosylation profile of the final product, this knowledge is often based on the final cumulative glycan profile at the end of the batch process. Building a temporal understanding of N‐glycosylation and how mAb glycoform composition responds to real‐time changes in the biomanufacturing process will help build integrated process models that may allow for glycosylation control to produce a more homogenous product. Here, we look at the effect of specific nutrient feed media additives (e.g., galactose, manganese) and feeding times on the N‐glycosylation pathway to modulate N‐glycosylation of a Herceptin biosimilar mAb (i.e., Trastuzumab). We deploy the N‐GLYcanyzer process analytical technology (PAT) to monitor glycoforms in near real‐time for bench‐scale bioprocesses operated in both fed‐batch and perfusion modes to build an understanding of how temporal changes in mAb N‐glycosylation are dependent on specific media additives. We find that Trastuzumab terminal galactosylation is sensitive to media feeding times and intracellular nucleotide sugar pools. Temporal analysis reveals an increased desirable production of single and double galactose‐occupied glycoforms over time under glucose‐starved fed‐batch cultures. Comparable galactosylation profiles were also observed between fed‐batch (nutrient‐limited) and perfusion (non‐nutrient‐limited) bioprocess conditions. In summary, our results demonstrate the utility of real‐time monitoring of mAb glycoforms and feeding critical cell culture nutrients under fed‐batch and perfusion bioprocessing conditions to produce higher‐quality biologics.

Biotechnology & Applied Microbiology↗

Exploring filamentous fungi depolymerization of corn stover in the context bioenergy queuing operations

Recalcitrance of lignocellulosic feedstocks to depolymerization is a significant barrier for bioenergy production approaches that require conversion of monomeric carbohydrates to renewable energy sources. This study assesses how low-cost modifications in the feedstock supply chain can be transformed into targeted pretreatments in the context of the entire bioenergy supply chain. The aim of this research is to overcome the physiochemical barriers in corn stover that necessitate increased severity in conversion in terms of chemical loading, temperature, and residence time. Corn stover samples were inoculated with a selective (Ceriporiopsis subvermispora) and non-selective (Phaenarochaete chrysosporium) lignin degrading filamentous fungal strains, then stored aerobically to determine the working envelope for fungal pretreatment to achieve lignin degradation. Dry matter loss and gross chemical makeup of corn stover varied by the length of treatment (2 and 4 weeks) and by the moisture content of the treated corn stover samples (40 and 60%, wet basis). Dry matter loss in P. chrysosporium inoculated biomass was elevated compared to the C. subvermispora inoculated biomass; however, treatment also induced additional chemical composition changes suggestive of depolymerization. Scanning electron microscope images reveal hyphae attached within cell lumen and suggest structural changes within P. chrysosporium treated corn stover after 60% moisture storage. These results highlight that fungal treatment approaches must balance loss of convertible material with the potential for reduction in recalcitrance. Techno-economic assessment (TEA) of fungal pretreatment in a short-term queuing system indicated the viability of this approach compared to conventional queuing operations. The total queuing system cost was estimated at $\$$1.65/tonne of biomass stored. After applying the credit of $\$$1.48/tonne from energy savings in the conversion phase using fungal pretreated biomass, the total system cost was $0.80 lower than traditional biomass queueing approach. While the TEA results suggested that treating biomass with C. subvermispora is the most economically viable storage method in the designed fungal-assisted queuing system, future research should focus on additional fungal depolymerization such as those observed in the P. chrysosporium inoculated biomass.

09 BIOMASS FUELS↗