Across-phase biomass pyrolysis stoichiometry, energy balance, and product formation kinetics

USDA-ARS?s Scientific Manuscript database

Predictive correlations between reactions occurring in the gas-, liquid- and solid-phases are necessary to economically utilize the thermochemical conversion of agricultural wastes impacting the food, water, and energy nexus. On the basis of an empirical mass balance (99.7%), this study established...

Marc Pomeroy | NREL

Science.gov Websites

sampling of on-stream components of thermochemical biomass conversion in real-time Affiliated Research Integration, Scale-Up, and Piloting Areas of Expertise Analytical sampling of hot gas and vapor phase products

Thermochemical Properties of the 1-Ethyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid under Conditions of Equilibrium with Atmospheric Moisture

NASA Astrophysics Data System (ADS)

Ramenskaya, L. M.; Grishina, E. P.; Kudryakova, N. O.

2018-01-01

Thermochemical properties of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquid [EMim]NTf2 containing moisture absorbed from the atmosphere (0.242 wt %) are investigated. The phase behavior and thermal stability relative to salt dried in vacuum are studied by means of thermogravimetry and differential scanning calorimetry at different heating and cooling rates. The glass transition, crystallization, and melting temperatures, the enthalpies of phase transitions, and the changes in heat capacity during the formation of glass are determined. It is established that the absorbed water crystallizes at a temperature of around -40.6°C and has virtually no effect on the thermal stability and phase behavior of the salt. Rapid cooling results in the ionic liquid transitioning into the glass state at -91.7 °C and the formation of three mesophases with different melting temperatures; one crystalline modification that melts at a temperature of -19.3°C forms upon slow cooling.

Coupled thermochemical, isotopic evolution and heat transfer simulations in highly irradiated UO2 nuclear fuel

NASA Astrophysics Data System (ADS)

Piro, M. H. A.; Banfield, J.; Clarno, K. T.; Simunovic, S.; Besmann, T. M.; Lewis, B. J.; Thompson, W. T.

2013-10-01

Predictive capabilities for simulating irradiated nuclear fuel behavior are enhanced in the current work by coupling thermochemistry, isotopic evolution and heat transfer. Thermodynamic models that are incorporated into this framework not only predict the departure from stoichiometry of UO2, but also consider dissolved fission and activation products in the fluorite oxide phase, noble metal inclusions, secondary oxides including uranates, zirconates, molybdates and the gas phase. Thermochemical computations utilize the spatial and temporal evolution of the fission and activation product inventory in the pellet, which is typically neglected in nuclear fuel performance simulations. Isotopic computations encompass the depletion, decay and transmutation of more than 2000 isotopes that are calculated at every point in space and time. These computations take into consideration neutron flux depression and the increased production of fissile plutonium near the fuel pellet periphery (i.e., the so-called “rim effect”). Thermochemical and isotopic predictions are in very good agreement with reported experimental measurements of highly irradiated UO2 fuel with an average burnup of 102 GW d t(U)-1. Simulation results demonstrate that predictions are considerably enhanced when coupling thermochemical and isotopic computations in comparison to empirical correlations. Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simunovic, Srdjan; Piro, Markus H.A.

Thermochimica is a software library that determines a unique combination of phases and their compositions at thermochemical equilibrium. Thermochimica can be used for stand-alone calculations or it can be directly coupled to other codes. This release of the software does not have a graphical user interface (GUI) and it can be executed from the command line or from an Application Programming Interface (API). Also, it is not intended for thermodynamic model development or for constructing phase diagrams. The main purpose of the software is to be directly coupled with a multi-physics code to provide material properties and boundary conditions formore » various physical phenomena. Significant research efforts have been dedicated to enhance computational performance through advanced algorithm development, such as improved estimation techniques and non-linear solvers. Various useful parameters can be provided as output from Thermochimica, such as: determination of which phases are stable at equilibrium, the mass of solution species and phases at equilibrium, mole fractions of solution phase constituents, thermochemical activities (which are related to partial pressures for gaseous species), chemical potentials of solution species and phases, and integral Gibbs energy (referenced relative to standard state). The overall goal is to provide an open source computational tool to enhance the predictive capability of multi-physics codes without significantly impeding computational performance.« less

Perspectives of advanced thermal management in solar thermochemical syngas production using a counter-flow solid-solid heat exchanger

NASA Astrophysics Data System (ADS)

Falter, Christoph; Sizmann, Andreas; Pitz-Paal, Robert

2017-06-01

A modular reactor model is presented for the description of solar thermochemical syngas production involving counter-flow heat exchangers that recuperate heat from the solid phase. The development of the model is described including heat diffusion within the reactive material as it travels through the heat exchanger, which was previously identified to be a possibly limiting factor in heat exchanger design. Heat transfer within the reactive medium is described by conduction and radiation, where the former is modeled with the three-resistor model and the latter with the Rosseland diffusion approximation. The applicability of the model is shown by the analysis of heat exchanger efficiency for different material thicknesses and porosities in a system with 8 chambers and oxidation and reduction temperatures of 1000 K and 1800 K, respectively. Heat exchanger efficiency is found to rise strongly for a reduction of material thickness, as the element mass is reduced and a larger part of the elements takes part in the heat exchange process. An increase of porosity enhances radiation heat exchange but deteriorates conduction. The overall heat exchange in the material is improved for high temperatures in the heat exchanger, as radiation dominates the energy transfer. The model is shown to be a valuable tool for the development and analysis of solar thermochemical reactor concepts involving heat exchange from the solid phase.

Test and evaluation of the Navy half-watt RTG. [Radioisotope Thermoelectric Generator

NASA Technical Reports Server (NTRS)

Rosell, F. E., Jr.; Lane, S. D.; Eggers, P. E.; Gawthrop, W. E.; Rouklove, P. G.; Truscello, V. C.

1976-01-01

The radioisotope thermoelectric generator (RTG) considered is to provide a continuous minimum power output of 0.5 watt at 6.0 to 8.5 volts for a minimum period of 15 years. The mechanical-electrical evaluation phase discussed involved the conduction of shock and vibration tests. The thermochemical-physical evaluation phase consisted of an analysis of the materials and the development of a thermal model. The thermoelectric evaluation phase included the accelerated testing of the thermoelectric modules.

A Computational Chemistry Database for Semiconductor Processing

NASA Technical Reports Server (NTRS)

Jaffe, R.; Meyyappan, M.; Arnold, J. O. (Technical Monitor)

1998-01-01

The concept of 'virtual reactor' or 'virtual prototyping' has received much attention recently in the semiconductor industry. Commercial codes to simulate thermal CVD and plasma processes have become available to aid in equipment and process design efforts, The virtual prototyping effort would go nowhere if codes do not come with a reliable database of chemical and physical properties of gases involved in semiconductor processing. Commercial code vendors have no capabilities to generate such a database, rather leave the task to the user of finding whatever is needed. While individual investigations of interesting chemical systems continue at Universities, there has not been any large scale effort to create a database. In this presentation, we outline our efforts in this area. Our effort focuses on the following five areas: 1. Thermal CVD reaction mechanism and rate constants. 2. Thermochemical properties. 3. Transport properties.4. Electron-molecule collision cross sections. and 5. Gas-surface interactions.

The Intramolecular Hydrogen Bond N-H···S in 2,2'-Diaminodiphenyl Disulfide: Experimental and Computational Thermochemistry.

PubMed

Ramos, Fernando; Flores, Henoc; Hernández-Pérez, Julio M; Sandoval-Lira, Jacinto; Camarillo, E Adriana

2018-01-11

The intramolecular hydrogen bond of the N-H···S type has been investigated sparingly by thermochemical and computational methods. In order to study this interaction, the standard molar enthalpies of formation in gaseous phase of diphenyl disulfide, 2,2'-diaminodiphenyl disulfide and 4,4'-diaminodiphenyl disulfide at T = 298.15 K were determined by experimental thermochemical methods and computational calculations. The experimental enthalpies of formation in gas-phase were obtained from enthalpies of formation in crystalline phase and enthalpies of sublimation. Enthalpies of formation in crystalline phase were obtained using rotatory bomb combustion calorimetry. By thermogravimetry, enthalpies of vaporization were obtained, and by combining them with enthalpies of fusion, the enthalpies of sublimation were calculated. The Gaussian-4 procedure and the atomization method were applied to obtain enthalpies of formation in gas-phase of the compounds under study. Theoretical and experimental values are in good agreement. Through natural bond orbital (NBO) analysis and a topological analysis of the electronic density, the intramolecular hydrogen bridge (N-H···S) in the 2,2'-diaminodiphenyl disulfide was confirmed. Finally, an enthalpic difference of 11.8 kJ·mol -1 between the 2,2'-diaminodiphenyl disulfide and 4,4'-diaminodiphenyl disulfide was found, which is attributed to the intramolecular N-H···S interaction.

Syngas Production By Thermochemical Conversion Of H2o And Co2 Mixtures Using A Novel Reactor Design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pearlman, Howard; Chen, Chien-Hua

The Department of Energy awarded Advanced Cooling Technologies, Inc. (ACT) an SBIR Phase II contract (#DE-SC0004729) to develop a high-temperature solar thermochemical reactor for syngas production using water and/or carbon dioxide as feedstocks. The technology aims to provide a renewable and sustainable alternative to fossil fuels, promote energy independence and mitigate adverse issues associated with climate change by essentially recycling carbon from carbon dioxide emitted by the combustion of hydrocarbon fuels. To commercialize the technology and drive down the cost of solar fuels, new advances are needed in materials development and reactor design, both of which are integral elements inmore » this program.« less

Wavelength Does Not Equal Pressure: Vertical Contribution Functions and Their Implications for Mapping Hot Jupiters

NASA Astrophysics Data System (ADS)

Dobbs-Dixon, Ian; Cowan, Nicolas B.

2017-12-01

Multi-band phase variations, in principle, allow us to infer the longitudinal temperature distributions of planets as a function of height in their atmospheres. For example, 3.6 μm emission originates from deeper layers of the atmosphere than 4.5 μm due to greater water vapor absorption at the longer wavelength. Because heat transport efficiency increases with pressure, we expect thermal phase curves at 3.6 μm to exhibit smaller amplitudes and greater phase offsets than at 4.5 μm—yet this trend is not observed. Of the seven hot Jupiters with full-orbit phase curves at 3.6 and 4.5 μm, all of them have greater phase amplitude at 3.6 μm than at 4.5 μm, while four of the seven exhibit a greater phase offset at 3.6 μm. We use a 3D radiative-hydrodynamic model to calculate theoretical phase curves of HD 189733b, assuming thermo-chemical equilibrium. The model exhibits temperature, pressure, and wavelength-dependent opacity, primarily driven by carbon chemistry: CO is energetically favored on the dayside, while CH4 is favored on the cooler nightside. Infrared opacity, therefore, changes by orders of magnitude between day and night, producing dramatic vertical shifts in the wavelength-specific photospheres, which would complicate eclipse or phase mapping with spectral data. The model predicts greater relative phase amplitude and greater phase offset at 3.6 μm than at 4.5 μm, in agreement with the data. Our model qualitatively explains the observed phase curves, but it is in tension with current thermo-chemical kinetics models that predict zonally uniform atmospheric composition due to the transport of CO from the hot regions of the atmosphere.

Olivine-modified spinel-spinel transitions in the system Mg2SiO4-Fe2SiO4: Calorimetric measurements, thermochemical calculation, and geophysical application

NASA Astrophysics Data System (ADS)

Akaogi, Masaki; Ito, Eiji; Navrotsky, Alexandra

1989-11-01

The olivine(α)-modified spinel(β)-spinel (γ) transitions in the system Mg2SiO4-Fe2SiO4 were studied by high-temperature solution calorimetry. Enthalpies of the β-γ and a α-γ transitions in Mg2SiO4 at 975 K and of the α-γ transition in Fe2SiO4 at 298 K were measured. The γ solid solution showed a positive enthalpy of mixing. Phase relations at high pressures and high temperatures were calculated from these thermochemical data including correction for the effect of nonideality of α, β, and γ solid solutions. The calculated phase diagrams agree well with those determined experimentally by Katsura and Ito very recently. The α - (Mg0.89, Fe0.11)2SiO4 transforms to β through a region of α+β without passing through the α+γ phase field at around 400 km depth in the mantle with an interval of about 18(±5) km. Temperatures at 390 and 650 km depths are estimated to be about 1673 and 1873 K, respectively, assuming an adiabatic geotherm.

Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry

DOE PAGES

Ruscic, Branko

2015-03-31

Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C–H, C–C, C–O, and O–H bond dissociation enthalpies at 298.15 K (BDE 298) and bond dissociation energies at 0 K (D 0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CH n, n = 4–0 species (methane, methyl, methylene, methylidyne, and carbon atom), C 2H n, n = 6–0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHmore » n, n = 4–0 species (methanol, hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO 2 and H 2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species.« less

Subscale solid motor nozzle tests, phase 4 and nozzle materials screening and thermal characterization, phase 5

NASA Technical Reports Server (NTRS)

Arnold, J.; Dodson, J.; Laub, B.

1979-01-01

Subscale solid motor nozzles containing a baseline material or low cost materials to be considered as potential replacements for the baseline material are designed and tested. Data are presented from tests of four identically designed 2.5 inch throat diameter nozzles and one 7 inch throat diameter nozzle. The screening of new candidate low cost materials, as well as their thermophysical and thermochemical characterization is also discussed.

Characterisation of two-stage ignition in diesel engine-relevant thermochemical conditions using direct numerical simulation

DOE PAGES

Krisman, Alex; Hawkes, Evatt R.; Talei, Mohsen; ...

2016-08-30

With the goal of providing a more detailed fundamental understanding of ignition processes in diesel engines, this study reports analysis of a direct numerical simulation (DNS) database. In the DNS, a pseudo turbulent mixing layer of dimethyl ether (DME) at 400 K and air at 900 K is simulated at a pressure of 40 atmospheres. At these conditions, DME exhibits a two-stage ignition and resides within the negative temperature coefficient (NTC) regime of ignition delay times, similar to diesel fuel. The analysis reveals a complex ignition process with several novel features. Autoignition occurs as a distributed, two-stage event. The high-temperaturemore » stage of ignition establishes edge flames that have a hybrid premixed/autoignition flame structure similar to that previously observed for lifted laminar flames at similar thermochemical conditions. In conclusion, a combustion mode analysis based on key radical species illustrates the multi-stage and multi-mode nature of the ignition process and highlights the substantial modelling challenge presented by diesel combustion.« less

Development of a Database of Thermochemical Parameters for Use with the SOLGASMIX Computer Program

DTIC Science & Technology

1988-07-01

TITANIUM CHLORIDE (TICL4) CL4Wl(CR) TUNGSTEN CHLORIDE (WCL4) CL4Wl(G) TUNGSTEN CHLORIDE (WCL4) CL4ZR1(CR) ZIRCONIUM CHLORIDE ( ZRCL4 ) CL4ZR1(G) ZIRCONIUM...CHLORIDE ( ZRCL4 ) % % % CL5MO1(CR) MOLYBDENUM CHLORIDE (MOCL5) CL5MO1(CR,L) MOLYBDENUM CHLORIDE (MOCL5) CL5MO1(G) MOLYBDENUM CHLORIDE (MOCL5) CL5MOI(L

Unique phase identification of trimetallic copper iron manganese oxygen carrier using simultaneous differential scanning calorimetry/thermogravimetric analysis during chemical looping combustion reactions with methane

DOE PAGES

Benincosa, William; Siriwardane, Ranjani; Tian, Hanjing; ...

2017-07-05

Chemical looping combustion (CLC) is a promising combustion technology that generates heat and sequestration-ready carbon dioxide that is undiluted by nitrogen from the combustion of carbonaceous fuels with an oxygen carrier, or metal oxide. This process is highly dependent on the reactivity and stability of the oxygen carrier. The development of oxygen carriers remains one of the major barriers for commercialization of CLC. Synthetic oxygen carriers, consisting of multiple metal components, have demonstrated enhanced performance and improved CLC operation compared to single metal oxides. However, identification of the complex mixed metal oxide phases that form after calcination or during CLCmore » reactions has been challenging. Without an understanding of the dominant metal oxide phase, it is difficult to determine reaction parameters and the oxygen carrier reduction pathway, which are necessary for CLC reactor design. This is particularly challenging for complex multi-component oxygen carriers such as copper iron manganese oxide (CuFeMnO 4). This study aims to differentiate the unique phase formation of a highly reactive, complex trimetallic oxygen carrier, CuFeMnO 4, from its single and bimetallic counterparts using thermochemical and reaction data obtained from simultaneous differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) during temperature programmed reductions (TPR) with methane. DSC/TGA experiments during TPR with methane provides heat flow data and corresponding reaction rate data that can be used to determine reaction routes and mechanisms during methane reduction. Furthermore, non-isothermal TPR data provides the advantage of distinguishing reactions that may not be observable in isothermal analysis. The detailed thermochemical and reaction data, obtained during TPR with methane, distinguished a unique reduction pathway for CuFeMnO 4 that differed from its single and bimetallic counterparts. This is remarkable since X-ray diffraction (XRD) data alone could not be used to distinguish the reactive trimetallic oxide phase due to overlapping peaks from various single and mixed metal oxides. The unique reduction pathway of CuFeMnO 4 was further characterized in this study using in-situ XRD TPR with methane to determine changes in the dominant trimetallic phase that influenced the thermochemical and reaction rate data.« less

Unique phase identification of trimetallic copper iron manganese oxygen carrier using simultaneous differential scanning calorimetry/thermogravimetric analysis during chemical looping combustion reactions with methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benincosa, William; Siriwardane, Ranjani; Tian, Hanjing

Chemical looping combustion (CLC) is a promising combustion technology that generates heat and sequestration-ready carbon dioxide that is undiluted by nitrogen from the combustion of carbonaceous fuels with an oxygen carrier, or metal oxide. This process is highly dependent on the reactivity and stability of the oxygen carrier. The development of oxygen carriers remains one of the major barriers for commercialization of CLC. Synthetic oxygen carriers, consisting of multiple metal components, have demonstrated enhanced performance and improved CLC operation compared to single metal oxides. However, identification of the complex mixed metal oxide phases that form after calcination or during CLCmore » reactions has been challenging. Without an understanding of the dominant metal oxide phase, it is difficult to determine reaction parameters and the oxygen carrier reduction pathway, which are necessary for CLC reactor design. This is particularly challenging for complex multi-component oxygen carriers such as copper iron manganese oxide (CuFeMnO 4). This study aims to differentiate the unique phase formation of a highly reactive, complex trimetallic oxygen carrier, CuFeMnO 4, from its single and bimetallic counterparts using thermochemical and reaction data obtained from simultaneous differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) during temperature programmed reductions (TPR) with methane. DSC/TGA experiments during TPR with methane provides heat flow data and corresponding reaction rate data that can be used to determine reaction routes and mechanisms during methane reduction. Furthermore, non-isothermal TPR data provides the advantage of distinguishing reactions that may not be observable in isothermal analysis. The detailed thermochemical and reaction data, obtained during TPR with methane, distinguished a unique reduction pathway for CuFeMnO 4 that differed from its single and bimetallic counterparts. This is remarkable since X-ray diffraction (XRD) data alone could not be used to distinguish the reactive trimetallic oxide phase due to overlapping peaks from various single and mixed metal oxides. The unique reduction pathway of CuFeMnO 4 was further characterized in this study using in-situ XRD TPR with methane to determine changes in the dominant trimetallic phase that influenced the thermochemical and reaction rate data.« less

Analysis of Efficiency of the Ship Propulsion System with Thermochemical Recuperation of Waste Heat

NASA Astrophysics Data System (ADS)

Cherednichenko, Oleksandr; Serbin, Serhiy

2018-03-01

One of the basic ways to reduce polluting emissions of ship power plants is application of innovative devices for on-board energy generation by means of secondary energy resources. The combined gas turbine and diesel engine plant with thermochemical recuperation of the heat of secondary energy resources has been considered. It is suggested to conduct the study with the help of mathematical modeling methods. The model takes into account basic physical correlations, material and thermal balances, phase equilibrium, and heat and mass transfer processes. The paper provides the results of mathematical modeling of the processes in a gas turbine and diesel engine power plant with thermochemical recuperation of the gas turbine exhaust gas heat by converting a hydrocarbon fuel. In such a plant, it is possible to reduce the specific fuel consumption of the diesel engine by 20%. The waste heat potential in a gas turbine can provide efficient hydrocarbon fuel conversion at the ratio of powers of the diesel and gas turbine engines being up to 6. When the diesel engine and gas turbine operate simultaneously with the use of the LNG vapor conversion products, the efficiency coefficient of the plant increases by 4-5%.

Thermochemical Compatibility and Oxidation Resistance of Advanced LWR Fuel Cladding

DOE PAGES

Besmann, T. M.; Yamamoto, Y.; Unocic, K. A.

2016-06-21

We assessed the thermochemical compatibility of potential replacement cladding materials for zirconium alloys in light water reactors. Considered were FeCrAl steel (similar to Kanthal APMT), Nb-1%Zr (similar to PWC-11), and a hybrid SiC-composite with a metallic barrier layer. The niobium alloy was also seen as requiring an oxidation protective layer, and a diffusion silicide was investigated. Metallic barrier layers for the SiC-composite reviewed included a FeCrAl alloy, Nb-1%Zr, and chromium. Thermochemical calculations were performed to determine oxidation behavior of the materials in steam, and for hybrid SiC-composites possible interactions between the metallic layer and SiC. Additionally, experimental exposures of SiC-alloymore » reaction couples at 673K, 1073K, and 1273K for 168 h in an inert atmosphere were made and microanalysis performed. Whereas all materials were determined to oxidize under higher oxygen partial pressures in the steam environment, these varied by material with expected protective oxides forming. Finally, the computed and experimental results indicate the formation of liquid phase eutectic in the FeCrAl-SiC system at the higher temperatures.« less

Removal of Oxygen from Electronic Materials by Vapor-Phase Processes

NASA Technical Reports Server (NTRS)

Palosz, Witold

1997-01-01

Thermochemical analyses of equilibrium partial pressures over oxides with and without the presence of the respective element condensed phase, and hydrogen, chalcogens, hydrogen chalcogenides, and graphite are presented. Theoretical calculations are supplemented with experimental results on the rate of decomposition and/or sublimation/vaporization of the oxides under dynamic vacuum, and on the rate of reaction with hydrogen, graphite, and chalcogens. Procedures of removal of a number of oxides under different conditions are discussed.

Thermochemical Users Facility | Bioenergy | NREL

Science.gov Websites

collaborate on research and development efforts or to use our equipment to test their materials and processes NREL's thermochemical process integration, scale-up, and piloting research. Schematic diagram of NRELs about NREL's thermochemical process integration, scale-up, and piloting research. Thermochemical

CFD studies on biomass thermochemical conversion.

PubMed

Wang, Yiqun; Yan, Lifeng

2008-06-01

Thermochemical conversion of biomass offers an efficient and economically process to provide gaseous, liquid and solid fuels and prepare chemicals derived from biomass. Computational fluid dynamic (CFD) modeling applications on biomass thermochemical processes help to optimize the design and operation of thermochemical reactors. Recent progression in numerical techniques and computing efficacy has advanced CFD as a widely used approach to provide efficient design solutions in industry. This paper introduces the fundamentals involved in developing a CFD solution. Mathematical equations governing the fluid flow, heat and mass transfer and chemical reactions in thermochemical systems are described and sub-models for individual processes are presented. It provides a review of various applications of CFD in the biomass thermochemical process field.

CFD Studies on Biomass Thermochemical Conversion

PubMed Central

Wang, Yiqun; Yan, Lifeng

2008-01-01

Thermochemical conversion of biomass offers an efficient and economically process to provide gaseous, liquid and solid fuels and prepare chemicals derived from biomass. Computational fluid dynamic (CFD) modeling applications on biomass thermochemical processes help to optimize the design and operation of thermochemical reactors. Recent progression in numerical techniques and computing efficacy has advanced CFD as a widely used approach to provide efficient design solutions in industry. This paper introduces the fundamentals involved in developing a CFD solution. Mathematical equations governing the fluid flow, heat and mass transfer and chemical reactions in thermochemical systems are described and sub-models for individual processes are presented. It provides a review of various applications of CFD in the biomass thermochemical process field. PMID:19325848

Comparison of Ablation Predictions for Carbonaceous Materials Using CEA and JANAF-Based Species Thermodynamics

NASA Technical Reports Server (NTRS)

Milos, Frank S.

2011-01-01

In most previous work at NASA Ames Research Center, ablation predictions for carbonaceous materials were obtained using a species thermodynamics database developed by Aerotherm Corporation. This database is derived mostly from the JANAF thermochemical tables. However, the CEA thermodynamics database, also used by NASA, is considered more up to date. In this work, the FIAT code was modified to use CEA-based curve fits for species thermodynamics, then analyses using both the JANAF and CEA thermodynamics were performed for carbon and carbon phenolic materials over a range of test conditions. The ablation predictions are comparable at lower heat fluxes where the dominant mechanism is carbon oxidation. However, the predictions begin to diverge in the sublimation regime, with the CEA model predicting lower recession. The disagreement is more significant for carbon phenolic than for carbon, and this difference is attributed to hydrocarbon species that may contribute to the ablation rate.

Entropy production in mesoscopic stochastic thermodynamics: nonequilibrium kinetic cycles driven by chemical potentials, temperatures, and mechanical forces

NASA Astrophysics Data System (ADS)

Qian, Hong; Kjelstrup, Signe; Kolomeisky, Anatoly B.; Bedeaux, Dick

2016-04-01

Nonequilibrium thermodynamics (NET) investigates processes in systems out of global equilibrium. On a mesoscopic level, it provides a statistical dynamic description of various complex phenomena such as chemical reactions, ion transport, diffusion, thermochemical, thermomechanical and mechanochemical fluxes. In the present review, we introduce a mesoscopic stochastic formulation of NET by analyzing entropy production in several simple examples. The fundamental role of nonequilibrium steady-state cycle kinetics is emphasized. The statistical mechanics of Onsager’s reciprocal relations in this context is elucidated. Chemomechanical, thermomechanical, and enzyme-catalyzed thermochemical energy transduction processes are discussed. It is argued that mesoscopic stochastic NET in phase space provides a rigorous mathematical basis of fundamental concepts needed for understanding complex processes in chemistry, physics and biology. This theory is also relevant for nanoscale technological advances.

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites

PubMed Central

2013-01-01

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction. PMID:23601907

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites

NASA Astrophysics Data System (ADS)

Wen, John Z.; Ringuette, Sophie; Bohlouli-Zanjani, Golnaz; Hu, Anming; Nguyen, Ngoc Ha; Persic, John; Petre, Catalin F.; Zhou, Y. Norman

2013-04-01

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction.

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites.

PubMed

Wen, John Z; Ringuette, Sophie; Bohlouli-Zanjani, Golnaz; Hu, Anming; Nguyen, Ngoc Ha; Persic, John; Petre, Catalin F; Zhou, Y Norman

2013-04-20

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction.

Thermochemical Kinetics of H2O and HNO3 on crystalline Nitric Acid Hydrates (alpha-, beta-NAT, NAD) in the range 175-200 K

NASA Astrophysics Data System (ADS)

Rossi, Michel J.; Iannarelli, Riccardo

2015-04-01

The growth of NAT (Nitric Acid Trihydrate, HNO3x3H2O) and NAD (Nitric Acid Dihydrate, HNO3x2H2O) on an ice substrate, the evaporative lifetime of NAT and NAD as well as the interconversion of alpha- and beta-NAT competing with evaporation and growth under UT/LS conditions depends on the interfacial kinetics of H2O and HNO3 vapor on the condensed phase. Despite the existence of some literature results we have embarked on a systematic investigation of the kinetics using a multidiagnostic experimental approach enabled by the simultaneous observation of both the gas (residual gas mass spectrometry) as well as the condensed phase (FTIR absorption in transmission). We report on thermochemically consistent mass accommodation coefficients alpha and absolute evaporation rates Rev/molecule s-1cm-3 as a function of temperature which yields the corresponding vapor pressures of both H2O and HNO3 in equilibrium with the crystalline phases, hence the term thermochemical kinetics. These results have been obtained using a stirred flow reactor (SFR) using a macroscopic pure ice film of 1 micron or so thickness as a starting substrate mimicking atmospheric ice particles and are reported in a phase diagram specifically addressing UT (Upper Troposphere)/LS (Lower Stratosphere) conditions as far as temperature and partial pressures are concerned. The experiments have been performed either at steady-state flow conditions or in transient supersaturation using a pulsed solenoid valve in order to generate gas pulses whose decay were subsequently monitored in real time. Special attention has been given to the effect of the stainless-steel vessel walls in that Langmuir adsorption isotherms for H2O and HNO3 have been used to correct for wall-adsorption of both probe gases. Typically, the accommodation coefficients of H2O and HNO3 are similar throughout the temperature range whereas the rates of evaporation Rev of H2O are significantly larger than for HNO3 thus leading to the difference in vapor pressure revealed in the phase diagram. A noteworthy effect seems to be that the accommodation coefficients obtained in pulsed gas admission experiments (transient supersaturation) lead to significantly lower values owing to surface saturation, especially in the case of the thermodynamically stable beta-NAT substrate.

Chemical vapor deposition modeling: An assessment of current status

NASA Technical Reports Server (NTRS)

Gokoglu, Suleyman A.

1991-01-01

The shortcomings of earlier approaches that assumed thermochemical equilibrium and used chemical vapor deposition (CVD) phase diagrams are pointed out. Significant advancements in predictive capabilities due to recent computational developments, especially those for deposition rates controlled by gas phase mass transport, are demonstrated. The importance of using the proper boundary conditions is stressed, and the availability and reliability of gas phase and surface chemical kinetic information are emphasized as the most limiting factors. Future directions for CVD are proposed on the basis of current needs for efficient and effective progress in CVD process design and optimization.

Investigation of La xSr 1-xCo yM 1-yO 3-δ (M = Mn Fe) perovskite materials as thermochemical energy storage media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babiniec, Sean Michael; Coker, Eric Nicholas; Miller, James E.

2015-06-23

Materials in the La xSr 1–xCo yMn 1–yO 3–δ (LSCM) and La xSr 1–xCo yFe 1–yO 3–δ (LSCF) families are candidates for high-temperature thermochemical energy storage due to their facility for cyclic endothermic reduction and exothermic oxidation. A set of 16 LSCM and 21 LSCF compositions were synthesized by a modified Pechini method and characterized by powder X-ray diffraction and thermogravimetric analysis. All materials were found to be various symmetries of the perovskite phase. LSCM was indexed as tetragonal, cubic, rhombohedral, or orthorhombic as a function of increased lanthanum content. For LSCF, compositions containing low lanthanum content were indexed asmore » cubic while materials with high lanthanum content were indexed as rhombohedral. An initial screening of redox activity was completed by thermogravimetric analysis for each composition. The top three compositions with the greatest recoverable redox capacity for each family were further characterized in equilibrium thermogravimetric experiments over a range of temperatures and oxygen partial pressures. As a result, these equilibrium experiments allowed the extraction of thermodynamic parameters for LSCM and LSCF compositions operated in thermochemical energy storage conditions.« less

Experimental and computational thermochemical study and solid-phase structure of 5,5-dimethylbarbituric acid.

PubMed

Roux, María Victoria; Notario, Rafael; Foces-Foces, Concepción; Temprado, Manuel; Ros, Francisco; Emel'yanenko, Vladimir N; Verevkin, Sergey P

2010-03-18

This paper reports an experimental and computational thermochemical study on 5,5-dimethylbarbituric acid and the solid-phase structure of the compound. The value of the standard (p(o) = 0.1 MPa) molar enthalpy of formation in the gas phase at T = 298.15 K has been determined. The energy of combustion was measured by static bomb combustion calorimetry, and from the result obtained, the standard molar enthalpy of formation in the crystalline state at T = 298.15 K was calculated as -(706.4 +/- 2.2) kJ x mol(-1). The enthalpy of sublimation was determined using a transference (transpiration) method in a saturated NB(2) stream, and a value of the enthalpy of sublimation at T = 298.15 K was derived as (115.8 +/- 0.5) kJ x mol(-1). From these results a value of -(590.6 +/- 2.3) kJ x mol(-1) for the gas-phase enthalpy of formation at T = 298.15 K was determined. Theoretical calculations at the G3 level were performed, and a study on molecular and electronic structure of the compound has been carried out. Calculated enthalpies of formation are in reasonable agreement with the experimental value. 5,5-Dimethylbarbituric acid was characterized by single crystal X-ray diffraction analysis. In the crystal structure, N-H...O=C hydrogen bonds lead to the formation of ribbons connected further by weak C-H...O=C hydrogen bonds into a three-dimensional network. The molecular and supramolecular structures observed in the solid state were also investigated in the gas phase by DFT calculations.

Air-water partition coefficients for a suite of polycyclic aromatic and other C10 through C20 unsaturated hydrocarbons.

PubMed

Rayne, Sierra; Forest, Kaya

2016-09-18

The air-water partition coefficients (Kaw) for 86 large polycyclic aromatic hydrocarbons and their unsaturated relatives were estimated using high-level G4(MP2) gas and aqueous phase calculations with the SMD, IEFPCM-UFF, and CPCM solvation models. An extensive method validation effort was undertaken which involved confirming that, via comparisons to experimental enthalpies of formation, gas-phase energies at the G4(MP2) level for the compounds of interest were at or near thermochemical accuracy. Investigations of the three solvation models using a range of neutral and ionic compounds suggested that while no clear preferential solvation model could be chosen in advance for accurate Kaw estimates of the target compounds, the employment of increasingly higher levels of theory would result in lower Kaw errors. Subsequent calculations on the polycyclic aromatic and unsaturated hydrocarbons at the G4(MP2) level revealed excellent agreement for the IEFPCM-UFF and CPCM models against limited available experimental data. The IEFPCM-UFF-G4(MP2) and CPCM-G4(MP2) solvation energy calculation approaches are anticipated to give Kaw estimates within typical experimental ranges, each having general Kaw errors of less than 0.5 log10 units. When applied to other large organic compounds, the method should allow development of a broad and reliable Kaw database for multimedia environmental modeling efforts on various contaminants.

High-Resolution Photoionization, Photoelectron and Photodissociation Studies. Determination of Accurate Energetic and Spectroscopic Database for Combustion Radicals and Molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ng, Cheuk-Yiu

2016-04-25

The main goal of this research program was to obtain accurate thermochemical and spectroscopic data, such as ionization energies (IEs), 0 K bond dissociation energies, 0 K heats of formation, and spectroscopic constants for radicals and molecules and their ions of relevance to combustion chemistry. Two unique, generally applicable vacuum ultraviolet (VUV) laser photoion-photoelectron apparatuses have been developed in our group, which have used for high-resolution photoionization, photoelectron, and photodissociation studies for many small molecules of combustion relevance.

Use of Tabulated Thermochemical Data for Pure Compounds

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.

1999-01-01

Thermodynamic data for inorganic compounds is found in a variety of tabulations and computer databases. An extensive listing of sources of inorganic thermodynamic data is provided. The three major tabulations are the JANAF tables. Thermodynamic Properties of Individual Substances, and the tabulation by Barin. The notation and choice of standard states is different in each of these tabulations, so combining data from the different tabulations is often a problem. By understanding the choice of standard states, it is possible to develop simple equations for conversion of the data from one form to another.

System and process for producing fuel with a methane thermochemical cycle

DOEpatents

Diver, Richard B.

2015-12-15

A thermochemical process and system for producing fuel are provided. The thermochemical process includes reducing an oxygenated-hydrocarbon to form an alkane and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. Another thermochemical process includes reducing a metal oxide to form a reduced metal oxide, reducing an oxygenated-hydrocarbon with the reduced metal oxide to form an alkane, and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. The system includes a reformer configured to perform a thermochemical process.

Thermochemical Conversion: Using Heat and Catalysts to Make Biofuels and Bioproducts

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

2013-07-29

This fact sheet discusses the Bioenergy Technologies Office's thermochemical conversion critical technology goal. And, how through the application of heat, robust thermochemical processes can efficiently convert a broad range of biomass.

Directly relating gas-phase cluster measurements to solution-phase hydrolysis, the absolute standard hydrogen electrode potential, and the absolute proton solvation energy.

PubMed

Donald, William A; Leib, Ryan D; O'Brien, Jeremy T; Williams, Evan R

2009-06-08

Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M(H(2)O)(24)(2+)(g) + e(-)(g)-->M(H(2)O)(24)(+)(g) and 2) M(H(2)O)(24)(2+)(g) + e(-)(g)-->MOH(H(2)O)(23)(+)(g) + H(g) and the hydrogen atom affinities of MOH(H(2)O)(23)(+)(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e(-)(g) (standard deviation of 0.02 V) and a real proton solvation free energy of -265 kcal mol(-1) are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution.

Directly Relating Gas-Phase Cluster Measurements to Solution-Phase Hydrolysis, the Absolute Standard Hydrogen Electrode Potential, and the Absolute Proton Solvation Energy

PubMed Central

Donald, William A.; Leib, Ryan D.; O’Brien, Jeremy T.; Williams, Evan R.

2009-01-01

Solution-phase, half-cell potentials are measured relative to other half-cell potentials, resulting in a thermochemical ladder that is anchored to the standard hydrogen electrode (SHE), which is assigned an arbitrary value of 0 V. A new method for measuring the absolute SHE potential is demonstrated in which gaseous nanodrops containing divalent alkaline-earth or transition-metal ions are reduced by thermally generated electrons. Energies for the reactions 1) M-(H2O)242+(g)+e−(g)→M(H2O)24+(g) and 2) M(H2O)242+(g)+e−(g)→MOH(H2O)23+(g)+H(g) and the hydrogen atom affinities of MOH(H2O)23+(g) are obtained from the number of water molecules lost through each pathway. From these measurements on clusters containing nine different metal ions and known thermochemical values that include solution hydrolysis energies, an average absolute SHE potential of +4.29 V vs. e−(g) (standard deviation of 0.02 V) and a real proton solvation free energy of −265 kcal mol−1 are obtained. With this method, the absolute SHE potential can be obtained from a one-electron reduction of nanodrops containing divalent ions that are not observed to undergo one-electron reduction in aqueous solution. PMID:19440999

The IUPAC Database of Rotational-Vibrational Energy Levels and Transitions of Water Isotopologues from Experiment and Theory

NASA Astrophysics Data System (ADS)

Császár, Attila G.; Furtenbacher, T.; Tennyson, Jonathan; Bernath, Peter F.; Brown, Linda R.; Campargue, Alain; Daumont, Ludovic; Gamache, Robert R.; Hodges, Joseph T.; Naumenko, Olga V.; Polyansky, Oleg L.; Rothman, Laurence S.; Vandaele, Ann Carine; Zobov, Nikolai F.

2014-06-01

The results of an IUPAC Task Group formed in 2004 on "A Database of Water Transitions from Experiment and Theory" (Project No. 2004-035-1-100) are presented. Energy levels and recommended labels involving exact and approximate quantum numbers for the main isotopologues of water in the gas phase, H216O, H218O, H217O, HD16O, HD18O, HD17O, D216O, D218O, and D217O, are determined from measured transition wavenumbers. The transition wavenumbers and energy levels are validated using the MARVEL (measured active rotational-vibrational energy levels) approach and first-principles nuclear motion computations. The extensive data, e.g., more than 200,000 transitions have been handled for H216O, including lines and levels that are required for analysis and synthesis of spectra, thermochemical applications, the construction of theoretical models, and the removal of spectral contamination by ubiquitous water lines. These datasets can also be used to assess where measurements are lacking for each isotopologue and to provide accurate frequencies for many yet-to-be measured transitions. The lack of high-quality frequency calibration standards in the near infrared is identified as an issue that has hindered the determination of high-accuracy energy levels at higher frequencies. The generation of spectra using the MARVEL energy levels combined with transition intensities computed using high accuracy ab initio dipole moment surfaces are discussed.

Thermochemical reactor systems and methods

DOEpatents

Lipinski, Wojciech; Davidson, Jane Holloway; Chase, Thomas Richard

2016-11-29

Thermochemical reactor systems that may be used to produce a fuel, and methods of using the thermochemical reactor systems, utilizing a reactive cylindrical element, an optional energy transfer cylindrical element, an inlet gas management system, and an outlet gas management system.

Silicon materials task of the low-cost solar array project. Phase 4: Effects of impurities and processing on silicon solar cells

NASA Technical Reports Server (NTRS)

Hopkins, R. H.; Hanes, M. H.; Davis, J. R.; Rohatgi, A.; Rai-Choudhury, P.; Mollenkopf, H. C.

1981-01-01

The effects of impurities, various thermochemical processes, and any impurity-process interactions upon the performance of terrestrial solar cells are defined. The results form a basis for silicon producers, wafer manufacturers, and cell fabricators to develop appropriate cost benefit relationships for the use of less pure, less costly solar grade silicon.

Li-SF(6) Combustion in Stored Chemical Energy Propulsion Systems

DTIC Science & Technology

1990-07-01

S 3. STRUCTURE OF SF6 3ETS IN MOLTEN LI ........... ................. 8 3.1 Mathematical Model ...ill - ABSTRACT Appropriate thermodynamic models and thermo-chemical data for multicompo- nents and immiscible phases have been Incorporated into a code...by a simplified integral model which was improved9 by the use of the local homogeneous flow approximation, equilibrium combustion model and Kc-C-g

Thermal Transport Properties in the Primary Gas-Phase Combustion Zone of Double-Base Propellant: A Sensitivity Study.

DTIC Science & Technology

1986-09-01

26-30, 1964. 17. D.R. Stull and H. Prophet, JANAF Thermochemical Tables, 2nd Ed., NSRDS- NBS-37, June 1957. 18. A.A. Zenin, "Structure of... Dean P.O. Box 48 1 Hercules, Inc. Linden, NJ 07036 Bacchus Works ATTN: K.P. McCarty Ford Aerospace and P.O. Box 98 Communications Corp. Magna, UT 84044

Thermochemical cycle analysis using linked CECS72 and HYDRGN computer programs

NASA Technical Reports Server (NTRS)

Donovan, L. F.

1977-01-01

A combined thermochemical cycle analysis computer program was designed. Input to the combined program is the same as input to the thermochemical cycle analysis program except that the extent of the reactions need not be specified. The combined program is designed to be run interactively from a computer time-sharing terminal. This mode of operation allows correction or modification of the cycle to take place during cycle analysis. A group of 13 thermochemical cycles was used to test the combined program.

CHEETAH: A next generation thermochemical code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fried, L.; Souers, P.

1994-11-01

CHEETAH is an effort to bring the TIGER thermochemical code into the 1990s. A wide variety of improvements have been made in Version 1.0. We have improved the robustness and ease of use of TIGER. All of TIGER`s solvers have been replaced by new algorithms. We find that CHEETAH solves a wider variety of problems with no user intervention (e.g. no guesses for the C-J state) than TIGER did. CHEETAH has been made simpler to use than TIGER; typical use of the code occurs with the new standard run command. CHEETAH will make the use of thermochemical codes more attractivemore » to practical explosive formulators. We have also made an extensive effort to improve over the results of TIGER. CHEETAH`s version of the BKW equation of state (BKWC) is able to accurately reproduce energies from cylinder tests; something that other BKW parameter sets have been unable to do. Calculations performed with BKWC execute very quickly; typical run times are under 10 seconds on a workstation. In the future we plan to improve the underlying science in CHEETAH. More accurate equations of state will be used in the gas and the condensed phase. A kinetics capability will be added to the code that will predict reaction zone thickness. Further ease of use features will eventually be added; an automatic formulator that adjusts concentrations to match desired properties is planned.« less

A thermochemical-biochemical hybrid processing of lignocellulosic biomass for producing fuels and chemicals.

PubMed

Shen, Yanwen; Jarboe, Laura; Brown, Robert; Wen, Zhiyou

2015-12-01

Thermochemical-biological hybrid processing uses thermochemical decomposition of lignocellulosic biomass to produce a variety of intermediate compounds that can be converted into fuels and chemicals through microbial fermentation. It represents a unique opportunity for biomass conversion as it mitigates some of the deficiencies of conventional biochemical (pretreatment-hydrolysis-fermentation) and thermochemical (pyrolysis or gasification) processing. Thermochemical-biological hybrid processing includes two pathways: (i) pyrolysis/pyrolytic substrate fermentation, and (ii) gasification/syngas fermentation. This paper provides a comprehensive review of these two hybrid processing pathways, including the characteristics of fermentative substrates produced in the thermochemical stage and microbial utilization of these compounds in the fermentation stage. The current challenges of these two biomass conversion pathways include toxicity of the crude pyrolytic substrates, the inhibition of raw syngas contaminants, and the mass-transfer limitations in syngas fermentation. Possible approaches for mitigating substrate toxicities are discussed. The review also provides a summary of the current efforts to commercialize hybrid processing. Copyright © 2015 Elsevier Inc. All rights reserved.

Development of a critically evaluated thermodynamic database for the systems containing alkaline-earth oxides

NASA Astrophysics Data System (ADS)

Shukla, Adarsh

In a thermodynamic system which contains several elements, the phase relationships among the components are usually very complex. Especially, systems containing oxides are generally very difficult to investigate owing to the very high experimental temperatures and corrosive action of slags. Due to such difficulties, large inconsistencies are often observed among the available experimental data. In order to investigate and understand the complex phase relationships effectively, it is very useful to develop thermodynamic databases containing optimized model parameters giving the thermodynamic properties of all phases as functions of temperature and composition. In a thermodynamic optimization, adjustable model parameters are calculated using, simultaneously, all available thermodynamic and phase-equilibrium data in order to obtain one set of model equations as functions of temperature and composition. Thermodynamic data, such as activities, can aid in the evaluation of the phase diagrams, and information on phase equilibria can be used to deduce thermodynamic properties. Thus, it is frequently possible to resolve discrepancies in the available data. From the model equations, all the thermodynamic properties and phase diagrams can be back-calculated, and interpolations and extrapolations can be made in a thermodynamically correct manner. The data are thereby rendered self-consistent and consistent with thermodynamic principles, and the available data are distilled into a small set of model parameters, ideal for computer storage. As part of a broader research project at the Centre de Recherche en Calcul Thermochimique (CRCT), Ecole Polytechnique to develop a thermodynamic database for multicomponent oxide systems, this thesis deals with the addition of components SrO and BaO to the existing multicomponent database of the SiO2-B2O3-Al2O 3-CaO-MgO system. Over the years, in collaboration with many industrial companies, a thermodynamic database for the SiO2-B2O 3-Al2O3-CaO-MgO system has been built quite satisfactorily. The aim of the present work was to improve the applicability of this five component database by adding SrO and BaO to it. The databases prepared in this work will be of special importance to the glass and steel industries. In the SiO2-B2O3-Al2O 3-CaO-MgO-BaO-SrO system there are 11 binary systems and 25 ternary systems which contain either BaO or SrO or both. For most of these binary systems, and for none of these ternary systems, is there a previous thermodynamic optimization available in the literature. In this thesis, thermodynamic evaluation and optimization for the 11 binary, 17 ternary and 5 quaternary BaO- and SrO- containing systems in the SiO2-B2O3-Al 2O3-CaO-MgO-BaO-SrO system is presented. All these thermodynamic optimizations were performed based on the experimental data available in the literature, except for the SrO-B2O3-SiO2 system. This latter system was optimized on the basis of a few experimental data points generated in the present work together with the data from the literature. In the present work, all the calculations were performed using the FactSage™ thermochemical software. The Modified Quasichemical Model (MQM), which is capable of taking short-range ordering into account, was used for the liquid phase. All the binary systems were critically evaluated and optimized using available phase equilibrium and thermodynamic data. The model parameters obtained as a result of this simultaneous optimization were used to represent the Gibbs energies of all phases as functions of temperature and composition. Optimized binary model parameters were used to estimate the thermodynamic properties of phases in the ternary systems. Proper “geometric” models were used for these estimations. Ternary phase diagram were calculated and compared with available experimental data. Wherever required, ternary interaction parameters were also added. The first part of this thesis comprises a general literature review on the subject of thermodynamic modeling and experimental techniques for phase diagram determination. The next chapters include the literature review and the thermodynamic optimizations of the various systems. The last part of the thesis is the presentation of experiments performed in the present work, by quenching and EPMA, in the SrO-B2O3-SiO2 system. The experiments were designed to generate the maximum amount of information with the minimum number of experiments using the thermodynamic optimization, based only on the data available in the literature, as a guide. These newly-obtained data improved the (preceding) thermodynamic optimization, based on the experimental data in the literature, of this ternary system.

Subscale Test Methods for Combustion Devices

NASA Technical Reports Server (NTRS)

Anderson, W. E.; Sisco, J. C.; Long, M. R.; Sung, I.-K.

2005-01-01

Stated goals for long-life LRE s have been between 100 and 500 cycles: 1) Inherent technical difficulty of accurately defining the transient and steady state thermochemical environments and structural response (strain); 2) Limited statistical basis on failure mechanisms and effects of design and operational variability; and 3) Very high test costs and budget-driven need to protect test hardware (aversion to test-to-failure). Ambitious goals will require development of new databases: a) Advanced materials, e.g., tailored composites with virtually unlimited property variations; b) Innovative functional designs to exploit full capabilities of advanced materials; and c) Different cycles/operations. Subscale testing is one way to address technical and budget challenges: 1) Prototype subscale combustors exposed to controlled simulated conditions; 2) Complementary to conventional laboratory specimen database development; 3) Instrumented with sensors to measure thermostructural response; and 4) Coupled with analysis

Thermochemical Conversion Techno-Economic Analysis | Bioenergy | NREL

Science.gov Websites

Conversion Techno-Economic Analysis Thermochemical Conversion Techno-Economic Analysis NREL's Thermochemical Conversion Analysis team focuses on the conceptual process design and techno-economic analysis , detailed process models, and TEA developed under this project provide insights into the potential economic

Thermochemical Studies of Epoxides and Related Compounds

PubMed Central

Morgan, Kathleen M.; Ellis, Jamie A.; Lee, Joseph; Fulton, Ashley; Wilson, Shavonda L.; Dupart, Patrick S.; Dastoori, Rosanna

2013-01-01

Gas phase heats of formation for the our butene oxide isomers are reported. They were obtained by measuring the condensed-phase heat of reduction to the corresponding alcohol using reaction calorimetry. Heats of vaporization were determined, and allow gas-phase heats of formation to be obtained. The experimental measurements are compared to calculations obtained using a variety of computational methods. Overall, the G3 and CBS-APNO methods agree quite well with the experimental data. The influence of alkyl substituents on epoxide stability is discussed. Comparisons to alkenes, cyclopropanes, aziridines, thiiranes and phosphiranes are also made. Isodesmic-type reactions were used to determine strain energies of the epoxides and related compounds with various substituents. PMID:23551240

Modelling of clay diagenesis using a combined approach of crystalchemistry and thermochemistry: a case study in the smectite illitization.

NASA Astrophysics Data System (ADS)

Geloni, Claudio; Previde Massara, Elisabetta; Di Paola, Eleonora; Ortenzi, Andrea; Gherardi, Fabrizio; Blanc, Philippe

2017-04-01

Diagenetic transformations occurring in clayey and arenaceous sediments is investigated in a number of hydrocarbon reservoirs with an integrated approach that combines mineralogical analysis, crystalchemistry, estimation of thermochemical parameters of clay minerals, and geochemical modelling. Because of the extremely variable crystalchemistry of clays, especially in the smectite - illite compositional range, the estimation of thermochemical parameters of site-specific clay-rich rocks is crucial to investigate water-rock equilibria and to predict mineralogical evolutionary patterns at the clay-sandstone interface. The task of estimating the thermochemical properties of clay minerals and predicting diagenetic reactions in natural reservoirs is accomplished through the implementation of an informatized, procedure (IP) that consists of: (i) laboratory analysis of smectite, illite and mixed layers (I/S) for the determination of their textural characteristics and chemical composition; (ii) estimation of the thermodynamic and structural parameters (enthalpy, entropy, and free energy of formation, thermal capacity, molar volume, molar weight) with a MS Excel tool (XLS) specifically developed at the French Bureau of Geological and Mining Researches (BRGM); (iii) usage of the SUPCRT (Johnson et al., 1992) software package (thereinafter, SSP) to derive log K values to be incorporated in thermodynamic databases of the standard geochemical codes; (iv) check of the consistency of the stability domains calculated with these log K values with relevant predominance diagrams; (v) final application of geochemical and reactive transport models to investigate the reactive mechanisms under different thermal conditions (40-150°C). All the simulations consider pore waters having roughly the same chemical composition of reservoir pore waters, and are performed with The Geochemist Workbench (Bethke and Yeakel, 2015), PHREEQC (Parkhurst, 1999) and TOUGHREACT (Xu, 2006). The overall procedure benefits from: (i) (minor) improvements of the I/O structure of the SSP; (ii) the development of a suite of python scripts to automate the steps needed to augment the thermodynamic database by integrating the external information provided by potential users with the XLS tool and the SSP; (iii) the creation of specific outputs to allow for more convenient handling and inspection of computed parameters of the thermodynamic database. A case study focused on non-isothermal smectite-illite transformation is presented to show the capability of our numerical models to account for clay compaction under 1D geometry conditions. This model considers fluid flow driven by the compaction of a clay layer, and chemistry-fluid flow mutual feedback with the underlying sandstone during the advancement of the diagenesis. Due to this complex interaction, as a result of the smectite-illite transformation in the clays, significant quartz cementation affects the sandstone adjacent to the compacting clay.

Three-Dimensional Modeling of Flow and Thermochemical Behavior in a Blast Furnace

NASA Astrophysics Data System (ADS)

Shen, Yansong; Guo, Baoyu; Chew, Sheng; Austin, Peter; Yu, Aibing

2015-02-01

An ironmaking blast furnace (BF) is a complex high-temperature moving bed reactor involving counter-, co- and cross-current flows of gas, liquid and solid, coupled with heat and mass exchange and chemical reactions. Two-dimensional (2D) models were widely used for understanding its internal state in the past. In this paper, a three-dimensional (3D) CFX-based mathematical model is developed for describing the internal state of a BF in terms of multiphase flow and the related thermochemical behavior, as well as process indicators. This model considers the intense interactions between gas, solid and liquid phases, and also their competition for the space. The model is applied to a BF covering from the burden surface at the top to the liquid surface in the hearth, where the raceway cavity is considered explicitly. The results show that the key in-furnace phenomena such as flow/temperature patterns and component distributions of solid, gas and liquid phases can be described and characterized in different regions inside the BF, including the gas and liquids flow circumferentially over the 3D raceway surface. The in-furnace distributions of key performance indicators such as reduction degree and gas utilization can also be predicted. This model offers a cost-effective tool to understand and control the complex BF flow and performance.

Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment

Treesearch

Shishir P. S. Chundawat; Bryon S. Donohoe; Leonardo da Costa Sousa; Thomas Elder; Umesh P. Agarwal; Fachuang Lu; John Ralph; Michael E. Himmel; Venkatesh Balan; Bruce E. Dale

2011-01-01

Deconstruction of lignocellulosic plant cell walls to fermentable sugars by thermochemical and/or biological means is impeded by several poorly understood ultrastructural and chemical barriers. A promising thermochemical pretreatment called ammonia fiber expansion (AFEX) overcomes the native recalcitrance of cell walls through subtle morphological and physicochemical...

Cesium Neonide: Molecule or Thermochemical Exercise?

ERIC Educational Resources Information Center

Blake, P. G.; Clack, D. W.

1982-01-01

Thermochemical cycles are used to decide which hypothetical compounds might exist and, if not, what is the factor that condemns them to non-existence. Hypothetical compounds of rare gases provide examples of the approach with added historical interest that thermochemical considerations led to prediction and demonstration that XePtF-6 was stable.…

Thermomechanical and Thermochemical Behavior of a Hafnium-20 Percent Tantalum Alloy. Ph.D. Thesis - North Carolina State Univ., Raleigh

NASA Technical Reports Server (NTRS)

Howell, J. P.

1971-01-01

An investigation was conducted to determine the thermomechanical and thermochemical behavior of a high temperature, oxidation resistant, hafnium-20 percent tantalum alloy. The elastic and shear moduli of this alloy were determined in air up to 1000 C and in vacuum up to 2000 C using a mechanical resonance technique. The internal friction of the alloy was measured up to temperatures greater than 1400 C. Room temperature stress-strain behavior of the oxidized and unoxidized alloy was established. The effect of annealing on the elastic and shear moduli of the extruded rod material was investigated. The martensitic-type phase transformation occurring in the alloy was studied using hot stage metallography and electron microscopy. Static oxidation tests were conducted on the alloy at temperatures from 1000 C to 1700 C with weight gain measurements made as a function of time and temperatures. Surface morphology studies were conducted on the oxide coatings formed at the different temperatures using scanning electron microscopy and X-ray diffraction techniques.

Experimental Studies on Mass Transport of Cadmium-Zinc Telluride by Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Palosz, W.; Szofran, F. R.; Lehoczky, S. L.

1995-01-01

Experimental studies on mass transport of ternary compound, Cd(1-x)Zn(x)Te by physical vapor transport (PVT) for source compositions up to X = 0.21 are presented. The effect of thermochemical (temperatures, vapor composition) and other factors (preparation of the source, crystal growth rate, temperature gradient) on composition and composition profiles of the grown crystals were investigated. A steep decrease in the mass flux with an increase in X(crystal) for X less than 0.1, and a difference in composition between the source and the deposited material have been observed. The composition profiles of the crystals were found to depend on the density and pretreatment of the source, and on the temperature gradient in the source zone. The homogeneity of the crystals improves at low undercoolings and/or when an appropriate excess of metal constituents is present in the vapor phase. The experimental results are in good agreement with our thermochemical model of this system.

Heat storage in alloy transformations

NASA Technical Reports Server (NTRS)

Birchenall, C. E.; Gueceri, S. I.; Farkas, D.; Labdon, M. B.; Nagaswami, N.; Pregger, B.

1981-01-01

The feasibility of using metal alloys as thermal energy storage media was determined. The following major elements were studied: (1) identification of congruently transforming alloys and thermochemical property measurements; (2) development of a precise and convenient method for measuring volume change during phase transformation and thermal expansion coefficients; (3) development of a numerical modeling routine for calculating heat flow in cylindrical heat exchangers containing phase change materials; and (4) identification of materials that could be used to contain the metal alloys. Several eutectic alloys and ternary intermetallic phases were determined. A method employing X-ray absorption techniques was developed to determine the coefficients of thermal expansion of both the solid and liquid phases and the volume change during phase transformation from data obtained during one continuous experimental test. The method and apparatus are discussed and the experimental results are presented. The development of the numerical modeling method is presented and results are discussed for both salt and metal alloy phase change media.

Study of the formation of thermochemical laser-induced periodic surface structures on Cr, Ti, Ni and NiCr films under femtosecond irradiation

NASA Astrophysics Data System (ADS)

Dostovalov, A. V.; Korolkov, V. P.; Terentyev, V. S.; Okotrub, K. A.; Dultsev, F. N.; Babin, S. A.

2017-07-01

The formation of femtosecond laser-induced periodic surface structures (LIPSS's) on Cr, Ti, Ni and NiCr films (with different Cr contents) is investigated. It is established that thermochemical LIPSS's with periods of 950, 930 and 980 nm are formed, respectively, on the surfaces of titanium, chromium, and nichrome (with a chromium content of 20%); however, thermochemical LIPSS's are not formed on the surfaces of nickel and nichrome with a low chromium content, although Raman data indicate that oxidation occurs in all cases. A weakly ordered ablated structure with a period of 250-300 nm is found to be formed on oxidised areas of thermochemical LIPSS's in the case of chromium and nichrome (80/20). Experimental data on selective etching of thermochemical LIPSS's on titanium and chromium films are presented.

Thermochemical conversion of biomass storage covers to reduce ammonia emissions from dairy manure Thermochemical conversion of biomass storage covers to reduce ammonia emissions from dairy manure

USDA-ARS?s Scientific Manuscript database

Manure storages, and in particular those storing digested manure, are a source of ammonia (NH3) emissions. Permeable manure storage covers can reduce NH3 emissions, however performance can decline as they degrade. Thermochemical conversion of biomass through pyrolysis and steam treatment could incre...

Evaluation of chemical, thermobaric and thermochemical pre-treatment on anaerobic digestion of high-fat cattle slaughterhouse waste.

PubMed

Harris, Peter W; Schmidt, Thomas; McCabe, Bernadette K

2017-11-01

This work aimed to enhance the anaerobic digestion of fat-rich dissolved air flotation (DAF) sludge through chemical, thermobaric, and thermochemical pre-treatment methods. Soluble chemical oxygen demand was enhanced from 16.3% in the control to 20.84% (thermobaric), 40.82% (chemical), and 50.7% (thermochemical). Pre-treatment altered volatile fatty acid concentration by -64% (thermobaric), 127% (chemical) and 228% (thermochemical). Early inhibition was reduced by 20% in the thermochemical group, and 100% in the thermobaric group. Specific methane production was enhanced by 3.28% (chemical), 8.32% (thermobaric), and 8.49% (thermochemical) as a result of pre-treatment. Under batch digestion, thermobaric pre-treatment demonstrated the greatest improvement in methane yield with respect to degree of pre-treatment applied. Thermobaric pre-treatment was also the most viable for implementation at slaughterhouses, with potential for heat-exchange to reduce pre-treatment cost. Further investigation into long-term impact of pre-treatments in semi-continuous digestion experiments will provide additional evaluation of appropriate pre-treatment options for high-fat slaughterhouse wastewater. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Thermal barrier coating life prediction model

NASA Technical Reports Server (NTRS)

Pilsner, B. H.; Hillery, R. V.; Mcknight, R. L.; Cook, T. S.; Kim, K. S.; Duderstadt, E. C.

1986-01-01

The objectives of this program are to determine the predominant modes of degradation of a plasma sprayed thermal barrier coating system, and then to develop and verify life prediction models accounting for these degradation modes. The program is divided into two phases, each consisting of several tasks. The work in Phase 1 is aimed at identifying the relative importance of the various failure modes, and developing and verifying life prediction model(s) for the predominant model for a thermal barrier coating system. Two possible predominant failure mechanisms being evaluated are bond coat oxidation and bond coat creep. The work in Phase 2 will develop design-capable, causal, life prediction models for thermomechanical and thermochemical failure modes, and for the exceptional conditions of foreign object damage and erosion.

Ceria based inverse opals for thermochemical fuel production: Quantification and prediction of high temperature behavior

NASA Astrophysics Data System (ADS)

Casillas, Danielle Courtney

Solar energy has the potential to supply more than enough energy to meet humanity's energy demands. Here, a method for thermochemical solar energy storage through fuel production is presented. A porous non-stoichiometric oxide, ceria, undergoes partial thermal reduction and oxidation with concentrated solar energy as a heat source, and water as an oxidant. The resulting yields for hydrogen fuel and oxygen are produced in two discrete steps, while the starting material maintains its original phase. Ordered porosity has been shown superior to random porosity for thermochemical fuel production applications, but stability limits for these structures are currently undefined. Ceria-based inverse opals are currently being investigated to assess the architectural influence on thermochemical hydrogen production. Low tortuosity and continuous interconnected pore network allow for facile gas transport and improved reaction kinetics. Ceria-based ordered materials have recently been shown to increase maximum hydrogen production over non-ordered porous ceria. Thermal stability of ordered porosity was quantified using quantitative image analysis. Fourier analysis was applied to SEM images of the material. The algorithm results in an order parameter gamma that describes the degree of long range order maintained by these structures, where gamma>4 signifies ordered porosity. According to this metric, a minimum zirconium content of 20 atomic percent (at%) is necessary for these architectures to survive aggressive annealing up to 1000°C. Zirconium substituted ceria (ZSC) with Zr loadings in excess of 20at% developed undesired tetragonal phases. Through gamma, we were able to find a balance between the benefit of zirconium additions on structural stability and its negative impact on phase. This work demonstrates the stability of seemingly delicate architectures, and the operational limit for ceria based inverse opals to be 1000°C for 1microm pore size. Inverse opals having sub-micron pores did not sustain ordered structures after heating, and those larger than 1microm had reinforced structural stability. Furthermore, this analysis was applied to materials which underwent isothermal hydrogen/water redox cycles. ZDC20 inverse opals having 300, 650 and 1000nm pore sizes maintained ordered porosity at 800°C, indicating a novel opportunity for use at higher temperatures. The mechanism of inverse opal degradation was investigated. Both in situ and ex situ electron microscopy studies were performed on inverse opals subjected to high temperatures. Coarsening by surface diffusion was found to be the dominant grain growth mechanism. The inverse opal grain growth mechanism was found to deviate from that of porous materials due to the high porosity and an upper limit to grain size caused by structural confinement. Furthermore, in situ experiments enabled correlation of nano-scale grain growth to micro-scale feature changes, resulting in an empirical relationship. Lastly, this dissertation presents an investigation of the effect of ordered porosity on hydrogen production rate and quantity. These results differ from those presented in literature, and an opportunity for further investigation is proposed.

Ablation Predictions for Carbonaceous Materials Using Two Databases for Species Thermodynamics

NASA Technical Reports Server (NTRS)

Milos, F. S.; Chen, Y.-K.

2013-01-01

During previous work at NASA Ames Research Center, most ablation predictions were obtained using a species thermodynamics database derived primarily from the JANAF thermochemical tables. However, the chemical equilibrium with applications thermodynamics database, also used by NASA, is considered more up to date. In this work, ablation analyses were performed for carbon and carbon phenolic materials using both sets of species thermodynamics. The ablation predictions are comparable at low and moderate heat fluxes, where the dominant mechanism is carbon oxidation. For high heat fluxes where sublimation is important, the predictions differ, with the chemical equilibrium with applications model predicting a lower ablation rate. The disagreement is greater for carbon phenolic than for carbon, and this difference is attributed to hydrocarbon species that may contribute to the ablation rate. Sample calculations for representative Orion and Stardust environments show significant differences only in the sublimation regime. For Stardust, if the calculations include a nominal environmental uncertainty for aeroheating, then the chemical equilibrium with applications model predicts a range of recession that is consistent with measurements for both heatshield cores.

Comparison between thermochemical and phase stability data for the quartz-coesite-stishovite transformations

NASA Technical Reports Server (NTRS)

Weaver, J. S.; Chipman, D. W.; Takahashi, T.

1979-01-01

Phase stability and elasticity data have been used to calculate the Gibbs free energy, enthalpy, and entropy changes at 298 K and 1 bar associated with the quartz-coesite and coesite-stishovite transformations in the system SiO2. For the quartz-coesite transformation, these changes disagree by a factor of two or three with those obtained by calorimetric techniques. The phase boundary for this transformation appears to be well determined by experiment; the discrepancy, therefore, suggests that the calorimetric data for coesite are in error. Although the calorimetric and phase stability data for the coesite-stishovite transformation yield the same transition pressure at 298 K, the phase-boundary slopes disagree by a factor of two. At present, it is not possible to determine which of the data are in error. Thus serious inconsistencies exist in the thermodynamic data for the polymorphic transformations of silica.

An analysis of hydrogen production via closed-cycle schemes. [thermochemical processings from water

NASA Technical Reports Server (NTRS)

Chao, R. E.; Cox, K. E.

1975-01-01

A thermodynamic analysis and state-of-the-art review of three basic schemes for production of hydrogen from water: electrolysis, thermal water-splitting, and multi-step thermochemical closed cycles is presented. Criteria for work-saving thermochemical closed-cycle processes are established, and several schemes are reviewed in light of such criteria. An economic analysis is also presented in the context of energy costs.

Experimental Demonstration of the Thermochemical Reduction of Ceria in a Solar Aerosol Reactor

PubMed Central

2016-01-01

We report on the experimental demonstration of an aerosol solar reactor for the thermal reduction of ceria, as part of a thermochemical redox cycle for splitting H2O and CO2. The concept utilizes a cavity-receiver enclosing an array of alumina tubes, each containing a downward gravity-driven aerosol flow of ceria particles countercurrent to an inert sweep gas flow for intrinsic separation of reduced ceria and oxygen. A 2 kWth lab-scale prototype with a single tube was tested under radiative fluxes approaching 4000 suns, yielding reaction extents of up to 53% of the thermodynamic equilibrium at 1919 K within residence times below 1 s. Upon thermal redox cycling, fresh primary particles of 2.44 μm mean size initially formed large agglomerates of 1000 μm mean size, then sintered into stable particles of 150 μm mean size. The reaction extent was primarily limited by heat transfer for large particles/agglomerates (mean size > 200 μm) and by the gas phase advection of product O2 for smaller particles. PMID:27853339

Experimental Demonstration of the Thermochemical Reduction of Ceria in a Solar Aerosol Reactor.

PubMed

Welte, Michael; Barhoumi, Rafik; Zbinden, Adrian; Scheffe, Jonathan R; Steinfeld, Aldo

2016-10-12

We report on the experimental demonstration of an aerosol solar reactor for the thermal reduction of ceria, as part of a thermochemical redox cycle for splitting H 2 O and CO 2 . The concept utilizes a cavity-receiver enclosing an array of alumina tubes, each containing a downward gravity-driven aerosol flow of ceria particles countercurrent to an inert sweep gas flow for intrinsic separation of reduced ceria and oxygen. A 2 kW th lab-scale prototype with a single tube was tested under radiative fluxes approaching 4000 suns, yielding reaction extents of up to 53% of the thermodynamic equilibrium at 1919 K within residence times below 1 s. Upon thermal redox cycling, fresh primary particles of 2.44 μm mean size initially formed large agglomerates of 1000 μm mean size, then sintered into stable particles of 150 μm mean size. The reaction extent was primarily limited by heat transfer for large particles/agglomerates (mean size > 200 μm) and by the gas phase advection of product O 2 for smaller particles.

Recent Advances in Modeling Hugoniots with Cheetah

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glaesemann, K R; Fried, L E

2005-07-26

We describe improvements to the Cheetah thermochemical-kinetics code's equilibrium solver to enable it to find a wider range of thermodynamic states. Cheetah supports a wide range of elements, condensed detonation products, and gas phase reactions. Therefore, Cheetah can be applied to a wide range of shock problems involving both energetic and non-energetic materials. An improve equation of state is also introduced. New experimental validations of Cheetah's equation of state methodology have been performed, including both reacted and unreacted Hugoniots.

Recent Advances in Modeling Hugoniots with Cheetah

NASA Astrophysics Data System (ADS)

Glaesemann, K. R.; Fried, L. E.

2006-07-01

We describe improvements to the Cheetah thermochemical-kinetics code's equilibrium solver to enable it to find a wider range of thermodynamic states. Cheetah supports a wide range of elements, condensed detonation products, and gas phase reactions. Therefore, Cheetah can be applied to a wide range of shock problems involving both energetic and non-energetic materials. An improve equation of state is also introduced. New experimental validations of Cheetah's equation of state methodology have been performed, including both reacted and unreacted Hugoniots.

Thermochemical analyses of the oxidative vaporization of metals and oxides by oxygen molecules and atoms

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Leisz, D. M.; Fryburg, G. C.; Stearns, C. A.

1977-01-01

Equilibrium thermochemical analyses are employed to describe the vaporization processes of metals and metal oxides upon exposure to molecular and atomic oxygen. Specific analytic results for the chromium-, platinum-, aluminum-, and silicon-oxygen systems are presented. Maximum rates of oxidative vaporization predicted from the thermochemical considerations are compared with experimental results for chromium and platinum. The oxidative vaporization rates of chromium and platinum are considerably enhanced by oxygen atoms.

Treatment of aqueous phase of bio-oil by granular activated carbon and evaluation of biogas production.

PubMed

Shanmugam, Saravanan R; Adhikari, Sushil; Wang, Zhouhang; Shakya, Rajdeep

2017-01-01

Hydrothermal liquefaction of wet biomass such as algae is a promising thermochemical process for the production of bio-oil. Bio-oil aqueous phase generated during liquefaction process is rich in complex organics and can be utilized for biogas production following its pre-treatment with granular activated carbon. In our study, use of 30% activated carbon resulted in higher chemical oxygen demand (COD) reduction (53±0.3%) from aqueous phase. Higher CH 4 production (84±12mL/gCOD) was also observed in 30% carbon-treated aqueous phase fed cultures, whereas only 32±6mLCH 4 /gCOD was observed in control (non-carbon treated) cultures. The results from this study indicate that almost 67±0.3% initial COD of aqueous phase can be reduced using a combination of both carbon treatment and biogas production. This study shows that aqueous phase can be utilized for CH 4 production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Assessment of analytical techniques for predicting solid propellant exhaust plumes

NASA Technical Reports Server (NTRS)

Tevepaugh, J. A.; Smith, S. D.; Penny, M. M.

1977-01-01

The calculation of solid propellant exhaust plume flow fields is addressed. Two major areas covered are: (1) the applicability of empirical data currently available to define particle drag coefficients, heat transfer coefficients, mean particle size and particle size distributions, and (2) thermochemical modeling of the gaseous phase of the flow field. Comparisons of experimentally measured and analytically predicted data are made. The experimental data were obtained for subscale solid propellant motors with aluminum loadings of 2, 10 and 15%. Analytical predictions were made using a fully coupled two-phase numerical solution. Data comparisons will be presented for radial distributions at plume axial stations of 5, 12, 16 and 20 diameters.

Non-stoichiometry in U 3Si 2

DOE PAGES

Middleburgh, Simon C.; Grimes, Robin W.; Lahoda, Ed J.; ...

2016-10-08

Uranium silicides, in particular U 3Si 2, are being explored as an advanced nuclear fuel with increased accident tolerance as well as competitive economics compared to the baseline UO 2 fuel. Here we use density functional theory calculations and thermochemical analysis to assess the stability of U 3Si 2 with respect to non-stoichiometry reactions in both the hypo- and hyper-stoichiometric regimes. We find that the degree of non-stoichiometry in U 3Si 2 is much smaller than in UO 2 and at most reaches a few percent at high temperature. Non-stoichiometry impacts fuel performance by determining whether the loss of uraniummore » due to fission leads to a non-stoichiometric U 3Si 2±x phase or precipitation of a second U-Si phase. Lastly, we also investigate the U 5Si 4 phase as a candidate for the equilibrium phase diagram.« less

Nitriding of AISI 4140 steel by a low energy broad ion source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ochoa, E. A.; Figueroa, C. A.; Alvarez, F.

2006-11-15

A comprehensive study of the thermochemical nitriding process of steel AISI 4140 by low energy ion implantation (Kaufmann cell) is reported. Different times of implantation were employed and the studied samples were characterized by x-ray diffraction, in situ photoemission electron spectroscopy, scanning electron microscopy, and hardness (nanoindentation) measurements. The linear relationship between nitrogen content and hardness was verified. The structure of the nitrided layer was characterized yielding that the compound layer is formed by coarse precipitates, around small grains, constituted principally by {epsilon}-Fe{sub 2-3}N and {gamma}-Fe{sub 4}N phases and the diffusion zone is formed by fine precipitates, around big grainsmore » of the original martensitic phase, constituted principally by {gamma}-Fe{sub 4}N phase. Finally, a diffusion model for multiphase systems was applied to determine effective diffusion coefficients of nitrogen in the different phases.« less

M3FT-15OR0202212: SUBMIT SUMMARY REPORT ON THERMODYNAMIC EXPERIMENT AND MODELING

DOE Office of Scientific and Technical Information (OSTI.GOV)

McMurray, Jake W.; Brese, Robert G.; Silva, Chinthaka M.

2015-09-01

Modeling the behavior of nuclear fuel with a physics-based approach uses thermodynamics for key inputs such as chemical potentials and thermal properties for phase transformation, microstructure evolution, and continuum transport simulations. Many of the lanthanide (Ln) elements and Y are high-yield fission products. The U-Y-O and U-Ln-O ternaries are therefore key subsystems of multi-component high-burnup fuel. These elements dissolve in the dominant urania fluorite phase affecting many of its properties. This work reports on an effort to assess the thermodynamics of the U-Pr-O and U-Y-O systems using the CALPHAD (CALculation of PHase Diagrams) method. The models developed within this frameworkmore » are capable of being combined and extended to include additional actinides and fission products allowing calculation of the phase equilibria, thermochemical and material properties of multicomponent fuel with burnup.« less

Physico-chemical and thermochemical studies of the hydrolytic conversion of amorphous tricalcium phosphate into apatite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somrani, Saida; Banu, Mihai; Jemal, Mohamed

2005-05-15

The conversion of amorphous tricalcium phosphate with different hydration ratio into apatite in water at 25 deg. C has been studied by microcalorimetry and several physical-chemical methods. The hydrolytic transformation was dominated by two strong exothermic events. A fast, relatively weak, wetting process and a very slow but strong heat release assigned to a slow internal rehydration and the crystallization of the amorphous phase into an apatite. The exothermic phenomenon related to the rehydration exceeded the crystalline transformation enthalpy. Rehydration occurred before the conversion of the amorphous phase into apatite and determined the advancement of the hydrolytic reaction. The apatiticmore » phases formed evolved slightly with time after their formation. The crystallinity increased whereas the amount of HPO{sub 4}{sup 2-} ion decreased. These data allow a better understanding of the behavior of biomaterials involving amorphous phases such as hydroxyapatite plasma-sprayed coatings.« less

Hugoniots of aerogels involving carbon and resorcinol formaldehyde

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hrubesh, L H; Ree, F H; Schmidt, R D

1999-06-24

Recently, a first-order phase transition is predicted in liquid carbon using atomistic simulation and Brenner's bond order potential. There are also experimental data suggesting a possibility for a first-order phase transition. In light of this, a thermochemical equilibrium code (CHEQ) is used to provide guidance to experiments to find a liquid-liquid phase change in carbon foam and carbon-rich aerogel, resorcinol formaldehyde. Isotherms and Hugoniots were computed based on the previous analysis by van Thiel and Ree. The present calculations predict the liquid-liquid-graphite triple point to be at 5000 K and 5.2 GPa and its critical point to be at 6000more » K and 8.8 GPa. The present Hugoniot calculations suggest that the liquid-liquid phase transition may be detected by performing a shock experiment with initial density of approximately 0.15 gm/cm{sup 3}.« less

A geophysical perspective on mantle water content and melting: Inverting electromagnetic sounding data using laboratory-based electrical conductivity profiles

NASA Astrophysics Data System (ADS)

Khan, A.; Shankland, T. J.

2012-02-01

This paper applies electromagnetic sounding methods for Earth's mantle to constrain its thermal state, chemical composition, and "water" content. We consider long-period inductive response functions in the form of C-responses from four stations distributed across the Earth (Europe, North America, Asia and Australia) covering a period range from 3.9 to 95.2 days and sensitivity to ~ 1200 km depth. We invert C-responses directly for thermo-chemical state using a self-consistent thermodynamic method that computes phase equilibria as functions of pressure, temperature, and composition (in the Na2O-CaO-FeO-MgO-Al2O3-SiO2 model system). Computed mineral modes are combined with recent laboratory-based electrical conductivity models from independent experimental research groups (Yoshino (2010) and Karato (2011)) to compute bulk conductivity structure beneath each of the four stations from which C-responses are estimated. To reliably allocate water between the various mineral phases we include laboratory-measured water partition coefficients for major upper mantle and transition zone minerals. This scheme is interfaced with a sampling-based algorithm to solve the resulting non-linear inverse problem. This approach has two advantages: (1) It anchors temperatures, composition, electrical conductivities, and discontinuities that are in laboratory-based forward models, and (2) At the same time it permits the use of geophysical inverse methods to optimize conductivity profiles to match geophysical data. The results show lateral variations in upper mantle temperatures beneath the four stations that appear to persist throughout the upper mantle and parts of the transition zone. Calculated mantle temperatures at 410 and 660 km depth lie in the range 1250-1650 °C and 1500-1750 °C, respectively, and generally agree with the experimentally-determined temperatures at which the measured phase reactions olivine → β-spinel and γ-spinel → ferropericlase + perovskite occur. The retrieved conductivity structures beneath the various stations tend to follow trends observed for temperature with the strongest lateral variations in the uppermost mantle; for depths > 300 km conductivities appear to depend less on the particular conductivity database. Conductivities at 410 km and at 660 km depth are found to agree overall with purely geophysically-derived global and semi-global one-dimensional conductivity models. Both electrical conductivity databases point to < 0.01 wt.% H2O in the upper mantle. For transition zone minerals results from the laboratory database of Yoshino (2010) suggest that a much higher water content (up to 2 wt.% H2O) is required than in the other database (Karato, 2011), which favors a relatively "dry" transition zone (< 0.01 wt.% H2O). Incorporating laboratory measurements of hydrous silicate melting relations and available conductivity data allows us to consider the possibility of hydration melting and a high-conductivity melt layer above the 410-km discontinuity. The latter appears to be 1) regionally localized and 2) principally a feature from the Yoshino (2010) database. Further, there is evidence of lateral heterogeneity: The mantle beneath southwestern North America and central China appears "wetter" than that beneath central Europe or Australia.

Thermochemical Production of Hydrogen from Water.

ERIC Educational Resources Information Center

Bamberger, C. E.; And Others

1978-01-01

Discusses the possible advantages of decomposing water by means of thermochemical cycles. Explains that, if energy consumption can be minimized, this method is capable of producing hydrogen more efficiently than electrolysis. (GA)

2011 Biomass Program Platform Peer Review. Thermochemical Conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grabowski, Paul E.

This document summarizes the recommendations and evaluations provided by an independent external panel of experts at the 2011 U.S. Department of Energy Biomass Program’s Thermochemical Conversion Platform Review meeting.

A first-principles study on new high-pressure metastable polymorphs of MoO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Becker, Nils; Dronskowski, Richard; Jülich-Aachen Research Alliance

The pressure-dependence of the stabilities of several MoO{sub 2} phases has been investigated by density-functional theory (GGA/PBE/PAW). Out of a set of 15 MX{sub 2} structures, the [SnO{sub 2}(II)], [α-PbO{sub 2}], and a modified rutile structure type were identified as possible metastable MoO{sub 2} polymorphs based on the analysis of thermodynamic properties and dynamic stability. High-pressure calculations suggest an orthorhombic TiO{sub 2} structure, dubbed [ortho-TiO{sub 2}], as a high-pressure polymorph at around 25 GPa. Furthermore, we find that the previously reported rutile-type MoO{sub 2} may be understood as a modified rutile type similar to the [VO{sub 2}] structure. - Graphicalmore » abstract: First-principles electronic structure and thermochemical calculations reveal four structure candidates as possible metastable polymorphs of MoO{sub 2}. Most promising is a distorted rutile-type similar to the known [VO{sub 2}] structure. An orthorhombic polymorph is proposed as a high-pressure polymorph. Display Omitted - Highlights: • Three possible metastable structure candidates for MoO{sub 2}. • Undistorted rutile type is improbable, a new distorted rutile-type MoO{sub 2} was suggested. • Orthorhombic phase of MoO{sub 2} (ortho-TiO{sub 2} type) should form at 25 GPa. • ab initio thermochemical data provided for MoO{sub 2}.« less

Mapping the Earth's thermochemical and anisotropic structure using global surface wave data

NASA Astrophysics Data System (ADS)

Khan, A.; Boschi, L.; Connolly, J. A. D.

2011-01-01

We have inverted global fundamental mode and higher-order Love and Rayleigh wave dispersion data jointly, to find global maps of temperature, composition, and radial seismic anisotropy of the Earth's mantle as well as their uncertainties via a stochastic sampling-based approach. We apply a self-consistent thermodynamic method to systematically compute phase equilibria and physical properties (P and S wave velocity, density) that depend only on composition (in the Na2-CaO-FeO-MgO-Al2O3-SiO2 model system), pressure, and temperature. Our 3-D maps are defined horizontally by 27 different tectonic regions and vertically by a number of layers. We find thermochemical differences between oceans and continents to extend down to ˜250 km depth, with continents and cratons appearing chemically depleted (high magnesium number (Mg #) and Mg/Si ratio) and colder (>100°C) relative to oceans, while young oceanic lithosphere is hotter than its intermediate age and old counterparts. We find what appears to be strong radial S wave anisotropy in the upper mantle down to ˜200 km, while there seems to be little evidence for shear anisotropy at greater depths. At and beneath the transition zone, 3-D heterogeneity is likely uncorrelated with surface tectonics; as a result, our tectonics-based parameterization is tenuous. Despite this weakness, constraints on the gross average thermochemical and anisotropic structure to ˜1300 km depth can be inferred, which appear to indicate that the compositions of the upper (low Mg# and high Mg/Si ratio) and lower mantle (high Mg# and low Mg/Si ratio) might possibly be distinct.

Constraints on core-mantle boundary topography from models of thermal and thermochemical convection

NASA Astrophysics Data System (ADS)

Deschamps, Frédéric; Rogister, Yves; Tackley, Paul J.

2018-01-01

Mantle flow induces dynamic topography at the core-mantle boundary (CMB), with distribution and amplitude that depend on details of the flow. To assess whether observations of CMB topography can give constraints on deep mantle structure, we determine CMB dynamic topography associated with different models of mantle convection, including thermochemical and purely thermal models. We investigate the influence of key controlling parameters, specifically the thermal viscosity ratio (ΔηT) and, for thermochemical models, the density contrast (ΔρC) and viscosity ratio (ΔηC) between primordial and regular materials. In purely thermal models, plume clusters induce positive topography with an amplitude that decreases with increasing ΔηT. In thermochemical models with moderate density contrasts, around 100-200 kg m-3, reservoirs of dense material induce depressions in CMB topography, surrounded by a ridge of positive topography. The average depression depth and ridge height increase with increasing ΔρC and ΔηC, but decrease with increasing ΔηT. We find that for purely thermal models or thermochemical models with ΔρC ˜ 90 kg m-3 and less, the long-wavelength (spherical harmonic degrees up to l = 4) dynamic topography and shear wave velocity anomalies predicted by thermochemical distributions anticorrelate. By contrast, for models with ΔρC ≥ 100 kg m-3 and ΔηC > 1, long-wavelength dynamic topography and shear wave velocity anomalies correlate well. This potentially provides a test to infer the nature, that is, either purely or mostly thermal (ΔρC ≤ 100 kg m-3 m-3) or strongly thermochemical (ΔρC ≥ 100 kg m-3), of the low shear wave velocity provinces observed by global tomographic images. The presence of post-perovskite, provided that its viscosity is similar to that of bridgmanite, does not alter these conclusions.

Status of the DOE /STOR/-sponsored national program on hydrogen production from water via thermochemical cycles

NASA Technical Reports Server (NTRS)

Baker, C. E.

1977-01-01

A pure thermochemical cycle is a system of linked regenerative chemical reactions which accepts only water and heat and produces hydrogen. Thermochemical cycles are potentially a more efficient and cheaper means of producing hydrogen from water than is the generation of electricity followed by electrolysis. The Energy Storage Systems Division of the Department of Energy is currently funding a national program on thermochemical hydrogen production. The National Aeronautics and Space Administration is responsible for the technical management of this program. The goal is to develop a cycle which can potentially operate with an efficiency greater than 40% using a heat source providing a maximum available temperature of 1150 K. A closed bench-scale demonstration of such a cycle would follow. This cycle would be labeled a 'reference cycle' and would serve as a baseline against which future cycles would be compared.

Methods of calculating engineering parameters for gas separations

NASA Technical Reports Server (NTRS)

Lawson, D. D.

1980-01-01

A group additivity method has been generated which makes it possible to estimate, from the structural formulas alone, the energy of vaporization and the molar volume at 25 C of many nonpolar organic liquids. From these two parameters and appropriate thermodynamic relationships it is then possible to predict the vapor pressure of the liquid phase and the solubility of various gases in nonpolar organic liquids. The data are then used to evaluate organic and some inorganic liquids for use in gas separation stages or as heat exchange fluids in prospective thermochemical cycles for hydrogen production.

Lunar and Planetary Science XXXVI, Part 8

NASA Technical Reports Server (NTRS)

2005-01-01

The following topics were discussed: Why Small is Beautiful, and How to Detect Another 10 Billion Small Main Belt Asteroids; Basalts in Mare Humorum and S.E. Procellarum; Basalts in Mare Serenitatis, Lacus Somniorum, Lacus Mortis and Part of Mare Tranquillitatis; Revised Thorium Abundances for Lunar Red Spots; Integrating Global-Scale Mission Datasets - Understanding the Martian Crust; Comparing Goldstone Solar System Radar Earth-based Observations of Mars with Orbital Datasets; Water Ice Clouds in the Martian Atmosphere: A View from MGS TES; Lunar Meteorite Northeast Africa 001: An Anorthositic Regolith Breccia with Mixed Highland/Mare Components; One Spectrometer, Two Spectra: Complementary Hemispherical Reflectance and Thermal Emission Spectroscopy Using a Single FTIR Instrument; Alteration Phases Associated with High Concentrations of Orthopyroxene and Olivine on Mars; Experimental Crystallization of Fe-rich Basalt: Application to Cooling Rate and Oxygen Fugacity of Nakhlite MIL-03346; Thermo-Chemical Convection in Europa s Icy Shell with Salinity; Tectonic Pressurization of Aquifers in the Formation of Mangala and Athabasca Valles on Mars; 3D Structural Interpretation of the Eagle Butte Impact Structure, Alberta, Canada; Ultraviolet Views of Enceladus, Tethys, and Dione; Crustal Plateaus as Ancient Large Impact Features: A Hypothesis; New Observations of Crustal Plateau Surface Histories, Venus: Implications for Crustal Plateau Hypotheses; Detailed Mineralogical Characterizations of Four S-Asteroids: 138 Tolosa, 306 Unitas, 346 Hermentaria, and 480 Hansa; Working with Planetary Coordinate Reference Systems; Bilingual Map of Mercury; and The Io Mountain Online Database.

Thermochemical and kinetic aspects of the sulfurization of Cu-Sb and Cu-Bi thin films

NASA Astrophysics Data System (ADS)

Colombara, Diego; Peter, Laurence M.; Rogers, Keith D.; Hutchings, Kyle

2012-02-01

CuSbS2 and Cu3BiS3 are being investigated as part of a search for new absorber materials for photovoltaic devices. Thin films of these chalcogenides were produced by conversion of stacked and co-electroplated metal precursor layers in the presence of elemental sulfur vapour. Ex-situ XRD and SEM/EDS analyses of the processed samples were employed to study the reaction sequence with the aim of achieving compact layer morphologies. A new “Time-Temperature-Reaction” (TTR) diagram and modified Pilling-Bedworth coefficients have been introduced for the description and interpretation of the reaction kinetics. For equal processing times, the minimum temperature required for CuSbS2 to appear is substantially lower than for Cu3BiS3, suggesting that interdiffusion across the interfaces between the binary sulfides is a key step in the formation of the ternary compounds. The effects of the heating rate and sulfur partial pressure on the phase evolution as well as the potential losses of Sb and Bi during the processes have been investigated experimentally and the results related to the equilibrium pressure diagrams obtained via thermochemical computation.

Application of thermochemical modeling to aircraft interior polymeric materials

DOT National Transportation Integrated Search

1982-06-01

This report summarizes the results from a twelve-month study of the feasibility of applying certain basic concepts in the thermochemical modeling to aircraft cabin fire safety. The concepts developed earlier on a NASA-sponsored program were applied t...

Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

NASA Astrophysics Data System (ADS)

Lany, Stephan

2018-02-01

The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.

Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

DOE PAGES

Lany, Stephan

2018-02-21

The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.

Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lany, Stephan

The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.

Thermochemical energy storage: Proceedings from the International Seminar on hermochemical Energy Storage

NASA Astrophysics Data System (ADS)

Wettermark, G.

1980-10-01

Energy storage problems are explored. Tomorrow's energy sources will provide a continuous flow of energy. Matching supply and demand will necessitate a wide range of storage capabilities. For storing heat thermochemical and economic solutions may take advantage of the various options inherent in this kind of storage, namely heat pumping, transport of heat and direct conversion to other desired forms of energy such as electricity and mechanical work. There is a need to regularly summarize the knowledge and research in the field of thermochemical energy storage in different parts of the world.

Renewable hydrogen production via thermochemical/electrochemical coupling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ambrosini, Andrea; Babiniec, Sean Michael; Miller, James E.

A coupled electrochemical/thermochemical cycle was investigated to produce hydrogen from renewable resources. Like a conventional thermochemical cycle, this cycle leverages chemical energy stored in a thermochemical working material that is reduced thermally by solar energy. However, in this concept, the stored chemical energy only needs to be partially, but not fully, capable of splitting steam to produce hydrogen. To complete the process, a proton-conducting membrane is driven to separate hydrogen as it is produced, thus shifting the thermodynamics toward further hydrogen production. This novel coupled-cycle concept provides several benefits. First, the required oxidation enthalpy of the reversible thermochemical material ismore » reduced, enabling the process to occur at lower temperatures. Second, removing the requirement for spontaneous steam-splitting widens the scope of materials compositions, allowing for less expensive/more abundant elements to be used. Lastly, thermodynamics calculations suggest that this concept can potentially reach higher efficiencies than photovoltaic-to-electrolysis hydrogen production methods. This Exploratory Express LDRD involved assessing the practical feasibility of the proposed coupled cycle. A test stand was designed and constructed and proton-conducting membranes were synthesized. While the full proof of concept was not achieved, the individual components of the experiment were validated and new capabilities that can be leveraged by a variety of programs were developed.« less

Thermo-Physical Properties of Intermediate Temperature Heat Pipe Fluids

NASA Technical Reports Server (NTRS)

Beach, Duane E. (Technical Monitor); Devarakonda, Angirasa; Anderson, William G.

2005-01-01

Heat pipes are among the most promising technologies for space radiator systems. The paper reports further evaluation of potential heat pipe fluids in the intermediate temperature range of 400 to 700 K in continuation of two recent reports. More thermo-physical property data are examined. Organic, inorganic, and elemental substances are considered. The evaluation of surface tension and other fluid properties are examined. Halides are evaluated as potential heat pipe fluids. Reliable data are not available for all fluids and further database development is necessary. Many of the fluids considered are promising candidates as heat pipe fluids. Water is promising as a heat pipe fluid up to 500 to 550 K. Life test data for thermo-chemical compatibility are almost non-existent.

Thermo-Physical Properties of Intermediate Temperature Heat Pipe Fluids

NASA Technical Reports Server (NTRS)

Devarakonda, Angirasa; Anderson, William G.

2004-01-01

Heat pipes are among the most promising technologies for space radiator systems. The paper reports further evaluation of potential heat pipe fluids in the intermediate temperature range of 400 to 700 K in continuation of two recent reports. More thermo-physical property data are examined. Organic, inorganic and elemental substances are considered. The evaluation of surface tension and other fluid properties are examined. Halides are evaluated as potential heat pipe fluids. Reliable data are not available for all fluids and further database development in necessary. Many of the fluids considered are promising candidates as heat pipe fluids. Water is promising as a heat pipe fluid up to 500-550 K. Life test data for thermo-chemical compatibility are almost non-existent.

Enthalpy of Formation of N 2 H 4 (Hydrazine) Revisited

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feller, David; Bross, David H.; Ruscic, Branko

2017-08-02

In order to address the accuracy of the long-standing experimental enthalpy of formation of gas-phase hydrazine, fully confirmed in earlier versions of Active Thermochemical Tables (ATcT), the provenance of that value is re-examined in light of new high-end calculations of the Feller-Peterson-Dixon (FPD) variety. An overly optimistic determination of the vaporization enthalpy of hydrazine, which created an unrealistically strong connection between the gas phase thermochemistry and the calorimetric results defining the thermochemistry of liquid hydrazine was identified as the probable culprit. The new enthalpy of formation of gas-phase hydrazine, based on balancing all available knowledge, was determined to be 111.57more » ± 0.47 kJ/mol at 0 K (97.41 kJ/mol at 298.15 K). Close agreement was found between the ATcT (even excluding the latest theoretical result) and FPD enthalpies.« less

Enthalpy of Formation of N2H4 (Hydrazine) Revisited.

PubMed

Feller, David; Bross, David H; Ruscic, Branko

2017-08-17

In order to address the accuracy of the long-standing experimental enthalpy of formation of gas-phase hydrazine, fully confirmed in earlier versions of Active Thermochemical Tables (ATcT), the provenance of that value is re-examined in light of new high-end calculations of the Feller-Peterson-Dixon (FPD) variety. An overly optimistic determination of the vaporization enthalpy of hydrazine, which created an unrealistically strong connection between the gas phase thermochemistry and the calorimetric results defining the thermochemistry of liquid hydrazine, was identified as the probable culprit. The new enthalpy of formation of gas-phase hydrazine, based on balancing all available knowledge, was determined to be 111.57 ± 0.47 kJ/mol at 0 K (97.42 ± 0.47 kJ/mol at 298.15 K). Close agreement was found between the ATcT (even excluding the latest theoretical result) and the FPD enthalpy.

Carbonate thermochemical cycle for the production of hydrogen

DOEpatents

Collins, Jack L [Knoxville, TN; Dole, Leslie R [Knoxville, TN; Ferrada, Juan J [Knoxville, TN; Forsberg, Charles W [Oak Ridge, TN; Haire, Marvin J [Oak Ridge, TN; Hunt, Rodney D [Oak Ridge, TN; Lewis, Jr, Benjamin E [Knoxville, TN; Wymer, Raymond G [Oak Ridge, TN

2010-02-23

The present invention is directed to a thermochemical method for the production of hydrogen from water. The method includes reacting a multi-valent metal oxide, water and a carbonate to produce an alkali metal-multi-valent metal oxide compound, carbon dioxide, and hydrogen.

Process development for elemental recovery from PGM tailings by thermochemical treatment: Preliminary major element extraction studies using ammonium sulphate as extracting agent.

PubMed

Mohamed, Sameera; van der Merwe, Elizabet M; Altermann, Wladyslaw; Doucet, Frédéric J

2016-04-01

Mine tailings can represent untapped secondary resources of non-ferrous, ferrous, precious, rare and trace metals. Continuous research is conducted to identify opportunities for the utilisation of these materials. This preliminary study investigated the possibility of extracting major elements from South African tailings associated with the mining of Platinum Group Metals (PGM) at the Two Rivers mine operations. These PGM tailings typically contain four major elements (11% Al2O3; 12% MgO; 22% Fe2O3; 34% Cr2O3), with lesser amounts of SiO2 (18%) and CaO (2%). Extraction was achieved via thermochemical treatment followed by aqueous dissolution, as an alternative to conventional hydrometallurgical processes. The thermochemical treatment step used ammonium sulphate, a widely available, low-cost, recyclable chemical agent. Quantification of the efficiency of the thermochemical process required the development and optimisation of the dissolution technique. Dissolution in water promoted the formation of secondary iron precipitates, which could be prevented by leaching thermochemically-treated tailings in 0.6M HNO3 solution. The best extraction efficiencies were achieved for aluminium (ca. 60%) and calcium (ca. 80%). 35% iron and 32% silicon were also extracted, alongside chromium (27%) and magnesium (25%). Thermochemical treatment using ammonium sulphate may therefore represent a promising technology for extracting valuable elements from PGM tailings, which could be subsequently converted to value-added products. However, it is not element-selective, and major elements were found to compete with the reagent to form water-soluble sulphate-metal species. Further development of this integrated process, which aims at achieving the full potential of utilisation of PGM tailings, is currently underway. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermodynamic Modeling of Ag-Ni System Combining Experiments and Molecular Dynamic Simulation

NASA Astrophysics Data System (ADS)

Rajkumar, V. B.; Chen, Sinn-wen

2017-04-01

Ag-Ni is a simple and important system with immiscible liquids and (Ag,Ni) phases. Previously, this system has been thermodynamically modeled utilizing certain thermochemical and phase equilibria information based on conjecture. An attempt is made in this study to determine the missing information which are difficult to measure experimentally. The boundaries of the liquid miscibility gap at high temperatures are determined using a pyrometer. The temperature of the liquid ⇌ (Ag) + (Ni) eutectic reaction is measured using differential thermal analysis. Tie-lines of the Ag-Ni system at 1023 K and 1473 K are measured using a conventional metallurgical method. The enthalpy of mixing of the liquid at 1773 K and the (Ag,Ni) at 973 K is calculated by molecular dynamics simulation using a large-scale atomic/molecular massively parallel simulator. These results along with literature information are used to model the Gibbs energy of the liquid and (Ag,Ni) by a calculation of phase diagrams approach, and the Ag-Ni phase diagram is then calculated.

Intro to NREL's Thermochemical Pilot Plant

ScienceCinema

Magrini, Kim

2018-02-13

NREL's Thermochemical Pilot Plant converts biomass into higher hydrocarbon fuels and chemicals.NREL is researching biomass pyrolysis. The lab is examining how to upgrade bio-oils via stabilization. Along with this, NREL is developing the engineering system requirements for producing these fuels and chemicals at larger scales.

Turning manure into biochar through thermochemical conversion has the potential to become an exciting new way to handle waste

USDA-ARS?s Scientific Manuscript database

The livestock sector remains vigilant to address effective manure treatment that also safeguards natural resources. Livestock operations must balance business concerns, efficient energy management and environmental stewardship. Fortunately, thermochemical conversion technologies for converting lives...

Comprehensive characterisation of sewage sludge for thermochemical conversion processes - Based on Singapore survey.

PubMed

Chan, Wei Ping; Wang, Jing-Yuan

2016-08-01

Recently, sludge attracted great interest as a potential feedstock in thermochemical conversion processes. However, compositions and thermal degradation behaviours of sludge were highly complex and distinctive compared to other traditional feedstock led to a need of fundamental research on sludge. Comprehensive characterisation of sludge specifically for thermochemical conversion was carried out for all existing Water Reclamation Plants in Singapore. In total, 14 sludge samples collected based on the type, plant, and batch categorisation. Existing characterisation methods for physical and chemical properties were analysed and reviewed using the collected samples. Qualitative similarities and quantitative variations of different sludge samples were identified and discussed. Oxidation of inorganic in sludge during ash forming analysis found to be causing significant deviations on proximate and ultimate analysis. Therefore, alternative parameters and comparison basis including Fixed Residues (FR), Inorganic Matters (IM) and Total Inorganics (TI) were proposed for better understanding on the thermochemical characteristics of sludge. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hybrid Thermochemical/Biological Processing

NASA Astrophysics Data System (ADS)

Brown, Robert C.

The conventional view of biorefineries is that lignocellulosic plant material will be fractionated into cellulose, hemicellulose, lignin, and terpenes before these components are biochemically converted into market products. Occasionally, these plants include a thermochemical step at the end of the process to convert recalcitrant plant components or mixed waste streams into heat to meet thermal energy demands elsewhere in the facility. However, another possibility for converting high-fiber plant materials is to start by thermochemically processing it into a uniform intermediate product that can be biologically converted into a bio-based product. This alternative route to bio-based products is known as hybrid thermochemical/biological processing. There are two distinct approaches to hybrid processing: (a) gasification followed by fermentation of the resulting gaseous mixture of carbon monoxide (CO), hydrogen (H2), and carbon dioxide (CO2) and (b) fast pyrolysis followed by hydrolysis and/or fermentation of the anhydrosugars found in the resulting bio-oil. This article explores this "cart before the horse" approach to biorefineries.

Approximate thermochemical tables for some C-H and C-H-O species

NASA Technical Reports Server (NTRS)

Bahn, G. S.

1973-01-01

Approximate thermochemical tables are presented for some C-H and C-H-O species and for some ionized species, supplementing the JANAF Thermochemical Tables for application to finite-chemical-kinetics calculations. The approximate tables were prepared by interpolation and extrapolation of limited available data, especially by interpolations over chemical families of species. Original estimations have been smoothed by use of a modification for the CDC-6600 computer of the Lewis Research Center PACl Program which was originally prepared for the IBM-7094 computer Summary graphs for various families show reasonably consistent curvefit values, anchored by properties of existing species in the JANAF tables.

Analysis of thermo-chemical nonequilibrium models for carbon dioxide flows

NASA Technical Reports Server (NTRS)

Rock, Stacey G.; Candler, Graham V.; Hornung, Hans G.

1992-01-01

The aerothermodynamics of thermochemical nonequilibrium carbon dioxide flows is studied. The chemical kinetics models of McKenzie and Park are implemented in separate three-dimensional computational fluid dynamics codes. The codes incorporate a five-species gas model characterized by a translational-rotational and a vibrational temperature. Solutions are obtained for flow over finite length elliptical and circular cylinders. The computed flowfields are then employed to calculate Mach-Zehnder interferograms for comparison with experimental data. The accuracy of the chemical kinetics models is determined through this comparison. Also, the methodology of the three-dimensional thermochemical nonequilibrium code is verified by the reproduction of the experiments.

Thermochemical conversion of waste tyres-a review.

PubMed

Labaki, Madona; Jeguirim, Mejdi

2017-04-01

A review of the energy recovery from waste tyres is presented and focuses on the three thermochemical processes used to valorise waste tyres: pyrolysis, gasification, and combustion/incineration. After recalling the chemical composition of tyres, the thermogravimetric behaviours of tyres or their components under different atmospheres are described. Different kinetic studies on the thermochemical processes are treated. Then, the three processes were investigated, with a particular attention given to the gasification, due to the information unavailability on this process. Pyrolysis is a thermochemical conversion to produce a hydrocarbon rich gas mixture, condensable liquids or tars, and a carbon-rich solid residue. Gasification is a form of pyrolysis, carried out at higher temperatures and under given atmosphere (air, steam, oxygen, carbon dioxide, etc.) in order to yield mainly low molecular weight gaseous products. Combustion is a process that needs a fuel and an oxidizer with an ignition system to produce heat and/or steam. The effects of various process parameters such as temperature, heating rate, residence time, catalyst addition, etc. on the energy efficiency and the products yields and characteristics are mainly reviewed. These thermochemical processes are considered to be the more attractive and practicable methods for recovering energy and material from waste tyres. For the future, they are the main promising issue to treat and valorise used tyres. However, efforts should be done in developing more efficient technical systems.

On the thermo-chemical origin of the stratified region at the top of the Earth's core

NASA Astrophysics Data System (ADS)

Nakagawa, Takashi

2018-03-01

I developed a combined model of the thermal and chemical evolution of the Earth's core and investigated its influence on a thermochemically stable region beneath the core-mantle boundary (CMB). The chemical effects of the growing stable region are caused by the equilibrium chemical reaction between silicate and the metallic core. The thermal effects can be characterized by the growth of the sub-isentropic shell, which may have a rapid growth rate compared to that of the chemically stable region. When the present-day CMB heat flow was varied, the origin of the stable region changed from chemical to thermochemical to purely thermal because the rapid growth of the sub-isentropic shell can replace the chemically stable region. Physically reasonable values of the present-day CMB heat flow that can maintain the geodynamo action over 4 billion years should be between 8 and 11 TW. To constrain the thickness of the thermochemically stable region beneath the CMB, the chemical diffusivity is important and should be ∼O(10-8) m2/s to obtain a thickness of the thermochemically stable region beneath the CMB consistent with that inferred from geomagnetic secular variations (140 km). However, the strength of the stable region found in this study is too high to be consistent with the constraint on the stability of the stable region inferred from geomagnetic secular variations.

Innovative solar thermochemical water splitting.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hogan, Roy E. Jr.; Siegel, Nathan P.; Evans, Lindsey R.

2008-02-01

Sandia National Laboratories (SNL) is evaluating the potential of an innovative approach for splitting water into hydrogen and oxygen using two-step thermochemical cycles. Thermochemical cycles are heat engines that utilize high-temperature heat to produce chemical work. Like their mechanical work-producing counterparts, their efficiency depends on operating temperature and on the irreversibility of their internal processes. With this in mind, we have invented innovative design concepts for two-step solar-driven thermochemical heat engines based on iron oxide and iron oxide mixed with other metal oxides (ferrites). The design concepts utilize two sets of moving beds of ferrite reactant material in close proximitymore » and moving in opposite directions to overcome a major impediment to achieving high efficiency--thermal recuperation between solids in efficient counter-current arrangements. They also provide inherent separation of the product hydrogen and oxygen and are an excellent match with high-concentration solar flux. However, they also impose unique requirements on the ferrite reactants and materials of construction as well as an understanding of the chemical and cycle thermodynamics. In this report the Counter-Rotating-Ring Receiver/Reactor/Recuperator (CR5) solar thermochemical heat engine and its basic operating principals are described. Preliminary thermal efficiency estimates are presented and discussed. Our ferrite reactant material development activities, thermodynamic studies, test results, and prototype hardware development are also presented.« less

Biomass for thermochemical conversion: targets and challenges

PubMed Central

Tanger, Paul; Field, John L.; Jahn, Courtney E.; DeFoort, Morgan W.; Leach, Jan E.

2013-01-01

Bioenergy will be one component of a suite of alternatives to fossil fuels. Effective conversion of biomass to energy will require the careful pairing of advanced conversion technologies with biomass feedstocks optimized for the purpose. Lignocellulosic biomass can be converted to useful energy products via two distinct pathways: enzymatic or thermochemical conversion. The thermochemical pathways are reviewed and potential biotechnology or breeding targets to improve feedstocks for pyrolysis, gasification, and combustion are identified. Biomass traits influencing the effectiveness of the thermochemical process (cell wall composition, mineral and moisture content) differ from those important for enzymatic conversion and so properties are discussed in the language of biologists (biochemical analysis) as well as that of engineers (proximate and ultimate analysis). We discuss the genetic control, potential environmental influence, and consequences of modification of these traits. Improving feedstocks for thermochemical conversion can be accomplished by the optimization of lignin levels, and the reduction of ash and moisture content. We suggest that ultimate analysis and associated properties such as H:C, O:C, and heating value might be more amenable than traditional biochemical analysis to the high-throughput necessary for the phenotyping of large plant populations. Expanding our knowledge of these biomass traits will play a critical role in the utilization of biomass for energy production globally, and add to our understanding of how plants tailor their composition with their environment. PMID:23847629

The use of poly-cation oxides to lower the temperature of two-step thermochemical water splitting

DOE PAGES

Zhai, Shang; Rojas, Jimmy; Ahlborg, Nadia; ...

2018-01-01

We report the discovery of a new class of oxides – poly-cation oxides (PCOs) – that consist of multiple cations and can thermochemically split water in a two-step cycle to produce hydrogen (H 2 ) and oxygen (O 2 ).

An Examination of the Phase Transition Thermodynamics of (S)- and (RS)-Naproxen as a Basis for the Design of Enantioselective Crystallization Processes.

PubMed

Buchholz, Hannes; Emel'yanenko, Vladimir N; Lorenz, Heike; Verevkin, Sergey P

2016-05-01

A detailed experimental analysis of the phase transition thermodynamics of (S)-naproxen and (RS)-naproxen is reported. Vapor pressures were determined experimentally via the transpiration method. Sublimation enthalpies were obtained from the vapor pressures and from independent TGA measurements. Thermodynamics of fusion which have been well-studied in the literature were systematically remeasured by DSC. Both sublimation and fusion enthalpies were adjusted to one reference temperature, T = 298 K, using measured heat capacities of the solid and the melt phase by DSC. Average values from the measurements and from literature data were suggested for the sublimation and fusion enthalpies. In order to prove consistency of the proposed values the vaporization enthalpies obtained by combination of both were compared to vaporization enthalpies obtained by the group-additivity method and the correlation-gas chromatography method. The importance of reliable and precise phase transition data for thermochemical calculations such as the prediction of solid/liquid phase behaviour of chiral compounds is highlighted. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Solvent Extraction of Sodium Hydroxide Using Alkylphenols and Fluorinated Alcohols: Understanding the Extraction Mechanism by Equilibrium Modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Hyun-Ah; Engle, Nancy L.; Bonnesen Peter V.

2004-03-29

In the present work, it has been the aim to examine extraction efficiencies of nine proton-ionizable alcohols (HAs) in 1-octanol and to identify both the controlling equilibria and predominant species involved in the extraction process within a thermochemical model. Distribution ratios for sodium (DNa) extraction were measured as a function of organic-phase HA and aqueous-phase NaOH molarity at 25 °C. Extraction efficiency follows the expected order of acidity of the HAs, 4-(tert-octyl) phenol (HA 1a) and 4-noctyl- a,a-bis-(trifluoromethyl)benzyl alcohol (HA 2a) being the most efficient extractants among the compounds tested. By use of the equilibrium-modeling program SXLSQI, a model formore » the extraction of NaOH has been advanced based on an ion-pair extraction by the diluent to give organic-phase Na+OH- and corresponding free ions and cation exchange by the weak acids to form monomeric organic-phase Na+A- and corresponding free organic-phase ions.« less

Engineering Design Elements of a Two-Phase Thermosyphon to Trannsfer NGNP Nuclear Thermal Energy to a Hydrogen Plant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piyush Sabharwal

2009-07-01

Two hydrogen production processes, both powered by a Next Generation Nuclear Plant (NGNP), are currently under investigation at Idaho National Laboratory. The first is high-temperature steam electrolysis, which uses both heat and electricity; the second is thermo-chemical production through the sulfur iodine process primarily using heat. Both processes require a high temperature (>850°C) for enhanced efficiency; temperatures indicative of the NGNP. Safety and licensing mandates prudently dictate that the NGNP and the hydrogen production facility be physically isolated, perhaps requiring separation of over 100 m.

Computer-Based Methods for Thermodynamic Analysis of Materials Processing.

DTIC Science & Technology

1983-11-30

metallic alloys (12,13), silicides (14),and oxynitride * . systems (15). - . 2. Thermochemical System Employed to Characterize Binary Ill-V Phase Diagrams The...reference to Figure I shows that the stable form of RbF is the sodium chloride S form. Table I shows that OGH -oS -RFRFLS-RFRFLM-12866-.381T J/g.at. (5...KF, BF=(I/3)8aF LF-(I/4)LaF3V PF-(113)PbF 2 S- Sodium Chloride Structures Stable form of NF, KE, RE and (;F L-Liquid, M-Stable form of ZF, KeStable form

Monte Carlo PDF method for turbulent reacting flow in a jet-stirred reactor

NASA Astrophysics Data System (ADS)

Roekaerts, D.

1992-01-01

A stochastic algorithm for the solution of the modeled scalar probability density function (PDF) transport equation for single-phase turbulent reacting flow is described. Cylindrical symmetry is assumed. The PDF is represented by ensembles of N representative values of the thermochemical variables in each cell of a nonuniform finite-difference grid and operations on these elements representing convection, diffusion, mixing and reaction are derived. A simplified model and solution algorithm which neglects the influence of turbulent fluctuations on mean reaction rates is also described. Both algorithms are applied to a selectivity problem in a real reactor.

Methods for calculation of engineering parameters for gas separation. [vapor pressure and solubility of gases in organic liquids

NASA Technical Reports Server (NTRS)

Lawson, D. D.

1979-01-01

A group additivity method is generated which allows estimation, from the structural formulas alone, of the energy of vaporization and the molar volume at 25 C of many nonpolar organic liquids. Using these two parameters and appropriate thermodynamic relations, the vapor pressure of the liquid phase and the solubility of various gases in nonpolar organic liquids are predicted. It is also possible to use the data to evaluate organic and some inorganic liquids for use in gas separation stages or liquids as heat exchange fluids in prospective thermochemical cycles for hydrogen production.

Thermochemical energy storage with ammonia: Aiming for the sunshot cost target

NASA Astrophysics Data System (ADS)

Lavine, Adrienne S.; Lovegrove, Keith M.; Jordan, Joshua; Anleu, Gabriela Bran; Chen, Chen; Aryafar, Hamarz; Sepulveda, Abdon

2016-05-01

Thermochemical energy storage has the potential to reduce the cost of concentrating solar thermal power. This paper presents recent advances in ammonia-based thermochemical energy storage (TCES), supported by an award from the U.S. Dept. of Energy SunShot program. Advances have been made in three areas: identification of promising approaches for underground containment of the gaseous products of the dissociation reaction, demonstration that ammonia synthesis can be used to generate steam for a supercritical-steam Rankine cycle, and a preliminary design for integration of the endothermic reactors within a tower receiver. Based on these advances, ammonia-based TCES shows promise to meet the 15/kWht SunShot cost target.

Multiscale modeling and experimental interpretation of perovskite oxide materials in thermochemical energy storage and conversion for application in concentrating solar power

NASA Astrophysics Data System (ADS)

Albrecht, Kevin J.

Decarbonization of the electric grid is fundamentally limited by the intermittency of renewable resources such as wind and solar. Therefore, energy storage will play a significant role in the future of grid-scale energy generation to overcome the intermittency issues. For this reason, concentrating solar power (CSP) plants have been a renewable energy generation technology of interest due to their ability to participate in cost effective and efficient thermal energy storage. However, the ability to dynamically dispatch a CSP plant to meet energy demands is currently limited by the large quantities of sensible thermal energy storage material needed in a molten salt plant. Perovskite oxides have been suggested as a thermochemical energy storage material to enhance the energy storage capabilities of particle-based CSP plants, which combine sensible and chemical modes of energy storage. In this dissertation, computational models are used to establish the thermochemical energy storage potential of select perovskite compositions, identify system configurations that promote high values of energy storage and solar-to-electric efficiency, assess the kinetic and transport limitation of the chemical mode of energy storage, and create receiver and reoxidation reactor models capable of aiding in component design. A methodology for determining perovskite thermochemical energy storage potential is developed based on point defect models to represent perovskite non-stoichiometry as a function of temperature and gas phase oxygen partial pressure. The thermodynamic parameters necessary for the model are extracted from non-stoichiometry measurements by fitting the model using an optimization routine. The procedure is demonstrated for Ca0.9Sr0.1MnO 3-d which displayed combined energy storage values of 705.7 kJ/kg -1 by cycling between 773 K and 0.21 bar oxygen to 1173 K and 10 -4 bar oxygen. Thermodynamic system-level models capable of exploiting perovskite redox chemistry for energy storage in CSP plants are presented. Comparisons of sweep gas and vacuum pumping reduction as well as hot storage conditions indicate that solar-to-electric efficiencies are higher for sweep gas reduction system at equivalent values of energy storage if the energy parasitics of commercially available devices are considered. However, if vacuum pump efficiency between 15% and 30% can be achieved, the reduction methods will be approximately equal. Reducing condition oxygen partial pressures below 10-3 bar for sweep gas reduction and 10-2 bar for vacuum pumping reduction result in large electrical parasitics, which significantly reduce solar-to-electric efficiency. A model based interpretation of experimental measurements made for perovskite redox cycling using sweep gas in a packed bed is presented. The model indicates that long reduction times for equilibrating perovskites with low oxygen partial pressure sweep gas, compared to reoxidation, are primarily due to the oxygen carrying capacity of high purity sweep gas and not surface kinetic limitations. Therefore, achieving rapid reduction in the limited receiver residence time will be controlled by the quantity of sweep gas introduced. Effective kinetic parameters considering surface reaction and radial particle diffusion are fit to the experimental data. Variable order rate expressions without significant particle radial diffusion limitations are shown to be capable of representing the reduction and oxidation data. Modeling of a particle reduction receiver using continuous flow of perovskite solid and sweep gas in counter-flow configuration has identified issues with managing the oxygen evolved by the solid as well as sweep gas flow rates. Introducing sweep gas quantities necessary for equilibrating the solid with oxygen partial pressures below 10-2 are shown to result in gas phase velocities above the entrainment velocity of 500 um particles. Receiver designs with considerations for gas management are investigated and the results indicate that degrees of reduction corresponding to only oxygen partial pressures of 10-2 bar are attained. Numerical investigation into perovskite thermochemical energy storage indicates that achieving high levels of reduction through sweep gas or vacuum pumping to lower gas phase oxygen partial pressure below 10-2 bar display issues with parasitic energy consumption and gas phase management. Therefore, focus on material development should place a premium on thermal reduction and reduction by shifting oxygen partial pressure between ambient and 10-2 bar. Such a material would enable the development of a system with high solar-to-electric efficiencies and degrees of reduction which are attainable in realistic component geometries.

The thermochemical, two-phase dynamics of subduction zones: results from new, fully coupled models

NASA Astrophysics Data System (ADS)

Rees Jones, D. W.; Katz, R. F.; May, D.; Tian, M.; Rudge, J. F.

2017-12-01

Subduction zones are responsible for most of Earth's subaerial volcanism. However, previous geodynamic modelling of subduction zones has largely neglected magmatism. We previously showed that magmatism has a significant thermal impact, by advecting sensible heat into the lithosphere beneath arc volcanos [1]. Inclusion of this effect helps reconcile subduction zone models with petrological and heat flow observations. Many important questions remain, including how magma-mantle dynamics of subduction zones affects the position of arc volcanos and the character of their lavas. In this presentation, we employ a fully coupled, thermochemical, two-phase flow theory to investigate the dynamics of subduction zones. We present the first results from our new software (SubFUSc), which solves the coupled equations governing conservation of mass, momentum, energy and chemical species. The presence and migration of partial melts affect permeability and mantle viscosity (both directly and through their thermal impact); these, in turn, feed back on the magma-mantle flow. Thus our fully coupled modelling improves upon previous two-phase models that decoupled the governing equations and fixed the thermal structure [2]. To capture phase change, we use a novel, simplified model of the mantle melting in the presence of volatile species. As in the natural system, volatiles are associated with low-degree melting at temperatures beneath the anhydrous solidus; dehydration reactions in the slab supply volatiles into the wedge, triggering silicic melting. We simulate the migration of melts under buoyancy forces and dynamic pressure gradients. We thereby demonstrate the dynamical controls on the pattern of subduction-zone volcanism (particularly its location, magnitude, and chemical composition). We build on our previous study of the thermal consequences of magma genesis and segregation. We address the question of what controls the location of arc volcanoes themselves [3]. [1] Rees Jones, D. W., Katz, R. F., Tian, M and Rudge, J. F. (2017). Thermal impact of magmatism in subduction zones. arxiv.org/abs/1701.02550 [2] Wilson, C. R., Spiegelman, M., van Keken, P. E., & Hacker, B. R. (2014). EPSL, doi:10.1016/j.epsl.2014.05.052 [3] England, P. C., Katz, Richard F. (2010). Nature, doi:10.1038/nature09417

CHEETAH 1.0 user`s manual

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fried, L.E.

1994-06-24

CHEETAH is an effort to bring the TIGER thermochemical code into the 1990s. A wide variety of improvements have been made in Version 1.0, and a host of others will be implemented in the future. In CHEETAH 1.0 I have improved the robustness and ease of use of TIGER. All of TIGER`s solvers have been replaced by new algorithms. I find that CHEETAH solves a wider variety of problems with no user intervention (e.g. no guesses for the C-J state) than TIGER did. CHEETAH has been made simpler to use than TIGER; typical use of the code occurs with themore » new standard run command. I hope that CHEETAH makes the use of thermochemical codes more attractive to practical explosive formulators. In the future I plan to improve the underlying science in CHEETAH. More accurate equations of state will be used in the gas and the condensed phase. A kinetics capability will be added to the code that will predict reaction zone thickness. CHEETAH is currently a numerical implementation of C-J theory. It will,become an implementation of ZND theory. Further ease of use features will eventually be added; an automatic formulator that adjusts concentrations to match desired properties is planned.« less

Solar photothermochemical alkane reverse combustion

PubMed Central

Chanmanee, Wilaiwan; Islam, Mohammad Fakrul; Dennis, Brian H.; MacDonnell, Frederick M.

2016-01-01

A one-step, gas-phase photothermocatalytic process for the synthesis of hydrocarbons, including liquid alkanes, aromatics, and oxygenates, with carbon numbers (Cn) up to C13, from CO2 and water is demonstrated in a flow photoreactor operating at elevated temperatures (180–200 °C) and pressures (1–6 bar) using a 5% cobalt on TiO2 catalyst and under UV irradiation. A parametric study of temperature, pressure, and partial pressure ratio revealed that temperatures in excess of 160 °C are needed to obtain the higher Cn products in quantity and that the product distribution shifts toward higher Cn products with increasing pressure. In the best run so far, over 13% by mass of the products were C5+ hydrocarbons and some of these, i.e., octane, are drop-in replacements for existing liquid hydrocarbons fuels. Dioxygen was detected in yields ranging between 64% and 150%. In principle, this tandem photochemical–thermochemical process, fitted with a photocatalyst better matched to the solar spectrum, could provide a cheap and direct method to produce liquid hydrocarbons from CO2 and water via a solar process which uses concentrated sunlight for both photochemical excitation to generate high-energy intermediates and heat to drive important thermochemical carbon-chain-forming reactions. PMID:26903631

An Atomistic-Scale Study for Thermal Conductivity and Thermochemical Compatibility in (DyY)Zr2O7 Combining an Experimental Approach with Theoretical Calculation.

PubMed

Qu, Liu; Choy, Kwang-Leong; Wheatley, Richard

2016-02-18

Ceramic oxides that have high-temperature capabilities can be deposited on the superalloy components in aero engines and diesel engines to advance engine efficiency and reduce fuel consumption. This paper aims to study doping effects of Dy(3+) and Y(3+)on the thermodynamic properties of ZrO2 synthesized via a sol-gel route for a better control of the stoichiometry, combined with molecular dynamics (MD) simulation for the calculation of theoretical properties. The thermal conductivity is investigated by the MD simulation and Clarke's model. This can improve the understanding of the microstructure and thermodynamic properties of (DyY)Zr2O7 (DYZ) at the atomistic level. The phonon-defect scattering and phonon-phonon scattering processes are investigated via the theoretical calculation, which provides an effective way to study thermal transport properties of ionic oxides. The measured and predicted thermal conductivity of DYZ is lower than that of 4 mol % Y2O3 stabilized ZrO2 (4YSZ). It is discovered that DYZ is thermochemically compatible with Al2O3 at 1300 °C, whereas at 1350 °C DYZ reacts with Al2O3 forming a small amount of new phases.

An Atomistic-Scale Study for Thermal Conductivity and Thermochemical Compatibility in (DyY)Zr2O7 Combining an Experimental Approach with Theoretical Calculation

PubMed Central

Qu, Liu; Choy, Kwang-Leong; Wheatley, Richard

2016-01-01

Ceramic oxides that have high-temperature capabilities can be deposited on the superalloy components in aero engines and diesel engines to advance engine efficiency and reduce fuel consumption. This paper aims to study doping effects of Dy3+ and Y3+on the thermodynamic properties of ZrO2 synthesized via a sol-gel route for a better control of the stoichiometry, combined with molecular dynamics (MD) simulation for the calculation of theoretical properties. The thermal conductivity is investigated by the MD simulation and Clarke’s model. This can improve the understanding of the microstructure and thermodynamic properties of (DyY)Zr2O7 (DYZ) at the atomistic level. The phonon-defect scattering and phonon-phonon scattering processes are investigated via the theoretical calculation, which provides an effective way to study thermal transport properties of ionic oxides. The measured and predicted thermal conductivity of DYZ is lower than that of 4 mol % Y2O3 stabilized ZrO2 (4YSZ). It is discovered that DYZ is thermochemically compatible with Al2O3 at 1300 °C, whereas at 1350 °C DYZ reacts with Al2O3 forming a small amount of new phases. PMID:26888438

Multiparameter spatio-thermochemical probing of flame–wall interactions advanced with coherent Raman imaging

DOE PAGES

Bohlin, Gustav Alexis; Jainski, Christopher; Patterson, Brian D.; ...

2016-08-10

Ultrabroadband coherent anti-Stokes Ra man spectroscopy (CARS) has been developed for one -dimensional imaging of temperature and major species distributions simultaneously in the near-wall region of a methane/air flame supported on a side-wall-quenching (SWQ) burner. Automatic temporal and spatial overlap of the ~7 femtosecond pump and Stokes pulses is achieved utilizing a two-beam CARS phase-matching scheme, and the crossed ~75 picosecond probe beam provide s excellent spatial sectioning of the probed location. Concurrent detection of N 2, O 2, H 2, CO, CO 2, and CH 4 is demonstrated while high-fidelity flame thermometry is assessed from the N 2 puremore » rotational S-branch in a one-dimensional -CARS imaging configuration. A methane/air premixed flame at lean, stoichiometric, and rich conditions ( Φ = 0.83, 1.0 , and 1.2) and Reynolds number = 5,000 is probed as it quenches against a cooled steel side- wall parallel to the flow providing a persistent flame-wall interaction. Here, an imaging resolution of better than 40 μm is achieved across the field -of-view, thus allowing thermochemical states (temperature and major species) of the thermal boundary layer to be resolved to within ~30 μm of the interface.« less

Multiparameter spatio-thermochemical probing of flame–wall interactions advanced with coherent Raman imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bohlin, Gustav Alexis; Jainski, Christopher; Patterson, Brian D.

Ultrabroadband coherent anti-Stokes Ra man spectroscopy (CARS) has been developed for one -dimensional imaging of temperature and major species distributions simultaneously in the near-wall region of a methane/air flame supported on a side-wall-quenching (SWQ) burner. Automatic temporal and spatial overlap of the ~7 femtosecond pump and Stokes pulses is achieved utilizing a two-beam CARS phase-matching scheme, and the crossed ~75 picosecond probe beam provide s excellent spatial sectioning of the probed location. Concurrent detection of N 2, O 2, H 2, CO, CO 2, and CH 4 is demonstrated while high-fidelity flame thermometry is assessed from the N 2 puremore » rotational S-branch in a one-dimensional -CARS imaging configuration. A methane/air premixed flame at lean, stoichiometric, and rich conditions ( Φ = 0.83, 1.0 , and 1.2) and Reynolds number = 5,000 is probed as it quenches against a cooled steel side- wall parallel to the flow providing a persistent flame-wall interaction. Here, an imaging resolution of better than 40 μm is achieved across the field -of-view, thus allowing thermochemical states (temperature and major species) of the thermal boundary layer to be resolved to within ~30 μm of the interface.« less

New method for the determination of metolachlor and buprofezin in natural water using orthophthalaldehyde by thermochemically-induced fluorescence derivatization (TIFD).

PubMed

Mendy, Alphonse; Thiaré, Diène Diégane; Sambou, Souleymane; Khonté, Abdourahmane; Coly, Atanasse; Gaye-Seye, Mame Diabou; Delattre, François; Tine, Alphonse

2016-05-01

Herbicide metolachlor (MET) and insecticide buprofezin (BUP) were determined in natural waters by means of a newly-developed, simple and sensitive thermochemically-induced fluorescence derivatization (TIFD) method. The TIFD approach is based on the thermolysis transformation of naturally non-fluorescent pesticides into fluorescent complex O-phthalaldehyde-thermoproduct(s) in water at 70°C for MET and at 80°C for BUP. The TIFD method was optimized with respect to the temperature, pH, complex formation kinetic and pesticides concentrations. The limit of detection (LOD=0.8ngmL(-1) for MET and 3.0ngmL(-1) for BUP) and quantification (LOQ=2.6ngmL(-1) for MET and 9.5 ngmL(-1) for BUP) values were low, and the relative standard deviation (RSD) values were small (between 1.2% and 1.8%), which indicates a good analytical sensitivity and a great repeatability of TIFD method. Recovery studies were performed on spiked well, sea and draining waters samples collected in the Niayes area by using the solid phase extraction (SPE) procedure. Satisfactory recovery results (84-118%) were obtained for the determination of MET and BUP in these natural waters. Copyright © 2016 Elsevier B.V. All rights reserved.

The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Beckett, J. R.; Stolper, E.

1994-01-01

Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical modes for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu(2+)/Eu(#+) decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phase condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect.

Thermochemistry analyses for transformation of C6 glucose compound into C9, C12 and C15 alkanes using density functional theory

NASA Astrophysics Data System (ADS)

Verma, Anand Mohan; Kishore, Nanda

2017-02-01

The hydrolysis of cellulose fraction of biomass yields C6 glucose which further can be transformed into long-chain hydrocarbons by C-C coupling. In this study, C6 glucose is transformed into three chain alkanes, namely, C9, C12 and C15 using C-C coupling reactions under the gas and aqueous phase milieus. The geometry optimisation and vibrational frequency calculations are carried out at well-known hybrid-GGA functional, B3LYP with the basis set of 6-31+g(d,p) under the density functional theory framework. The single point energetics are calculated at M05-2X/6-311+g(3df,2p) level of theory. All thermochemical properties are calculated over a wide range of temperature between 300 and 900 K at an interval of 100 K. The thermochemistry suggested that the aqueous phase behaviour is suitable for the hydrolysis of sugar into long-chain alkanes compared to gas-phase environment. The hydrodeoxygenation reactions under each reaction pathway are found as most favourable reactions in both phases; however, aqueous phase dominates over gas phase in all discussed thermodynamic parameters.

Design principles of perovskites for solar-driven thermochemical splitting of CO2† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7ta02081c

PubMed Central

Ezbiri, Miriam; Takacs, Michael; Stolz, Boris; Lungthok, Jeffrey; Steinfeld, Aldo

2017-01-01

Perovskites are attractive redox materials for thermo/electrochemical fuel synthesis. To design perovskites with balanced redox energetics for thermochemically splitting CO2, the activity of lattice oxygen vacancies and stability against crystal phase changes and detrimental carbonate formation are predicted for a representative range of perovskites by electronic structure computations. Systematic trends in these materials properties when doping with selected metal cations are described in the free energy range defined for isothermal and temperature-swing redox cycles. To confirm that the predicted materials properties root in the bulk chemical composition, selected perovskites are synthesized and characterized by X-ray diffraction, transmission electron microscopy, and thermogravimetric analysis. On one hand, due to the oxidation equilibrium, none of the investigated compositions outperforms non-stoichiometric ceria – the benchmark redox material for CO2 splitting with temperature-swings in the range of 800–1500 °C. On the other hand, certain promising perovskites remain redox-active at relatively low oxide reduction temperatures at which ceria is redox-inactive. This trade-off in the redox energetics is established for YFeO3, YCo0.5Fe0.5O3 and LaFe0.5Ni0.5O3, identified as stable against phase changes and capable to convert CO2 to CO at 600 °C and 10 mbar CO in CO2, and to being decomposed at 1400 °C and 0.1 mbar O2 with an enthalpy change of 440–630 kJ mol–1 O2. PMID:29456856

Organochlorines in surface soil at electronic-waste wire burning sites and metal contribution evaluated using quantitative X-ray speciation

NASA Astrophysics Data System (ADS)

Fujimori, Takashi; Takigami, Hidetaka; Takaoka, Masaki

2013-04-01

Heavy metals and toxic chlorinated aromatic compounds (aromatic-Cls) such as dioxins and polychlorinated biphenyls (PCBs) are found at high concentrations and persist in surface soil at wire burning sites (WBSs) in developing countries in which various wire cables are recycled to yield pure metals. Chlorine K-edge near-edge X-ray absorption fine structure (NEXAFS) is used to detect the specific chemical form of Cl and estimate its amount using a spectrum jump in the solid phase. Quantitative X-ray speciation of Cl was applied to study the mechanisms of aromatic-Cls formation in surface soil at WBSs in Southeast Asia. Relationships between aromatic-Cls and chlorides of heavy metals were evaluated because heavy metals are promoters of the thermochemical solid-phase formation of aromatic-Cls.

Silicon materials task of the low cost solar array project. Phase 3: Effect of impurities and processing on silicon solar cells

NASA Technical Reports Server (NTRS)

Hopkins, R. H.; Davis, J. R.; Blais, P. D.; Rohatgi, A.; Campbell, R. B.; Rai-Choudhury, P.; Mollenkopf, H. C.; Mccormick, J. R.

1979-01-01

The 13th quarterly report of a study entitled an Investigation of the Effects of Impurities and Processing on Silicon Solar Cells is given. The objective of the program is to define the effects of impurities, various thermochemical processes and any impurity-process interactions on the performance of terrestrial silicon solar cells. The Phase 3 program effort falls in five areas: (1) cell processing studies; (2) completion of the data base and impurity-performance modeling for n-base cells; (3) extension of p-base studies to include contaminants likely to be introduced during silicon production, refining or crystal growth; (4) anisotropy effects; and (5) a preliminary study of the permanence of impurity effects in silicon solar cells. The quarterly activities for this report focus on tasks (1), (3) and (4).

Neutralization and Acid Dissociation of Hydrogen Carbonate Ion: A Thermochemical Approach

ERIC Educational Resources Information Center

Koga, Nobuyoshi; Shigedomi, Kana; Kimura, Tomoyasu; Tatsuoka, Tomoyuki; Mishima, Saki

2013-01-01

A laboratory inquiry into the thermochemical relationships in the reaction between aqueous solutions of NaHCO[subscript 3] and NaOH is described. The enthalpy change for this reaction, delta[subscript r]H, and that for neutralization of strong acid and NaOH(aq), delta[subscript n]H, are determined calorimetrically; the explanation for the…

Thermochemical properties of flame gases from fine wildland fuels

Treesearch

Frank A. Albini

1979-01-01

Describes a theoretical model for calculating thermochemical properties of the gaseous fuel that burns in the free flame at the edge of a spreading fire in fine forest fuels. Predicted properties are the heat of combustion, stoichiometric air/fuel mass ratio, mass-averaged temperature, and mass fraction of unburned fuel in the gas mixture emitted from the flame-...

Development and application of computational aerothermodynamics flowfield computer codes

NASA Technical Reports Server (NTRS)

Venkatapathy, Ethiraj

1992-01-01

Presented is a collection of papers on research activities carried out during the funding period of October 1991 to March 1992. Topics covered include: blunt body flows in thermochemical equilibrium; thermochemical relaxation in high enthalpy nozzle flow; single expansion ramp nozzle simulations; lunar return aerobraking; line boundary problem for three dimensional grids; and unsteady shock induced combustion.

Torrefaction? What’s that?

Treesearch

D. Mitchell; T. Elder

2010-01-01

Torrefaction is a thermo-chemical process that reduces the moisture content of wood and transforms it into a brittle, char-type material. The thermo-chemical process can reduce the mass of wood by 20-30% resulting in a denser, higher-valued product that can be transported more economically than traditional wood chips. Through torrefaction, wood may retain 90% of the...

Development of a practical photochemical energy storage system. Quarterly report. [Interconversion between norbornadiene and quadricyclene for thermochemical heat storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hautala, R.R.; Kutal, C.R.

1977-06-15

Research on polymeric organic sensitizers and polymeric inorganic sensitizers for the conversion of norbornadine to quadricyclene and catalysts for the conversion of quadricyclene to norbornadine is described. The interconversion of norbornadine and quadricyclene is studied for its possible use for thermochemical solar energy storage. (WHK)

Thermodynamic properties of minerals

USGS Publications Warehouse

Robie, Richard A.

1962-01-01

In the ten years since the publication of the national Bureau of Standards comprehensive tables of thermochemical properties, by Rossini and other (1952), a very large body of modern calorimetric and equilibrium data has become available. Because of the complex interrelations among many thermochemical data and the necessity for internal consistency among these values, a complete revision of this standard reference is required. This is also true of the summaries of thermochemical data for the sulfides (Richardson and Jeffes 1952) and for the oxides (Coughlin 1954). The following tables present critically selected values for the heat and free energy of formation, the logarithm of the equilibrium constant of formation Log Kf, the entropy and the molar volume, at 298.15°K (25.0°C) and one atmosphere for minerals.

Quantitative Thermochemical Measurements in High-Pressure Gaseous Combustion

NASA Technical Reports Server (NTRS)

Kojima, Jun J.; Fischer, David G.

2012-01-01

We present our strategic experiment and thermochemical analyses on combustion flow using a subframe burst gating (SBG) Raman spectroscopy. This unconventional laser diagnostic technique has promising ability to enhance accuracy of the quantitative scalar measurements in a point-wise single-shot fashion. In the presentation, we briefly describe an experimental methodology that generates transferable calibration standard for the routine implementation of the diagnostics in hydrocarbon flames. The diagnostic technology was applied to simultaneous measurements of temperature and chemical species in a swirl-stabilized turbulent flame with gaseous methane fuel at elevated pressure (17 atm). Statistical analyses of the space-/time-resolved thermochemical data provide insights into the nature of the mixing process and it impact on the subsequent combustion process in the model combustor.

Multiple sulfur isotopes monitor fluid evolution of an Archean orogenic gold deposit

NASA Astrophysics Data System (ADS)

LaFlamme, Crystal; Sugiono, Dennis; Thébaud, Nicolas; Caruso, Stefano; Fiorentini, Marco; Selvaraja, Vikraman; Jeon, Heejin; Voute, François; Martin, Laure

2018-02-01

The evolution of a gold-bearing hydrothermal fluid from its source to the locus of gold deposition is complex as it experiences rapid changes in thermochemical conditions during ascent through the crust. Although it is well established that orogenic gold deposits are generated during time periods of abundant crustal growth and/or reworking, the source of fluid and the thermochemical processes that control gold precipitation remain poorly understood. In situ analyses of multiple sulfur isotopes offer a new window into the relationship between source reservoirs of Au-bearing fluids and the thermochemical processes that occur along their pathway to the final site of mineralisation. Whereas δ34S is able to track changes in the evolution of the thermodynamic conditions of ore-forming fluids, Δ33S is virtually indelible and can uniquely fingerprint an Archean sedimentary reservoir that has undergone mass independent fractionation of sulfur (MIF-S). We combine these two tracers (δ34S and Δ33S) to characterise a gold-bearing laminated quartz breccia ore zone and its sulfide-bearing alteration halo in the (+6 Moz Au) structurally-controlled Archean Waroonga deposit located in the Eastern Goldfields Superterrane of the Yilgarn Craton, Western Australia. Over 250 analyses of gold-associated sulfides yield a δ34S shift from what is interpreted as an early pre-mineralisation phase, with chalcopyrite-pyrrhotite (δ34S = +0.7‰ to +2.9‰) and arsenopyrite cores (δ34S = ∼-0.5‰), to a syn-mineralisation stage, reflected in Au-bearing arsenopyrite rims (δ34S = -7.6‰ to +1.5‰). This shift coincides with an unchanging Δ33S value (Δ33S = +0.3‰), both temporally throughout the Au-hosting hydrothermal sulfide paragenesis and spatially across the Au ore zone. These results indicate that sulfur is at least partially recycled from MIF-S-bearing Archean sediments. Further, the invariant nature of the observed MIF-S signature demonstrates that sulfur is derived from a homogeneous MIF-S-bearing fluid reservoir at depth, rather than being locally sourced at the site of Au precipitation. Finally, by constraining the MIF-S-bearing sulfur source to a fixed reservoir, we are able to display the thermochemical evolution of the ore fluid in δ34S space and capture the abrupt change in oxidation state that causes Au precipitation. Our results highlight the importance of constraining multiple sulfur isotopes in space and time in order to elucidate the source and evolution of any given Au-bearing fluid.

Improving Students' Chemical Literacy Levels on Thermochemical and Thermodynamics Concepts through a Context-Based Approach

ERIC Educational Resources Information Center

Cigdemoglu, Ceyhan; Geban, Omer

2015-01-01

The aim of this study was to delve into the effect of context-based approach (CBA) over traditional instruction (TI) on students' chemical literacy level related to thermochemical and thermodynamics concepts. Four eleventh-grade classes with 118 students in total taught by two teachers from a public high school in 2012 fall semester were enrolled…

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, Carlos E.

1980-01-01

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Cascading pressure reactor and method for solar-thermochemical reactions

DOEpatents

Ermanoski, Ivan

2017-11-14

Reactors and methods for solar thermochemical reactions are disclosed. The reactors and methods include a cascade of reduction chambers at successively lower pressures that leads to over an order of magnitude pressure decrease compared to a single-chambered design. The resulting efficiency gains are substantial, and represent an important step toward practical and efficient solar fuel production on a large scale.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, C.E.

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Evaluation energy efficiency of bioconversion knot rejects to ethanol in comparison to other thermochemically pretreated biomass

Treesearch

Zhaojiang Wang; Menghua Qin; J.Y. Zhu; Guoyu Tian; Zongquan Li

2013-01-01

Rejects from sulfite pulp mill that otherwise would be disposed of by incineration were converted to ethanol by a combined physical–biological process that was comprised of physical refining and simultaneous saccharification and fermentation (SSF). The energy efficiency was evaluated with comparison to thermochemically pretreated biomass, such as those pretreated by...

Using a Laboratory Inquiry with High School Students to Determine the Reaction Stoichiometry of Neutralization by a Thermochemical Approach

ERIC Educational Resources Information Center

Journal of Chemical Education, 2015

2015-01-01

This paper presents the design and practical application of a laboratory inquiry at high school chemistry level for systematic chemistry learning, as exemplified by a thermochemical approach to the reaction stoichiometry of neutralization using Job's method of continuous variation. In the laboratory inquiry, students are requested to propose the…

Experimental and thermodynamic study of Co-Fe and Mn-Fe based mixed metal oxides for thermochemical energy storage application

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-06-01

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications.

Thermochemical recovery of heat contained in flue gases by means of bioethanol conversion

NASA Astrophysics Data System (ADS)

Pashchenko, D. I.

2013-06-01

In the present paper consideration is being given to the use of bioethanol in the schemes of thermochemical recovery of heat contained in exit flue gases. Schematic diagrams illustrate the realization of thermochemical heat recovery by implementing ethanol steam conversion and conversion of ethanol by means of products of its complete combustion. The feasibility of attaining a high degree of recovery of heat contained in flue gases at the moderate temperature (up to 450°C) of combustion components is demonstrated in the example of the energy balance of the system for thermochemical heat recovery. The simplified thermodynamic analysis of the process of ethanol steam conversion was carried out in order to determine possible ranges of variation of process variables (temperature, pressure, composition) of a reaction mixture providing the efficient heat utilization. It was found that at the temperature above 600 K the degree of ethanol conversion is near unity. The equilibrium composition of products of reaction of ethanol steam conversion has been identified for different temperatures at which the process occurs at the ratio H2O/EtOH = 1 and at the pressure of 0.1 MPa. The obtained results of calculation agree well with the experimental data.

Optimized structure and thermochemical properties of flavonoids determined by the CHIH(medium) DFT model chemistry versus experimental techniques

NASA Astrophysics Data System (ADS)

Mendoza-Wilson, Ana María.; Lardizabal-Gutiérrez, Daniel; Torres-Moye, Enrique; Fuentes-Cobas, Luis; Balandrán-Quintana, René R.; Camacho-Dávila, Alejandro; Quintero-Ramos, Armando; Glossman-Mitnik, Daniel

2007-12-01

The purpose of this work was to evaluate the accuracy of the CHIH(medium)-DFT model chemistry (PBEg/CBSB2 ∗∗//PBEg/CBSB4) in the determination of the optimized structure and thermochemical properties of heterocyclic systems of medium size such as flavonoids, wherefore were selected three of the most abundant flavonoids in vegetable tissues, and which posses the higher antioxidant activity: quercetin, (+)-catechin and cyanidin. As reference systems were employed three cyclic compounds: phenol, catechol and resorcinol. The thermochemical properties evaluated were enthalpy of formation, bond dissociation enthalpy (BDE) and ionization potential (IP), following the scheme of isodesmic reactions. The theoretical results were compared with experimental data generated by X-ray diffraction and calorimetric techniques realized in part by us, whereas other data were taken from the literature. The results obtained in this work reveal that the CHIH(medium)-DFT model chemistry represents an accurate computational tool to calculate structural and thermochemical properties in the studied flavonoid and reference compounds. The average absolute deviation of enthalpy of formation for reference compounds was 3.0 kcal/mol, 2.64 kcal/mol for BDE, and 2.97 kcal/mol for IP.

Spectroscopic notes of Methyl Red (MR) dye.

PubMed

El-Mansy, M A M; Yahia, I S

2014-09-15

In the present work, a combined experimental and theoretical study on molecular structure and vibrational frequencies of MR were reported. The FT-IR spectrum of MR is recorded in the solid phase. The equilibrium geometries, harmonic vibrational frequencies, thermo-chemical parameters, total dipole moment and HOMO-LUMO energies are calculated by DFT/B3LYP utilizing 6-311G(d,p) basis set. Results showed that MR is highly recommended to be a promising structure for many applications in optoelectronic devices due to its high calculated dipole moment value (7.2 Debye) and lower HOMO-LUMO energy gap of 3.5 eV. Copyright © 2014 Elsevier B.V. All rights reserved.

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2

PubMed Central

Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C.; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J.; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J.

2017-01-01

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source. PMID:28233864

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2.

PubMed

Colombara, Diego; Berner, Ulrich; Ciccioli, Andrea; Malaquias, João C; Bertram, Tobias; Crossay, Alexandre; Schöneich, Michael; Meadows, Helene J; Regesch, David; Delsante, Simona; Gigli, Guido; Valle, Nathalie; Guillot, Jérome; El Adib, Brahime; Grysan, Patrick; Dale, Phillip J

2017-02-24

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se 2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu 2 ZnSnS 4 ) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.

Estimates of thermochemical relaxation lengths behind normal shock waves relevant to manned lunar and Mars return missions, the aeroassist flight experiment, and Mars entry

NASA Technical Reports Server (NTRS)

Howe, John T.

1991-01-01

Thermochemical relaxation distances behind the strong normal shock waves associated with vehicles that enter the Earth atmosphere upon returning from a manned lunar or Mars mission are estimated. The relaxation distances for a Mars entry are estimated as well, in order to highlight the extent of the relaxation phenomena early in currently envisioned space exploration studies. The thermochemical relaxation length for the Aeroassist Flight Experiment is also considered. These estimates provide an indication as to whether finite relaxation needs to be considered in subsequent detailed analyses. For the Mars entry, relaxation phenomena that are fully coupled to the flow field equations are used. The relaxation-distance estimates can be scaled to flight conditions other than those discussed.

Thermochemical parameters of minerals from oxygen-buffered hydrothermal equilibrium data: Method, application to annite and almandine

USGS Publications Warehouse

Zen, E.-A.

1973-01-01

Reversed univariant hydrothermal phase-equilibrium reactions, in which a redox reaction occurs and is controlled by oxygen buffers, can be used to extract thermochemical data on minerals. The dominant gaseous species present, even for relatively oxidizing buffers such as the QFM buffer, are H2O and H2; the main problem is to calculate the chemical potentials of these components in a binary mixture. The mixing of these two species in the gas phase was assumed by Eugster and Wones (1962) to be ideal; this assumption allows calculation of the chemical potentials of the two components in a binary gas mixture, using data in the literature. A simple-mixture model of nonideal mixing, such as that proposed by Shaw (1967), can also be combined with the equations of state for oxygen buffers to permit derivation of the chemical potentials of the two components. The two mixing models yield closely comparable results for the more oxidizing buffers such as the QFM buffer. For reducing buffers such as IQF, the nonideal-mixing correction can be significant and the Shaw model is better. The procedure of calculation of mineralogical thermochemical data, in reactions where hydrogen and H2O simultaneously appear, is applied to the experimental data on annite, given by Wones et al. (1971), and on almandine, given by Hsu (1968). For annite the results are: Standard entropy of formation from the elements, Sf0 (298, 1)=-283.35??2.2 gb/gf, S0 (298, 1) =+92.5 gb/gf. Gf0 (298, 1)=-1148.2??6 kcal, and Hf0 (298, 1)=-1232.7??7 kcal. For almandine, the calculation takes into account the mutual solution of FeAl2O4 (Hc) in magnetite and of Fe3O4 (Mt) in hercynite and the temperature dependence of this solid solution, as given by Turnock and Eugster (1962); the calculations assume a regular-solution model for this binary spinel system. The standard entropy of formation of almandine, Sf,A0 (298, 1) is -272.33??3 gb/gf. The third law entropy, S0 (298, 1) is +68.3??3 gb/gf, a value much less than the oxide-sum estimate but the deviation is nearly the same as that of grossularite, referring to a comparable set of oxide standard states. The Gibbs free energy Gf,A0 (298, 1) is -1192.36??4 kcal, and the enthalpy Hf,A0 (298, 1) is -1273.56??5 kcal. ?? 1973 Springer-Verlag.

Phase Equilibria Diagrams Database

National Institute of Standards and Technology Data Gateway

SRD 31 NIST/ACerS Phase Equilibria Diagrams Database (PC database for purchase)   The Phase Equilibria Diagrams Database contains commentaries and more than 21,000 diagrams for non-organic systems, including those published in all 21 hard-copy volumes produced as part of the ACerS-NIST Phase Equilibria Diagrams Program (formerly titled Phase Diagrams for Ceramists): Volumes I through XIV (blue books); Annuals 91, 92, 93; High Tc Superconductors I & II; Zirconium & Zirconia Systems; and Electronic Ceramics I. Materials covered include oxides as well as non-oxide systems such as chalcogenides and pnictides, phosphates, salt systems, and mixed systems of these classes.

Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

NASA Technical Reports Server (NTRS)

Ota, K.; Conger, W. L.

1977-01-01

The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

Status of the DOE (STOR)-sponsored national program on hydrogen production from water via thermochemical cycles

NASA Technical Reports Server (NTRS)

Baker, C. E.

1977-01-01

The program structure is presented. The activities of the thermochemical cycles program are grouped according to the following categories: (1) specific cycle development, (2) support research and technology, (3) cycle evaluation. Specific objectives and status of on-going activities are discussed. Chemical reaction series for the production of hydrogen are presented. Efficiency and economic evaluations are also discussed.

The African and Pacific Superplumes and Thermochemical Piles and Their Relationship to Supercontinent Pangea

NASA Astrophysics Data System (ADS)

Zhong, S.; Leng, W.; Zhang, N.; McNamara, A. K.

2008-12-01

The long-wavelength structure for the present-day Earth's mantle is characterized by circum-Pacific subduction and the antipodal African and Pacific superplumes. The African and Pacific superplumes are anchored on two major thermochemical piles that extend from the core-mantle boundary (CMB) to possibly >500 km above CMB. These two superplumes are where most of large igneous provinces (LIPs) and plume-related volcanism are originated in the last 250 Ma. The thermochemical piles may provide distinct geochemical signatures observed in oceanic island basalts, although it remains controversial whether the piles consist of primordial mantle materials or recycled crust and lithosphere. Geodynamic modeling has demonstrated that the main structural features of the mantle including the circum-Pacific subduction, African and Pacific superplumes, and the thermochemical piles, are closely related to mantle convection associated with plate motion history for the last 120 Ma. However, outstanding questions remain. When did the African and Pacific superplumes and thermochemical piles start to take the current forms? How stable and stationary have they been in the mantle? How are they related to the observations of tectonics and volcanism priori to 120 Ma ago? Our recent studies on long-wavelength mantle convection and supercontinent cycles suggest that the African and Pacific superplumes and thermochemical piles are dynamic features and that they may move laterally in response to mantle flow associated with surface plate motion, such as past subduction and convergence between Laurentia and Gondwana. In particular, our studies suggest that the African superplume and pile did not form until Laurentia and Gondwana collided to form Pangea, while the Pacific anomaly may have been there for a longer time. Our results also suggest that, after lengthy convergence between Laurentia and Gondwana that pushed away the pile materials away from the African hemisphere, later subduction surrounding Pangea may not bring enough chemically dense mantle materials to form the African pile, if the pile consists of the primordial mantle, thus suggesting an origin of the recycled crust and lithosphere for the pile. While focusing on the African anomaly, we will also discuss potential ways to constrain the evolution of the Pacific superplume and pile.

Thermodynamic study of (anthracene + benzo[a]pyrene) solid mixtures

PubMed Central

Rice, James W.; Suuberg, Eric M.

2010-01-01

To characterize better the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the {anthracene (1) + benzo[a]pyrene (2)} system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at x1 = 0.26. The eutectic mixture is an amorphous solid that lacks organized crystal structure and melts between T = (414 and 420) K. For mixtures that contain 0.10 < x1 < 0.90, the enthalpy of fusion is dominated by that of the eutectic. Solid-vapor equilibrium studies show that mixtures of anthracene and benzo[a]pyrene at x1 < 0.10 sublime at the vapor pressure of pure benzo[a]pyrene. These results suggest that the solid-vapor equilibrium of benzo[a]pyrene is not significantly influenced by moderate levels of anthracene in the crystal structure. PMID:20814451

Thermochemical properties of silver tellurides including empressite (AgTe) and phase diagrams for Ag-Te and Ag-Te-O

NASA Astrophysics Data System (ADS)

Voronin, Mikhail V.; Osadchii, Evgeniy G.; Brichkina, Ekaterina A.

2017-10-01

This study compiles original experimental and literature data on the thermodynamic properties (ΔfG°, S°, ΔfH°) of silver tellurides (α-Ag2Te, β-Ag2Te, Ag1.9Te, Ag5Te3, AgTe) obtained by the method of solid-state galvanic cell with the RbAg4I5 and AgI solid electrolytes. The thermodynamic data for empressite (AgTe, pure fraction from Empress Josephine Mine, Colorado USA) have been obtained for the first time by the electrochemical experiment with the virtual reaction Ag + Te = AgTe. The Ag-Te phase diagrams in the T - x and log fTe2 (gas) - 1/ T coordinates have been refined, and the ternary Ag-Te-O diagrams with Ag-Te-TeO2 (paratellurite) composition range have been calculated.

Comparative life cycle assessment of lignocellulosic ethanol production: biochemical versus thermochemical conversion.

PubMed

Mu, Dongyan; Seager, Thomas; Rao, P Suresh; Zhao, Fu

2010-10-01

Lignocellulosic biomass can be converted into ethanol through either biochemical or thermochemical conversion processes. Biochemical conversion involves hydrolysis and fermentation while thermochemical conversion involves gasification and catalytic synthesis. Even though these routes produce comparable amounts of ethanol and have similar energy efficiency at the plant level, little is known about their relative environmental performance from a life cycle perspective. Especially, the indirect impacts, i.e. emissions and resource consumption associated with the production of various process inputs, are largely neglected in previous studies. This article compiles material and energy flow data from process simulation models to develop life cycle inventory and compares the fossil fuel consumption, greenhouse gas emissions, and water consumption of both biomass-to-ethanol production processes. The results are presented in terms of contributions from feedstock, direct, indirect, and co-product credits for four representative biomass feedstocks i.e., wood chips, corn stover, waste paper, and wheat straw. To explore the potentials of the two conversion pathways, different technological scenarios are modeled, including current, 2012 and 2020 technology targets, as well as different production/co-production configurations. The modeling results suggest that biochemical conversion has slightly better performance on greenhouse gas emission and fossil fuel consumption, but that thermochemical conversion has significantly less direct, indirect, and life cycle water consumption. Also, if the thermochemical plant operates as a biorefinery with mixed alcohol co-products separated for chemicals, it has the potential to achieve better performance than biochemical pathway across all environmental impact categories considered due to higher co-product credits associated with chemicals being displaced. The results from this work serve as a starting point for developing full life cycle assessment model that facilitates effective decision-making regarding lignocellulosic ethanol production.

Definitive Ideal-Gas Thermochemical Functions of the H216O Molecule

NASA Astrophysics Data System (ADS)

Furtenbacher, Tibor; Szidarovszky, Tamás; Hrubý, Jan; Kyuberis, Aleksandra A.; Zobov, Nikolai F.; Polyansky, Oleg L.; Tennyson, Jonathan; Császár, Attila G.

2016-12-01

A much improved temperature-dependent ideal-gas internal partition function, Qint(T), of the H216O molecule is reported for temperatures between 0 and 6000 K. Determination of Qint(T) is principally based on the direct summation technique involving all accurate experimental energy levels known for H216O (almost 20 000 rovibrational energies including an almost complete list up to a relative energy of 7500 cm-1), augmented with a less accurate but complete list of first-principles computed rovibrational energy levels up to the first dissociation limit, about 41 000 cm-1 (the latter list includes close to one million bound rovibrational energy levels up to J = 69, where J is the rotational quantum number). Partition functions are developed for ortho- and para-H216O as well as for their equilibrium mixture. Unbound rovibrational states of H216O above the first dissociation limit are considered using an approximate model treatment. The effect of the excited electronic states on the thermochemical functions is neglected, as their contribution to the thermochemical functions is negligible even at the highest temperatures considered. Based on the high-accuracy Qint(T) and its first two moments, definitive results, in 1 K increments, are obtained for the following thermochemical functions: Gibbs energy, enthalpy, entropy, and isobaric heat capacity. Reliable uncertainties (approximately two standard deviations) are estimated as a function of temperature for each quantity determined. These uncertainties emphasize that the present results are the most accurate ideal-gas thermochemical functions ever produced for H216O. It is recommended that the new value determined for the standard molar enthalpy increment at 298.15 K, 9.904 04 ± 0.000 01 kJ mol-1, should replace the old CODATA datum, 9.905 ± 0.005 kJ mol-1.

Comparative Life Cycle Assessment of Lignocellulosic Ethanol Production: Biochemical Versus Thermochemical Conversion

NASA Astrophysics Data System (ADS)

Mu, Dongyan; Seager, Thomas; Rao, P. Suresh; Zhao, Fu

2010-10-01

Lignocellulosic biomass can be converted into ethanol through either biochemical or thermochemical conversion processes. Biochemical conversion involves hydrolysis and fermentation while thermochemical conversion involves gasification and catalytic synthesis. Even though these routes produce comparable amounts of ethanol and have similar energy efficiency at the plant level, little is known about their relative environmental performance from a life cycle perspective. Especially, the indirect impacts, i.e. emissions and resource consumption associated with the production of various process inputs, are largely neglected in previous studies. This article compiles material and energy flow data from process simulation models to develop life cycle inventory and compares the fossil fuel consumption, greenhouse gas emissions, and water consumption of both biomass-to-ethanol production processes. The results are presented in terms of contributions from feedstock, direct, indirect, and co-product credits for four representative biomass feedstocks i.e., wood chips, corn stover, waste paper, and wheat straw. To explore the potentials of the two conversion pathways, different technological scenarios are modeled, including current, 2012 and 2020 technology targets, as well as different production/co-production configurations. The modeling results suggest that biochemical conversion has slightly better performance on greenhouse gas emission and fossil fuel consumption, but that thermochemical conversion has significantly less direct, indirect, and life cycle water consumption. Also, if the thermochemical plant operates as a biorefinery with mixed alcohol co-products separated for chemicals, it has the potential to achieve better performance than biochemical pathway across all environmental impact categories considered due to higher co-product credits associated with chemicals being displaced. The results from this work serve as a starting point for developing full life cycle assessment model that facilitates effective decision-making regarding lignocellulosic ethanol production.

In vivo comparison of simultaneous versus sequential injection technique for thermochemical ablation in a porcine model.

PubMed

Cressman, Erik N K; Shenoi, Mithun M; Edelman, Theresa L; Geeslin, Matthew G; Hennings, Leah J; Zhang, Yan; Iaizzo, Paul A; Bischof, John C

2012-01-01

To investigate simultaneous and sequential injection thermochemical ablation in a porcine model, and compare them to sham and acid-only ablation. This IACUC-approved study involved 11 pigs in an acute setting. Ultrasound was used to guide placement of a thermocouple probe and coaxial device designed for thermochemical ablation. Solutions of 10 M acetic acid and NaOH were used in the study. Four injections per pig were performed in identical order at a total rate of 4 mL/min: saline sham, simultaneous, sequential, and acid only. Volume and sphericity of zones of coagulation were measured. Fixed specimens were examined by H&E stain. Average coagulation volumes were 11.2 mL (simultaneous), 19.0 mL (sequential) and 4.4 mL (acid). The highest temperature, 81.3°C, was obtained with simultaneous injection. Average temperatures were 61.1°C (simultaneous), 47.7°C (sequential) and 39.5°C (acid only). Sphericity coefficients (0.83-0.89) had no statistically significant difference among conditions. Thermochemical ablation produced substantial volumes of coagulated tissues relative to the amounts of reagents injected, considerably greater than acid alone in either technique employed. The largest volumes were obtained with sequential injection, yet this came at a price in one case of cardiac arrest. Simultaneous injection yielded the highest recorded temperatures and may be tolerated as well as or better than acid injection alone. Although this pilot study did not show a clear advantage for either sequential or simultaneous methods, the results indicate that thermochemical ablation is attractive for further investigation with regard to both safety and efficacy.

a Protocol for High-Accuracy Theoretical Thermochemistry

NASA Astrophysics Data System (ADS)

Welch, Bradley; Dawes, Richard

2017-06-01

Theoretical studies of spectroscopy and reaction dynamics including the necessary development of potential energy surfaces rely on accurate thermochemical information. The Active Thermochemical Tables (ATcT) approach by Ruscic^{1} incorporates data for a large number of chemical species from a variety of sources (both experimental and theoretical) and derives a self-consistent network capable of making extremely accurate estimates of quantities such as temperature dependent enthalpies of formation. The network provides rigorous uncertainties, and since the values don't rely on a single measurement or calculation, the provenance of each quantity is also obtained. To expand and improve the network it is desirable to have a reliable protocol such as the HEAT approach^{2} for calculating accurate theoretical data. Here we present and benchmark an approach based on explicitly-correlated coupled-cluster theory and vibrational perturbation theory (VPT2). Methyldioxy and Methyl Hydroperoxide are important and well-characterized species in combustion processes and begin the family of (ethyl-, propyl-based, etc) similar compounds (much less is known about the larger members). Accurate anharmonic frequencies are essential to accurately describe even the 0 K enthalpies of formation, but are especially important for finite temperature studies. Here we benchmark the spectroscopic and thermochemical accuracy of the approach, comparing with available data for the smallest systems, and comment on the outlook for larger systems that are less well-known and characterized. ^{1}B. Ruscic, Active Thermochemical Tables (ATcT) values based on ver. 1.118 of the Thermochemical Network (2015); available at ATcT.anl.gov ^{2}A. Tajti, P. G. Szalay, A. G. Császár, M. Kállay, J. Gauss, E. F. Valeev, B. A. Flowers, J. Vázquez, and J. F. Stanton. JCP 121, (2004): 11599.

Material Analysis of Coated Siliconized Silicon Carbide (SiSiC) Honeycomb Structures for Thermochemical Hydrogen Production

PubMed Central

Neises-von Puttkamer, Martina; Simon, Heike; Schmücker, Martin; Roeb, Martin; Sattler, Christian; Pitz-Paal, Robert

2013-01-01

In the present work, thermochemical water splitting with siliconized silicon carbide (SiSiC) honeycombs coated with a zinc ferrite redox material was investigated. The small scale coated monoliths were tested in a laboratory test-rig and characterized by X-ray diffractometry (XRD) and Scanning Electron Microscopy (SEM) with corresponding micro analysis after testing in order to characterize the changes in morphology and composition. Comparison of several treated monoliths revealed the formation of various reaction products such as SiO2, zircon (ZrSiO4), iron silicide (FeSi) and hercynite (FeAl2O4) indicating the occurrence of various side reactions between the different phases of the coating as well as between the coating and the SiSiC substrate. The investigations showed that the ferrite is mainly reduced through reaction with silicon (Si), which is present in the SiSiC matrix, and silicon carbide (SiC). These results led to the formulation of a new redox mechanism for this system in which Zn-ferrite is reduced through Si forming silicon dioxide (SiO2) and through SiC forming SiO2 and carbon monoxide. A decline of hydrogen production within the first 20 cycles is suggested to be due to the growth of a silicon dioxide and zircon layer which acts as a diffusion barrier for the reacting specie. PMID:28809316

Material Analysis of Coated Siliconized Silicon Carbide (SiSiC) Honeycomb Structures for Thermochemical Hydrogen Production.

PubMed

Neises-von Puttkamer, Martina; Simon, Heike; Schmücker, Martin; Roeb, Martin; Sattler, Christian; Pitz-Paal, Robert

2013-01-31

In the present work, thermochemical water splitting with siliconized silicon carbide (SiSiC) honeycombs coated with a zinc ferrite redox material was investigated. The small scale coated monoliths were tested in a laboratory test-rig and characterized by X-ray diffractometry (XRD) and Scanning Electron Microscopy (SEM) with corresponding micro analysis after testing in order to characterize the changes in morphology and composition. Comparison of several treated monoliths revealed the formation of various reaction products such as SiO₂, zircon (ZrSiO₄), iron silicide (FeSi) and hercynite (FeAl₂O₄) indicating the occurrence of various side reactions between the different phases of the coating as well as between the coating and the SiSiC substrate. The investigations showed that the ferrite is mainly reduced through reaction with silicon (Si), which is present in the SiSiC matrix, and silicon carbide (SiC). These results led to the formulation of a new redox mechanism for this system in which Zn-ferrite is reduced through Si forming silicon dioxide (SiO₂) and through SiC forming SiO₂ and carbon monoxide. A decline of hydrogen production within the first 20 cycles is suggested to be due to the growth of a silicon dioxide and zircon layer which acts as a diffusion barrier for the reacting specie.

Thermo-optical properties of residential coals and combustion aerosols

NASA Astrophysics Data System (ADS)

Pintér, Máté; Ajtai, Tibor; Kiss-Albert, Gergely; Kiss, Diána; Utry, Noémi; Janovszky, Patrik; Palásti, Dávid; Smausz, Tomi; Kohut, Attila; Hopp, Béla; Galbács, Gábor; Kukovecz, Ákos; Kónya, Zoltán; Szabó, Gábor; Bozóki, Zoltán

2018-04-01

In this study, we present the inherent optical properties of carbonaceous aerosols generated from various coals (hard through bituminous to lignite) and their correlation with the thermochemical and energetic properties of the bulk coal samples. The nanoablation method provided a unique opportunity for the comprehensive investigation of the generated particles under well controlled laboratory circumstances. First, the wavelength dependent radiative features (optical absorption and scattering) and the size distribution (SD) of the generated particulate matter were measured in-situ in aerosol phase using in-house developed and customised state-of-the-art instrumentation. We also investigated the morphology and microstructure of the generated particles using Transmission Electron Microscopy (TEM) and Electron Diffraction (ED). The absorption spectra of the measured samples (quantified by Absorption Angström Exponent (AAE)) were observed to be distinctive. The correlation between the thermochemical features of bulk coal samples (fixed carbon (FC) to volatile matter (VM) ratio and calorific value (CV)) and the AAE of aerosol assembly were found to be (r2 = 0.97 and r2 = 0.97) respectively. Lignite was off the fitted curves in both cases most probably due to its high optically inactive volatile material content. Although more samples are necessary to be investigated to draw statistically relevant conclusion, the revealed correlation between CV and Single Scattering Albedo (SSA) implies that climatic impact of coal combusted aerosol could depend on the thermal and energetic properties of the bulk material.

Numerical study on the thermo-chemically driven Geodynamo

NASA Astrophysics Data System (ADS)

Trümper, Tobias; Hansen, Ulrich

2014-05-01

In our numerical study we consider magneto-convection in the Earth's outer core driven by buoyancy induced by heterogeneities both in the thermal and the chemical field. The outer core is thus treated as a self-gravitating, rotating, spherical shell with unstable thermal and chemical gradients across its radius. The thermal gradient is maintained by secular cooling of the core and the release of latent heat at the inner core freezing front. Simultaneously, the concentration of the light constituents of the liquid phase increases at the inner core boundary since only a smaller fraction of the light elements can be incorporated during solidification. Thus, the inner core boundary constitutes a source of compositional buoyancy. The molecular diffusivities of the driving agents differ by some orders of magnitude so that a double-diffusive model is employed in order to study the flow dynamics of this system. We investigate the influence of different thermo-chemical driving scenarios on the structure of the flow and the internal magnetic field. A constant ratio of the diffusivities (Le=10) and a constant Ekman number (Ek=10-4) are adopted. Apart from testing different driving scenarios, the double-diffusive approach also allows to implement distinct boundary conditions on temperature and composition. Isochemical and fixed chemical flux boundary conditions are implemented in order to investigate their respective influence on the flow and magnetic field generation.

Thermochemically evolved nanoplatelets of bismuth selenide with enhanced thermoelectric figure of merit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ali, Zulfiqar; Cao, Chuanbao, E-mail: cbcao@bit.edu.cn; Butt, Faheem K.

We firstly present a simple thermochemical method to fabricate high-quality Bi{sub 2}Se{sub 3} nanoplatelets with enhanced figure of merit using elemental bismuth and selenium powders as precursors. The crystal structure of as synthesized products is characterized via X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM) measurements. Morphological and chemical synthetic parameters are investigated through a series of experiments; thickness and composition of the platelets are well controlled in large scale production. Subsequently spark plasma sintering (SPS) is performed to fabricate n-type nanostructured bulk thermoelectric materials. Raman Spectroscopy of the two selected samples with approximatelymore » of 50 and 100 nm thicknesses shows three vibrational modes. The lower thickness sample exhibits the maximum red shift of about 2.17 cm{sup -1} and maximum broadening of about 10 cm{sup -1} by in-plane vibrational mode E{sup 2}{sub g}. The enhanced value of figure of merit ∼0.41 is obtained for pure phase bismuth selenide to the best of our knowledge. We observe metallic conduction behavior while semiconducting behavior for nanostructured bismuth selenide is reported elsewhere which could be due to different synthetic techniques adopted. These results clearly suggest that our adopted synthetic technique has profound effect on the electronic and thermoelectric transport properties of this material.« less

Visualizing lignin coalescence and migration through maize cell walls following thermochemical pretreatment.

PubMed

Donohoe, Bryon S; Decker, Stephen R; Tucker, Melvin P; Himmel, Michael E; Vinzant, Todd B

2008-12-01

Plant cell walls are composed primarily of cellulose, hemicelluloses, lignins, and pectins. Of these components, lignins exhibit unique chemistry and physiological functions. Although lignins can be used as a product feedstock or as a fuel, lignins are also generally seen as a barrier to efficient enzymatic breakdown of biomass to sugars. Indeed, many pretreatment strategies focus on removing a significant fraction of lignin from biomass to better enable saccharification. In order to better understand the fate of biomass lignins that remain with the solids following dilute acid pretreatment, we undertook a structural investigation to track lignins on and in biomass cell walls. SEM and TEM imaging revealed a range of droplet morphologies that appear on and within cell walls of pretreated biomass; as well as the specific ultrastructural regions that accumulate the droplets. These droplets were shown to contain lignin by FTIR, NMR, antibody labeling, and cytochemical staining. We provide evidence supporting the idea that thermochemical pretreatments reaching temperatures above the range for lignin phase transition cause lignins to coalesce into larger molten bodies that migrate within and out of the cell wall, and can redeposit on the surface of plant cell walls. This decompartmentalization and relocalization of lignins is likely to be at least as important as lignin removal in the quest to improve the digestibility of biomass for sugars and fuels production.

A theoretical thermochemical study of solute-solvent dielectric effects in the displacement of codon-anticodon base pairs

NASA Astrophysics Data System (ADS)

Monajjemi, M.; Razavian, M. H.; Mollaamin, F.; Naderi, F.; Honarparvar, B.

2008-12-01

Quantum-chemical solvent effect theories describe the electronic structure of a molecular subsystem embedded in a solvent or other molecular environment. The solvation of biomolecules is important in molecular biology, since numerous processes involve proteins interacting in changing solvent-solute systems. In this theoretical study, we focus on mRNA-tRNA base pairs as a fundamental step in protein synthesis influenced by hydrogen bonding between two antiparallel trinucleotides, namely, the mRNA codon and tRNA anticodon. We use the mean reaction field theories, which describe electrostatic and polarization interactions between solute and solvent in the AAA, UUU, AAG, and UUC triplex sequences optimized in various solvent media such as water, dimethylsulfoxide, methanol, ethanol, and cyclopean using the self-consistent reaction field model. This process depends on either the reaction potential function of the solvent or charge transfer operators that appear in solute-solvent interaction. Because of codon and anticodon biological criteria, we performed nonempirical quantum-mechanical calculations at the BLYP and B3LYP/3-21G, 6-31G, and 6-31G* levels of theory in the gas phase and five solvents at three temperatures. Finally, to obtain more information, we calculated thermochemical parameters to find that the dielectric constant of solvents plays an important role in the displacement of amino acid sequences on codon-anticodon residues in proteins, which can cause some mutations in humans.

Methodology Report for H2SModel

DTIC Science & Technology

2012-01-01

thermochemical) cal (thermochemical/ cm2) curie degree (angl e ) degree Fahrenheit electron volt erg erg/second foot foot- pound- force gal l... Dosimetry ) model developed by Asgharian ([7, 10]) . First, transport of H2S in the lung is modeled by the area-averaged convective-diffusion equation...performance. Technical Report DNA TR 85 52, Defense Nuclear Agency, Washington, D.C. , 1984. [10] Asgharian, B., et al. Multiple Path Particle Dosimetry

A comparison of producer gas, biochar, and activated carbon from two distributed scale thermochemical conversion systems used to process forest biomass

Treesearch

Nathaniel Anderson; J. Greg Jones; Deborah Page-Dumroese; Daniel McCollum; Stephen Baker; Daniel Loeffler; Woodam Chung

2013-01-01

Thermochemical biomass conversion systems have the potential to produce heat, power, fuels and other products from forest biomass at distributed scales that meet the needs of some forest industry facilities. However, many of these systems have not been deployed in this sector and the products they produce from forest biomass have not been adequately described or...

Observations of Circumstellar Thermochemical Equilibrium: The Case of Phosphorus

NASA Technical Reports Server (NTRS)

Milam, Stefanie N.; Charnley, Steven B.

2011-01-01

We will present observations of phosphorus-bearing species in circumstellar envelopes, including carbon- and oxygen-rich shells 1. New models of thermochemical equilibrium chemistry have been developed to interpret, and constrained by these data. These calculations will also be presented and compared to the numerous P-bearing species already observed in evolved stars. Predictions for other viable species will be made for observations with Herschel and ALMA.

Linking lowermost mantle structure, core-mantle boundary heat flux and mantle plume formation

NASA Astrophysics Data System (ADS)

Li, Mingming; Zhong, Shijie; Olson, Peter

2018-04-01

The dynamics of Earth's lowermost mantle exert significant control on the formation of mantle plumes and the core-mantle boundary (CMB) heat flux. However, it is not clear if and how the variation of CMB heat flux and mantle plume activity are related. Here, we perform geodynamic model experiments that show how temporal variations in CMB heat flux and pulses of mantle plumes are related to morphologic changes of the thermochemical piles of large-scale compositional heterogeneities in Earth's lowermost mantle, represented by the large low shear velocity provinces (LLSVPs). We find good correlation between the morphologic changes of the thermochemical piles and the time variation of CMB heat flux. The morphology of the thermochemical piles is significantly altered during the initiation and ascent of strong mantle plumes, and the changes in pile morphology cause variations in the local and the total CMB heat flux. Our modeling results indicate that plume-induced episodic variations of CMB heat flux link geomagnetic superchrons to pulses of surface volcanism, although the relative timing of these two phenomena remains problematic. We also find that the density distribution in thermochemical piles is heterogeneous, and that the piles are denser on average than the surrounding mantle when both thermal and chemical effects are included.

Lignin structural alterations in thermochemical pretreatments with limited delignification

DOE PAGES

Pu, Yunqiao; Hu, Fan; Huang, Fang; ...

2015-08-02

Lignocellulosic biomass has a complex and rigid cell wall structure that makes biomass recalcitrant to biological and chemical degradation. Among the three major structural biopolymers (i.e., cellulose, hemicellulose and lignin) in plant cell walls, lignin is considered the most recalcitrant component and generally plays a negative role in the biochemical conversion of biomass to biofuels. The conversion of biomass to biofuels through a biochemical platform usually requires a pretreatment stage to reduce the recalcitrance. Pretreatment renders compositional and structural changes of biomass with these changes ultimately govern the efficiency of the subsequent enzymatic hydrolysis. Dilute acid, hot water, steam explosion,more » and ammonia fiber expansion pretreatments are among the leading thermochemical pretreatments with a limited delignification that can reduce biomass recalcitrance. Practical applications of these pretreatment are rapidly developing as illustrated by recent commercial scale cellulosic ethanol plants. While these thermochemical pretreatments generally lead to only a limited delignification and no significant change of lignin content in the pretreated biomass, the lignin transformations that occur during these pretreatments and the roles they play in recalcitrance reduction is an important research aspect. This review highlights recent advances in our understanding of lignin alterations during these limited delignification thermochemical pretreatments, with emphasis on lignin chemical structures, molecular weights, and redistributions in the pretreated biomass.« less

Water Footprint and Land Requirement of Solar Thermochemical Jet-Fuel Production.

PubMed

Falter, Christoph; Pitz-Paal, Robert

2017-11-07

The production of alternative fuels via the solar thermochemical pathway has the potential to provide supply security and to significantly reduce greenhouse gas emissions. H 2 O and CO 2 are converted to liquid hydrocarbon fuels using concentrated solar energy mediated by redox reactions of a metal oxide. Because attractive production locations are in arid regions, the water footprint and the land requirement of this fuel production pathway are analyzed. The water footprint consists of 7.4 liters per liter of jet fuel of direct demand on-site and 42.4 liters per liter of jet fuel of indirect demand, where the dominant contributions are the mining of the rare earth oxide ceria, the manufacturing of the solar concentration infrastructure, and the cleaning of the mirrors. The area-specific productivity is found to be 33 362 liters per hectare per year of jet fuel equivalents, where the land coverage is mainly due to the concentration of solar energy for heat and electricity. The water footprint and the land requirement of the solar thermochemical fuel pathway are larger than the best power-to-liquid pathways but an order of magnitude lower than the best biomass-to-liquid pathways. For the production of solar thermochemical fuels arid regions are best-suited, and for biofuels regions of a moderate and humid climate.

Revisiting the BaO2/BaO redox cycle for solar thermochemical energy storage.

PubMed

Carrillo, A J; Sastre, D; Serrano, D P; Pizarro, P; Coronado, J M

2016-03-21

The barium peroxide-based redox cycle was proposed in the late 1970s as a thermochemical energy storage system. Since then, very little attention has been paid to such redox couples. In this paper, we have revisited the use of reduction-oxidation reactions of the BaO2/BaO system for thermochemical heat storage at high temperatures. Using thermogravimetric analysis, reduction and oxidation reactions were studied in order to find the main limitations associated with each process. Furthermore, the system was evaluated through several charge-discharge stages in order to analyse its possible degradation after repeated cycling. Through differential scanning calorimetry the heat stored and released were also determined. Oxidation reaction, which was found to be slower than reduction, was studied in more detail using isothermal tests. It was observed that the rate-controlling step of BaO oxidation follows zero-order kinetics, although at high temperatures a deviation from Arrhenius behaviour was observed probably due to hindrances to anionic oxygen diffusion caused by the formation of an external layer of BaO2. This redox couple was able to withstand several redox cycles without deactivation, showing reaction conversions close to 100% provided that impurities are previously eliminated through thermal pre-treatment, demonstrating the feasibility of this system for solar thermochemical heat storage.

Binary Phase Diagrams and Thermodynamic Properties of Silicon and Essential Doping Elements (Al, As, B, Bi, Ga, In, N, P, Sb and Tl)

PubMed Central

Mostafa, Ahmad; Medraj, Mamoun

2017-01-01

Fabrication of solar and electronic silicon wafers involves direct contact between solid, liquid and gas phases at near equilibrium conditions. Understanding of the phase diagrams and thermochemical properties of the Si-dopant binary systems is essential for providing processing conditions and for understanding the phase formation and transformation. In this work, ten Si-based binary phase diagrams, including Si with group IIIA elements (Al, B, Ga, In and Tl) and with group VA elements (As, Bi, N, P and Sb), have been reviewed. Each of these systems has been critically discussed on both aspects of phase diagram and thermodynamic properties. The available experimental data and thermodynamic parameters in the literature have been summarized and assessed thoroughly to provide consistent understanding of each system. Some systems were re-calculated to obtain a combination of the best evaluated phase diagram and a set of optimized thermodynamic parameters. As doping levels of solar and electronic silicon are of high technological importance, diffusion data has been presented to serve as a useful reference on the properties, behavior and quantities of metal impurities in silicon. This paper is meant to bridge the theoretical understanding of phase diagrams with the research and development of solar-grade silicon production, relying on the available information in the literature and our own analysis. PMID:28773034

Research, Development, and Field Testing of Thermochemical Recuperation for High Temperature Furnace

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurek, Harry; Kozlov, Aleksandr

Gas Technology Institute (GTI) evaluated the technical and economic feasibility of utilizing a non-catalytic ThermoChemical Recuperation System (TCRS) to recover a significant amount of energy from the waste gases of natural gas fired steel reheat furnaces. The project was related to DOE-AMO’s (formerly known as ITP) one of the technical areas of interest: Technologies to improve energy efficiency and reduce the carbon footprint of equipment currently used in energy-intensive industries such as iron and steel, and reduce by at least 30% energy consumption and carbon dioxide emission compared to the conventional technologies. ThermoChemical Recuperation (TCR) is a technique that recoversmore » sensible heat in the exhaust gas from an industrial process, furnace, engine etc., when a hydrocarbon fuel is used for combustion. TCR enables waste heat recovery by both combustion air preheat and hydrocarbon fuel (natural gas, for example) reforming into a higher calorific fuel. The reforming process uses hot flue gas components (H2O and CO2) or steam to convert the fuel into a combustible mixture of hydrogen (H2), carbon monoxide (CO), and some unreformed hydrocarbons (CnHm). Reforming of natural gas with recycled exhaust gas or steam can significantly reduce fuel consumption, CO2 emissions and cost as well as increase process thermal efficiency. The calorific content of the fuel can be increased by up to ~28% with the TCR process if the original source fuel is natural gas. In addition, the fuel is preheated during the TCR process adding sensible heat to the fuel. The Research and Development work by GTI was proposed to be carried out in three Phases (Project Objectives). • Phase I: Develop a feasibility study consisting of a benefits-derived economic evaluation of a ThermoChemical Recuperation (TCR) concept with respect to high temperature reheat furnace applications within the steel industry (and cross-cutting industries). This will establish the design parameters and potential performance of TCR. • Phase II: Conduct research and development to take the validated technology concept from Phase I to a developmental state for a Phase 3, prototype field test. • Phase III: Design, fabricate, and prototype field testing of the TCR unit close coupled to an existing high temperature reheat furnace at a steel company for evaluation under industrial conditions The project was initiated on September 30, 2008. The report of Phase I results and conclusions was issued on October 30, 2009. The findings were reviewed by the project partners and the collective recommendation was to proceed with Phase II. Upon the work-conclusion, the Phase II report was issued on March 5, 2012. The scope of work involved the physical testing of a laboratory scale Recuperative Reformer (RR) to validate predicted performances from the feasibility study in Phase I (26% fuel reduction). Although the testing was a successful validation (21% fuel reduction mode), a technical issue 5 arose, namely a Methane Reforming Rate (MRR) roll off or non-sustaining of the methane reforming rate. GTI’s preliminary conclusions were that mechanism(s) producing the methane reforming rate reduction were not entirely known or understood and the chemical kinetics that triggered the roll off mechanism and/or other mechanisms needed to be further evaluated. GTI developed a plan to uncover the reason(s) for not sustaining a satisfactory Methane Reforming Rate (MRR) of the laboratory scale recuperator reformer (RR). The extended testing program consisted primarily of four tasks based on expected outcomes at that time. The project partners reviewed the proposal and recommended the proposed work extension to proceed and suspension of Phase III pending further review of the results of this work identified as Task 2.5. Additional Temperature Threshold Testing was undertaken by GTI and simultaneously independent analysis was carried out by the University of California Davis. Upon completion of the work, the Phase II - Task 2.5 - Extended TCR Testing Report was issued on July 10, 2013. As a result of the work performed in Phase II, Task 2.5, the end conclusion was that temperature dependency has been affirmed, but with temperatures within the recuperative reformer with higher criticality than the flue gas temperature entering into the recuperative reformer. GTI’s further conclusion is that adjustments to the lab recuperative reformer design, given the three-heat exchanger-configuration, remains a valid constraint, and therefore, it would be necessary to scale up to a field experiment capacity level. Design modifications to the recuperative reformer would likely be necessary requiring re-examining space velocity (residence time), heat transfer surface area, plus other considerations, so that a target “temperature profile envelope” within the recuperative reformer would be broad enough to perform satisfactorily in the field with varying flue gas exit temperatures from the majority of the reheat furnace population. A project review meeting was held with the project partners July 17, 2013. Task 2.5 results were reviewed along with the conclusions and recommendations. GTI proposed three field experiment options for Phase III. On the basis of successful sets of Temperature Threshold Tests (TTT), measured results demonstrated that the current design can capably be scaled up and GTI recommended consideration of these three options for a Phase III field experiment. Option 1: Production furnace ~250 MMBtu/h Option 2: Production furnace ~100 - 200 MMBtu/h Option 3: Production furnace ~50 - 100 MMBtu/h The project partners’ resulting unanimous recommendation was to provisionally proceed with Phase 3 – Option 3. Subsequently, after further deliberation, review and analysis of their respective field experiment sites, the three steel industry partners determined not to continue to Phase III of the project for both technical reasons and reasons of process economics, i.e., limited applicability of TCR technology due to higher exhaust gas temperature ranges and sensitivity to natural gas prices. As of this report, the current natural gas price is lower than the $6.03 per 6 MMBtu projected to return positive NPVs for implementing TCR technology. Accordingly, the project work was terminated effective December 31, 2013.« less

Mass-dependent and Mass-independent Sulphur Isotope Fractionation Accompanying Thermal- and Photo-chemical Decomposition of Sulphur Bearing Organic Compounds

NASA Astrophysics Data System (ADS)

Oduro, Harry; Izon, Gareth; Ono, Shuhei

2014-05-01

The bimodal S-isotope record, specifically the transition from mass independent (MIF) to mass dependent fractionation (MDF), is perhaps the most widely cited line of evidence for an irreversible rise in atmospheric oxygen at ca. 2.4Ga. The production and preservation of S-MIF, manifested in both Δ33S and Δ36S, within the geological record are linked to atmospheric O2 via a number of arguments. However, to date, the only mechanism capable of generating S-MIF consistent with the Archaean sedimentary records involves gas-phase ultraviolet irradiation of SO21 photolysis. More recently, Δ33S S-MIF trends have been reported from en vitro thermochemical sulphate reduction (TSR) experiments, prompting authors to question the importance of S-MIF as a proxy for Earth oxidation2. Importantly, whilst emerging TSR experiments3,4 affirm the reported Δ33S trends2, these experiments fail to identify correlated S-MIF between Δ33S and Δ36S values3,4. Realization that S-MIF is confined to Δ33S during TSR, precludes TSR as a mechanism responsible for the origin of the Archaean S-MIF record but strongly suggests the effect originating from a magnetic isotope effect (MIE) associated with 33S nucleus3,4. Clearly, photochemical and thermochemical processes impart different Δ36S/Δ33S trends with significant variation in δ34S; however, a complete experimental elucidation of mechanisms responsible for the S-MIF and S-MIE signatures is lacking. Interestingly, a complete understanding of the S-isotope chemistry during thermal- and photo-chemical decomposition may reveal wavelength and thermal dependence archived in the sedimentary record. Here we extend the experimental database to explore the magnitude and sign of Δ36S/Δ33S and δ34S produced during both photo- and thermochemical processes. Here the organic sulphur compounds (OSC) utilized in these experiments carries diagnostic Δ36S/Δ33S patterns that differ from those reported from photolysis experiment SO2 and from the Archaean sedimentary record. Further thermal decomposition of several sulphur containing compounds with; 1) an aliphatic-S (e.g., diphenyl disulphide), 2) tri-substituted aromatic-S (trithiane), and S-amino acids (e.g., cysteine, methionine, taurine, and glutathionine) were tested for four S-isotope fractionation under vacuum. Among these, aromatic trithiane produced anomalous 33S up to 1.3‰, indicating thermal decomposition through radical chemistry, producing S-MIE. While taurine with sulphonic acid (R-SO2OH) functional groups yielded S-MDF up to 15‰ (between the AVS and the residual OSC), which is consistent with estimated zero-point energy shifts for thiol (R-SH), and thiyl (R-S-CH3) groups of cysteine and methionine, respectively. These results suggest that OSC might undergo either thermal or photochemical decomposition and the S-MIF, S-MDF, and S-MIE signatures may be archived in the geologic record. The emerging mechanisms responsible for these isotope signals and their implications will be discussed in more detail. Ultimately this work offers a framework where these signals can be used as a diagnostic marker to distinguish between thermo- and photochemical processes. References: 1. Farquhar et al., Science 2000 2. Watanabe et al., Science 2010; 3. Oduro et al., PNAS 2011; 4. Kopf and Ono, GCA 2012.

Experimental aspects of the thermochemical conversion of solar energy - Decarbonation of CaCO3

NASA Astrophysics Data System (ADS)

Flamant, G.; Hernandez, D.; Bonet, C.; Traverse, J.-P.

1980-01-01

The feasibility of thermochemical conversion of concentrated solar energy is investigated. Consideration is given to heterogeneous systems in the range 500-1500 C. A reaction volume is on a laboratory scale about 30 cu cm. An experimental set-up selected is a fluid bed and a rotary kiln. An endothermal reaction, namely, decarbonation of CaCO3, is selected as a possible application for solar power plants.

Materials-Related Aspects of Thermochemical Water and Carbon Dioxide Splitting: A Review

PubMed Central

Roeb, Martin; Neises, Martina; Monnerie, Nathalie; Call, Friedemann; Simon, Heike; Sattler, Christian; Schmücker, Martin; Pitz-Paal, Robert

2012-01-01

Thermochemical multistep water- and CO2-splitting processes are promising options to face future energy problems. Particularly, the possible incorporation of solar power makes these processes sustainable and environmentally attractive since only water, CO2 and solar power are used; the concentrated solar energy is converted into storable and transportable fuels. One of the major barriers to technological success is the identification of suitable active materials like catalysts and redox materials exhibiting satisfactory durability, reactivity and efficiencies. Moreover, materials play an important role in the construction of key components and for the implementation in commercial solar plants. The most promising thermochemical water- and CO2-splitting processes are being described and discussed with respect to further development and future potential. The main materials-related challenges of those processes are being analyzed. Technical approaches and development progress in terms of solving them are addressed and assessed in this review.

Surface thermochemical effects on TPS-coupled aerothermodynamics in hypersonic Martian gas flow

NASA Astrophysics Data System (ADS)

Yang, Xiaofeng; Gui, Yewei; Tang, Wei; Du, Yanxia; Liu, Lei; Xiao, Guangming; Wei, Dong

2018-06-01

This paper deals with the surface thermochemical effects on TPS-coupled aerothermodynamics in hypersonic Martian gas flow. An interface condition with finite-rate thermochemistry was established to balance the three-dimensional Navier-Stokes solver and TPS thermal response solver, and a series of coupled simulations of chemical non-equilibrium aerothermodynamics and structure heat transfer with various surface catalycities were performed for hypersonic Mars entries. The analysis of surface thermochemistry reveals that the surface chemical reactions have great contribution to aerodynamic heating, and the temperature-dependence of finite-rate catalysis highly influences the evolution of the coupling aerodynamic heating in the coupling process. For fixed free stream parameters with proper catalytic excitation energy, a "leap" phenomenon of the TPS-coupled heat flux with the coupling time appears in the initial stage of the coupling process, due to the strong thermochemical effects on the TPS surface.

Thermochemical pretreatments for enhancing succinic acid production from industrial hemp (Cannabis sativa L.).

PubMed

Gunnarsson, Ingólfur B; Kuglarz, Mariusz; Karakashev, Dimitar; Angelidaki, Irini

2015-04-01

The aim of this study was to develop an efficient thermochemical method for treatment of industrial hemp biomass, in order to increase its bioconversion to succinic acid. Industrial hemp was subjected to various thermochemical pretreatments using 0-3% H2SO4, NaOH or H2O2 at 121-180°C prior to enzymatic hydrolysis. The influence of the different pretreatments on hydrolysis and succinic acid production by Actinobacillus succinogenes 130Z was investigated in batch mode, using anaerobic bottles and bioreactors. Enzymatic hydrolysis and fermentation of hemp material pretreated with 3% H2O2 resulted in the highest overall sugar yield (73.5%), maximum succinic acid titer (21.9 g L(-1)), as well as the highest succinic acid yield (83%). Results obtained clearly demonstrated the impact of different pretreatments on the bioconversion efficiency of industrial hemp into succinic acid. Copyright © 2015. Published by Elsevier Ltd.

Thermochemical conversion of microalgal biomass into biofuels: a review.

PubMed

Chen, Wei-Hsin; Lin, Bo-Jhih; Huang, Ming-Yueh; Chang, Jo-Shu

2015-05-01

Following first-generation and second-generation biofuels produced from food and non-food crops, respectively, algal biomass has become an important feedstock for the production of third-generation biofuels. Microalgal biomass is characterized by rapid growth and high carbon fixing efficiency when they grow. On account of potential of mass production and greenhouse gas uptake, microalgae are promising feedstocks for biofuels development. Thermochemical conversion is an effective process for biofuel production from biomass. The technology mainly includes torrefaction, liquefaction, pyrolysis, and gasification. Through these conversion technologies, solid, liquid, and gaseous biofuels are produced from microalgae for heat and power generation. The liquid bio-oils can further be upgraded for chemicals, while the synthesis gas can be synthesized into liquid fuels. This paper aims to provide a state-of-the-art review of the thermochemical conversion technologies of microalgal biomass into fuels. Detailed conversion processes and their outcome are also addressed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Development and application of computational aerothermodynamics flowfield computer codes

NASA Technical Reports Server (NTRS)

Venkatapathy, Ethiraj

1993-01-01

Computations are presented for one-dimensional, strong shock waves that are typical of those that form in front of a reentering spacecraft. The fluid mechanics and thermochemistry are modeled using two different approaches. The first employs traditional continuum techniques in solving the Navier-Stokes equations. The second-approach employs a particle simulation technique (the direct simulation Monte Carlo method, DSMC). The thermochemical models employed in these two techniques are quite different. The present investigation presents an evaluation of thermochemical models for nitrogen under hypersonic flow conditions. Four separate cases are considered. The cases are governed, respectively, by the following: vibrational relaxation; weak dissociation; strong dissociation; and weak ionization. In near-continuum, hypersonic flow, the nonequilibrium thermochemical models employed in continuum and particle simulations produce nearly identical solutions. Further, the two approaches are evaluated successfully against available experimental data for weakly and strongly dissociating flows.

Comparative studies on thermochemical characterization of corn stover pretreated by white-rot and brown-rot fungi.

PubMed

Zeng, Yelin; Yang, Xuewei; Yu, Hongbo; Zhang, Xiaoyu; Ma, Fuying

2011-09-28

The effects of white-rot and brown-rot fungal pretreatment on the chemical composition and thermochemical conversion of corn stover were investigated. Fungus-pretreated corn stover was analyzed by Fourier transform infrared spectroscopy and X-ray diffraction analysis to characterize the changes in chemical composition. Differences in thermochemical conversion of corn stover after fungal pretreatment were investigated using thermogravimetric and pyrolysis analysis. The results indicated that the white-rot fungus Irpex lacteus CD2 has great lignin-degrading ability, whereas the brown-rot fungus Fomitopsis sp. IMER2 preferentially degrades the amorphous regions of the cellulose. The biopretreatment favors thermal decomposition of corn stover. The weight loss of IMER2-treated acid detergent fiber became greater, and the oil yield increased from 32.7 to 50.8%. After CD2 biopretreatment, 58% weight loss of acid detergent lignin was achieved and the oil yield increased from 16.8 to 26.8%.

Thermochemical water decomposition. [hydrogen separation for energy applications

NASA Technical Reports Server (NTRS)

Funk, J. E.

1977-01-01

At present, nearly all of the hydrogen consumed in the world is produced by reacting hydrocarbons with water. As the supply of hydrocarbons diminishes, the problem of producing hydrogen from water alone will become increasingly important. Furthermore, producing hydrogen from water is a means of energy conversion by which thermal energy from a primary source, such as solar or nuclear fusion of fission, can be changed into an easily transportable and ecologically acceptable fuel. The attraction of thermochemical processes is that they offer the potential for converting thermal energy to hydrogen more efficiently than by water electrolysis. A thermochemical hydrogen-production process is one which requires only water as material input and mainly thermal energy, or heat, as an energy input. Attention is given to a definition of process thermal efficiency, the thermodynamics of the overall process, the single-stage process, the two-stage process, multistage processes, the work of separation and a process evaluation.

Vapour growth of argyrodite-type ionic conductors Cu 6PS 5Hal

NASA Astrophysics Data System (ADS)

Fiechter, S.; Eckstein, J.; Nitsche, R.

1983-03-01

Cu 6PS 5Hal compounds (with Hal = Cl, Br or I) have been crystallized around 950 K by CVT with P, S and Hal (and combinations thereof). Chemical insight into the transport processes was gained from dissociation pressure measurements and spectroscopic vapour analysis. Lacking thermochemical data of the compounds were obtained from Cp measurements. Models, derived for the CVT mechanisms, yield transport rates and directions which agree qualitatively with experiments. The main vapour species (for Hal = C1) are PSCI 3, S 2, PCI 3, P 4S 3 and (CuCl) 3. With a surplus of CuHal, VLS growth via liquid CuHal/Cu 2S phases was observed.

Characterization of urania vaporization with transpiration coupled thermogravimetry

DOE PAGES

McMurray, J. W.

2015-12-05

Determining equilibrium vapor pressures of materials is made easier by transpiration measurements. However, the traditional technique involves condensing the volatiles entrained in a carrier gas outside of the hot measurement zone. One potential problem is deposition en route to a cooled collector. Thermogravimetric analysis (TGA) can be used to measure in situ mass loss due to vaporization and therefore obviate the need to analyze the entire gas train due to premature plating of vapor species. Therefore, a transpiration coupled TGA technique was used to determine equilibrium pressures of UO3 gas over fluorite structure UO2+x and U3O8 at T = (1573more » and 1773) K. Moreover, we compared to calculations from models and databases in the open literature. Our study gives clarity to the thermochemical data for UO3 gas and validates the mass loss transpiration method using thermogravimetry for determining equilibrium vapor pressures of non-stoichiometric oxides.« less

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

NASA Technical Reports Server (NTRS)

Ahlborg, Nadia L.; Zhu, Dongming

2013-01-01

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

FY06 L2C2 HE program report Zaug et al.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zaug, J M; Crowhurst, J C; Howard, W M

2008-08-01

The purpose of this project is to advance the improvement of LLNL thermochemical computational models that form the underlying basis or input for laboratory hydrodynamic simulations. Our general work approach utilizes, by design, tight experimental-theoretical research interactions that allow us to not empirically, but rather more scientifically improve LLNL computational results. The ultimate goal here is to confidently predict through computer models, the performance and safety parameters of currently maintained, modified, and newly designed stockpile systems. To attain our goal we make relevant experimental measurements on candidate detonation products constrained under static high-pressure and temperature conditions. The reduced information frommore » these measurements is then used to construct analytical forms that describe the potential surface (repulsive energy as a function of interatomic separation distance) of single and mixed fluid or detonation product species. These potential surface shapes are also constructed using input from well-trusted shock wave physics and assorted thermodynamic data available in the open literature. Our potential surfaces permit one to determine the equations of state (P,V,T), the equilibrium chemistry, phase, and chemical interactions of detonation products under a very wide range of extreme pressure temperature conditions. Using our foundation of experimentally refined potential surfaces we are in a position to calculate, with confidence, the energetic output and chemical speciation occurring from a specific combustion and/or detonation reaction. The thermochemical model we developed and use for calculating the equilibrium chemistry, kinetics, and energy from ultrafast processes is named 'Cheetah'. Computational results from our Cheetah code are coupled to laboratory ALE3D hydrodynamic simulation codes where the complete response behavior of an existing or proposed system is ultimately predicted. The Cheetah thermochemical code is also used by well over 500 U.S. government DoD and DOE community users who calculate the chemical properties of detonated high explosives, propellants, and pyrotechnics. To satisfy the growing needs of LLNL and the general user community we continue to improve the robustness of our Cheetah code. The P-T range of current speed of sound experiments will soon be extended by a factor of four and our recently developed technological advancements permit us to, for the first time, study any chemical specie or fluid mixture. New experiments will focus on determining the miscibility or coexistence curves of detonation product mixtures. Our newly constructed ultrafast laser diagnostics will permit us to determine what chemical species exist under conditions approaching Chapman-Jouguet (CJ) detonation states. Furthermore we will measure the time evolution of candidate species and use our chemical kinetics data to develop new and validate existing rate laws employed in future versions of our Cheetah thermochemical code.« less

Development of efficient, integrated cellulosic biorefineries : LDRD final report.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teh, Kwee-Yan; Hecht, Ethan S.; Shaddix, Christopher R.

2010-09-01

Cellulosic ethanol, generated from lignocellulosic biomass sources such as grasses and trees, is a promising alternative to conventional starch- and sugar-based ethanol production in terms of potential production quantities, CO{sub 2} impact, and economic competitiveness. In addition, cellulosic ethanol can be generated (at least in principle) without competing with food production. However, approximately 1/3 of the lignocellulosic biomass material (including all of the lignin) cannot be converted to ethanol through biochemical means and must be extracted at some point in the biochemical process. In this project we gathered basic information on the prospects for utilizing this lignin residue material inmore » thermochemical conversion processes to improve the overall energy efficiency or liquid fuel production capacity of cellulosic biorefineries. Two existing pretreatment approaches, soaking in aqueous ammonia (SAA) and the Arkenol (strong sulfuric acid) process, were implemented at Sandia and used to generated suitable quantities of residue material from corn stover and eucalyptus feedstocks for subsequent thermochemical research. A third, novel technique, using ionic liquids (IL) was investigated by Sandia researchers at the Joint Bioenergy Institute (JBEI), but was not successful in isolating sufficient lignin residue. Additional residue material for thermochemical research was supplied from the dilute-acid simultaneous saccharification/fermentation (SSF) pilot-scale process at the National Renewable Energy Laboratory (NREL). The high-temperature volatiles yields of the different residues were measured, as were the char combustion reactivities. The residue chars showed slightly lower reactivity than raw biomass char, except for the SSF residue, which had substantially lower reactivity. Exergy analysis was applied to the NREL standard process design model for thermochemical ethanol production and from a prototypical dedicated biochemical process, with process data supplied by a recent report from the National Research Council (NRC). The thermochemical system analysis revealed that most of the system inefficiency is associated with the gasification process and subsequent tar reforming step. For the biochemical process, the steam generation from residue combustion, providing the requisite heating for the conventional pretreatment and alcohol distillation processes, was shown to dominate the exergy loss. An overall energy balance with different potential distillation energy requirements shows that as much as 30% of the biomass energy content may be available in the future as a feedstock for thermochemical production of liquid fuels.« less

Processing of CuInSe{sub 2}-based solar cells: Characterization of deposition processes in terms of chemical reaction analyses. Phase 2 Annual Report, 6 May 1996--5 May 1997

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, T.

This report describes research performed by the University of Florida during Phase 2 of this subcontract. First, to study CIGS, researchers adapted a contactless, nondestructive technique previously developed for measuring photogenerated excess carrier lifetimes in SOI wafers. This dual-beam optical modulation (DBOM) technique was used to investigate the differences between three alternative methods of depositing CdS (conventional chemical-bath deposition [CBD], metal-organic chemical vapor deposition [MOCVD], and sputtering). Second, a critical assessment of the Cu-In-Se thermochemical and phase diagram data using standard CALPHAD procedures is being performed. The outcome of this research will produce useful information on equilibrium vapor compositions (requiredmore » annealing ambients, Sex fluxes from effusion cells), phase diagrams (conditions for melt-assisted growth), chemical potentials (driving forces for diffusion and chemical reactions), and consistent solution models (extents of solid solutions and extending phase diagrams). Third, an integrated facility to fabricate CIS PV devices was established that includes migration-enhanced epitaxy (MEE) for deposition of CIS, a rapid thermal processing furnace for absorber film formation, sputtering of ZnO, CBD or MOCVD of CdS, metallization, and pattern definition.« less

Dynamics of Compressible Convection and Thermochemical Mantle Convection

NASA Astrophysics Data System (ADS)

Liu, Xi

The Earth's long-wavelength geoid anomalies have long been used to constrain the dynamics and viscosity structure of the mantle in an isochemical, whole-mantle convection model. However, there is strong evidence that the seismically observed large low shear velocity provinces (LLSVPs) in the lowermost mantle are chemically distinct and denser than the ambient mantle. In this thesis, I investigated how chemically distinct and dense piles influence the geoid. I formulated dynamically self-consistent 3D spherical convection models with realistic mantle viscosity structure which reproduce Earth's dominantly spherical harmonic degree-2 convection. The models revealed a compensation effect of the chemically dense LLSVPs. Next, I formulated instantaneous flow models based on seismic tomography to compute the geoid and constrain mantle viscosity assuming thermochemical convection with the compensation effect. Thermochemical models reconcile the geoid observations. The viscosity structure inverted for thermochemical models is nearly identical to that of whole-mantle models, and both prefer weak transition zone. Our results have implications for mineral physics, seismic tomographic studies, and mantle convection modelling. Another part of this thesis describes analyses of the influence of mantle compressibility on thermal convection in an isoviscous and compressible fluid with infinite Prandtl number. A new formulation of the propagator matrix method is implemented to compute the critical Rayleigh number and the corresponding eigenfunctions for compressible convection. Heat flux and thermal boundary layer properties are quantified in numerical models and scaling laws are developed.

Solar thermochemical splitting of water to generate hydrogen

PubMed Central

Rao, C. N. R.; Dey, Sunita

2017-01-01

Solar photochemical means of splitting water (artificial photosynthesis) to generate hydrogen is emerging as a viable process. The solar thermochemical route also promises to be an attractive means of achieving this objective. In this paper we present different types of thermochemical cycles that one can use for the purpose. These include the low-temperature multistep process as well as the high-temperature two-step process. It is noteworthy that the multistep process based on the Mn(II)/Mn(III) oxide system can be carried out at 700 °C or 750 °C. The two-step process has been achieved at 1,300 °C/900 °C by using yttrium-based rare earth manganites. It seems possible to render this high-temperature process as an isothermal process. Thermodynamics and kinetics of H2O splitting are largely controlled by the inherent redox properties of the materials. Interestingly, under the conditions of H2O splitting in the high-temperature process CO2 can also be decomposed to CO, providing a feasible method for generating the industrially important syngas (CO+H2). Although carbonate formation can be addressed as a hurdle during CO2 splitting, the problem can be avoided by a suitable choice of experimental conditions. The choice of the solar reactor holds the key for the commercialization of thermochemical fuel production. PMID:28522461

Computational Modeling as a Design Tool in Microelectronics Manufacturing

NASA Technical Reports Server (NTRS)

Meyyappan, Meyya; Arnold, James O. (Technical Monitor)

1997-01-01

Plans to introduce pilot lines or fabs for 300 mm processing are in progress. The IC technology is simultaneously moving towards 0.25/0.18 micron. The convergence of these two trends places unprecedented stringent demands on processes and equipments. More than ever, computational modeling is called upon to play a complementary role in equipment and process design. The pace in hardware/process development needs a matching pace in software development: an aggressive move towards developing "virtual reactors" is desirable and essential to reduce design cycle and costs. This goal has three elements: reactor scale model, feature level model, and database of physical/chemical properties. With these elements coupled, the complete model should function as a design aid in a CAD environment. This talk would aim at the description of various elements. At the reactor level, continuum, DSMC(or particle) and hybrid models will be discussed and compared using examples of plasma and thermal process simulations. In microtopography evolution, approaches such as level set methods compete with conventional geometric models. Regardless of the approach, the reliance on empricism is to be eliminated through coupling to reactor model and computational surface science. This coupling poses challenging issues of orders of magnitude variation in length and time scales. Finally, database development has fallen behind; current situation is rapidly aggravated by the ever newer chemistries emerging to meet process metrics. The virtual reactor would be a useless concept without an accompanying reliable database that consists of: thermal reaction pathways and rate constants, electron-molecule cross sections, thermochemical properties, transport properties, and finally, surface data on the interaction of radicals, atoms and ions with various surfaces. Large scale computational chemistry efforts are critical as experiments alone cannot meet database needs due to the difficulties associated with such controlled experiments and costs.

Experimental and theoretical investigation of the elastic moduli of silicate glasses and crystals

NASA Astrophysics Data System (ADS)

Philipps, Katharina; Stoffel, Ralf Peter; Dronskowski, Richard; Conradt, Reinhard

2017-02-01

A combined quantum-mechanical and thermodynamic approach to the mechanical properties of multicomponent silicate glasses is presented. Quantum chemical calculations based on density-functional theory (DFT) on various silicate systems were performed to explore the crystalline polymorphs existing for a given chemical composition. These calculations reproduced the properties of known polymorphs even in systems with extensive polymorphism, like MgSiO3. Properties resting on the atomic and electronic structure, i.e., molar volumes (densities) and bulk moduli were predicted correctly. The theoretical data (molar equilibrium volumes, bulk moduli) were then used to complement the available experimental data. In a phenomenological evaluation, experimental data of bulk moduli, a macroscopic property resting on phononic structure, were found to linearly scale with the ratios of atomic space demand to actual molar volume in a universal way. Silicates ranging from high-pressure polymorphs to glasses were represented by a single master line. This suggests that above the Debye limit (in practice: above room temperature), the elastic waves probe the short range order coordination polyhedra and their next-neighbor linkage only, while the presence or absence of an extended translational symmetry is irrelevant. As a result, glasses can be treated - with respect to the properties investigated - as commensurable members of polymorphic series. Binary glasses fit the very same line as their one-component end-members, again both in the crystalline and glassy state. Finally, it is shown that the macroscopic properties of multicomponent glasses also are linear superpositions of the properties of their constitutional phases (as determined from phase diagrams or by thermochemical calculations) taken in their respective glassy states. This is verified experimentally for heat capacities and Young’s moduli of industrial glass compositions. It can be concluded, that the combined quantum mechanical and thermochemical approach is a truly quantitative approach for the design of glasses with desired mechanical properties, e.g., for the development of high-modulus glasses.

Thermochemical Assessment of Oxygen Gettering by SiC or ZrC in PuO2-x TRISO Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Besmann, Theodore M

2010-01-01

Particulate nuclear fuel in a modular helium reactor is being considered for the consumption of excess plutonium and related transuranics. In particular, efforts to largely consume transuranics in a single-pass will require the fuel to undergo very high burnup. This deep burn concept will thus make the proposed plutonia TRISO fuel particularly likely to suffer kernel migration where carbon in the buffer layer and inner pyrolytic carbon layer is transported from the high temperature side of the particle to the low temperature side. This phenomenon is oberved to cause particle failure and therefore must be mitigated. The addition of SiCmore » or ZrC in the oxide kernel or in a layer in communication with the kernel will lower the oxygen potential and therefore prevent kernel migration, and this has been demonstrated with SiC. In this work a thermochemical analysis was performed to predict oxygen potential behavior in the plutonia TRISO fuel to burnups of 50% FIMA with and without the presence of oxygen gettering SiC and ZrC. Kernel migration is believed to be controlled by CO gas transporting carbon from the hot side to the cool side, and CO pressure is governed by the oxygen potential in the presence of carbon. The gettering phases significantly reduce the oxygen potential and thus CO pressure in an otherwise PuO2-x kernel, and prevent kernel migration by limiting CO gas diffusion through the buffer layer. The reduction in CO pressure can also reduce the peak pressure within the particles by ~50%, thus reducing the likelihood of pressure-induced particle failure. A model for kernel migration was used to semi-quantitatively assess the effect of controlling oxygen potential with SiC or ZrC and did demonstrated the dramatic effect of the addition of these phases on carbon transport.« less

Compositional and stable carbon isotopic fractionation during non-autocatalytic thermochemical sulfate reduction by gaseous hydrocarbons

USGS Publications Warehouse

Xia, Xinyu; Ellis, Geoffrey S.; Ma, Qisheng; Tang, Yongchun

2014-01-01

The possibility of autocatalysis during thermochemical sulfate reduction (TSR) by gaseous hydrocarbons was investigated by examination of previously reported laboratory and field data. This reaction was found to be a kinetically controlled non-autocatalytic process, and the apparent lack of autocatalysis is thought to be due to the absence of the required intermediate species. Kinetic parameters for chemical and carbon isotopic fractionations of gaseous hydrocarbons affected by TSR were calculated and found to be consistent with experimentally derived values for TSR involving long-chain hydrocarbons. Model predictions based on these kinetic values indicate that TSR by gaseous hydrocarbon requires high-temperature conditions. The oxidation of C2–5 hydrocarbons by sulfate reduction is accompanied by carbon isotopic fractionation with the residual C2–5 hydrocarbons becoming more enriched in 13C. Kinetic parameters were calculated for the stable carbon isotopic fractionation of gaseous hydrocarbons that have experienced TSR. Model predictions based on these kinetics indicate that it may be difficult to distinguish the effects of TSR from those of thermal maturation at lower levels of hydrocarbon oxidation; however, unusually heavy δ13C2+ values (>−10‰) can be diagnostic of high levels of conversion (>50%). Stoichiometric and stable carbon isotopic data show that methane is stable under the investigated reaction conditions and is likely a product of TSR by other gaseous hydrocarbons rather than a significant reactant. These results indicate that the overall TSR reaction mechanism for oxidation of organic substrates containing long-chain hydrocarbons involves three distinct phases as follows: (1) an initial slow and non-autocatalytic stage characterized by the reduction of reactive sulfate by long-chain saturated hydrocarbons; (2) a second autocatalytic reaction phase dominated by reactions involving reduced sulfur species and partially oxidized hydrocarbons; (3) and a final, or late-stage, TSR reaction in which hydrocarbon oxidation continues at a slower rate via the non-autocatalytic reduction of sulfate by gaseous hydrocarbons.

Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species.

PubMed

Klippenstein, Stephen J; Harding, Lawrence B; Ruscic, Branko

2017-09-07

The fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds to essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H 2 , CH 4 , H 2 O, and NH 3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zero-point energy, core-valence, relativistic, and diagonal Born-Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0-1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.

Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klippenstein, Stephen J.; Harding, Lawrence B.; Ruscic, Branko

Here, the fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds tomore » essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H 2, CH 4, H 2O, and NH 3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zeropoint energy, core–valence, relativistic, and diagonal Born–Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0–1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.« less

Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species

DOE PAGES

Klippenstein, Stephen J.; Harding, Lawrence B.; Ruscic, Branko

2017-07-31

Here, the fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds tomore » essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H 2, CH 4, H 2O, and NH 3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zeropoint energy, core–valence, relativistic, and diagonal Born–Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0–1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.« less

Solar thermochemical reactor, methods of manufacture and use thereof and thermogravimeter

DOEpatents

Klausner, James F.; Petrasch, Joerg

2017-06-06

A solar thermochemical reactor contains an outer member, an inner member disposed within an outer member, wherein the outer member surrounds the inner member and wherein the outer member has an aperture for receiving solar radiation. An inner cavity and an outer cavity are formed by the inner member and outer member and a reactive material that is capable of being magnetically stabilized is disposed in the outer cavity between the inner member and the outer member.

Synfuels from fusion: using the tandem mirror reactor and a thermochemical cycle to produce hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Werner, R.W.

1982-11-01

This study is concerned with the following area: (1) the tandem mirror reactor and its physics; (2) energy balance; (3) the lithium oxide canister blanket system; (4) high-temperature blanket; (5) energy transport system-reactor to process; (6) thermochemical hydrogen processes; (7) interfacing the GA cycle; (8) matching power and temperature demands; (9) preliminary cost estimates; (10) synfuels beyond hydrogen; and (11) thermodynamics of the H/sub 2/SO/sub 4/-H/sub 2/O system. (MOW)

Nonequilibrium thermo-chemical calculations using a diagonal implicit scheme

NASA Technical Reports Server (NTRS)

Imlay, Scott T.; Roberts, Donald W.; Soetrisno, Moeljo; Eberhardt, Scott

1991-01-01

A recently developed computer program for hypersonic vehicle flow analysis is described. The program uses a diagonal implicit algorithm to solve the equations of viscous flow for a gas in thermochemical nonequilibrium. The diagonal scheme eliminates the expense of inverting large block matrices that arise when species conservation equations are introduced. The program uses multiple zones of grids patched together and includes radiation wall and rarefied gas boundary conditions. Solutions are presented for hypersonic flows of air and hydrogen air mixtures.

Biological lignocellulose solubilization: Comparative evaluation of biocatalysts and enhancement via cotreatment

DOE PAGES

Paye, Julie M. D.; Guseva, Anna; Hammer, Sarah K.; ...

2016-01-12

Feedstock recalcitrance is the most important barrier impeding cost-effective production of cellulosic biofuels. Pioneer commercial cellulosic ethanol facilities employ thermochemical pretreatment and addition of fungal cellulase, reflecting the main research emphasis in the field. However, it has been suggested that it may be possible to process cellulosic biomass without thermochemical pretreatment using thermophilic, cellulolytic bacteria. Thus, to further explore this idea, we examine the ability of various biocatalysts to solubilize autoclaved but otherwise unpretreated cellulosic biomass under controlled but not industrial conditions.

High Efficiency Solar Thermochemical Reactor for Hydrogen Production.

DOE Office of Scientific and Technical Information (OSTI.GOV)

McDaniel, Anthony H.

2017-09-30

This research and development project is focused on the advancement of a technology that produces hydrogen at a cost that is competitive with fossil-based fuels for transportation. A twostep, solar-driven WS thermochemical cycle is theoretically capable of achieving an STH conversion ratio that exceeds the DOE target of 26% at a scale large enough to support an industrialized economy [1]. The challenge is to transition this technology from the laboratory to the marketplace and produce hydrogen at a cost that meets or exceeds DOE targets.

Effect of Thermochemical Synthetic Conditions on the Structure and Dielectric Properties of Ga1.9Fe0.1O3 Compounds.

PubMed

Roy, Swadipta; Ramana, C V

2018-02-05

We report on the tunable and controlled dielectric properties of iron (Fe)-doped gallium oxide (Ga 2 O 3 ; Ga 1.9 Fe 0.1 O 3 , referred to as GFO) inorganic compounds. The GFO materials were synthesized using a standard high-temperature, solid-state chemical reaction method by varying the thermochemical processing conditions, namely, different calcination and sintering environments. Structural characterization by X-ray diffraction revealed that GFO compounds crystallize in the β-Ga 2 O 3 phase. The Fe doping has induced slight lattice strain in GFO, which is evident in structural analysis. The effect of the sintering temperature (T sint ), which was varied in the range of 900-1200 °C, is significant, as revealed by electron microscopy analysis. T sint influences the grain size and microstructure evolution, which, in turn, influences the dielectric and electrical properties of GFO compounds. The energy-dispersive X-ray spectrometry and mapping data demonstrate the uniform distribution of the elemental composition over the microstructure. The temperature- and frequency-dependent dielectric measurements indicate the characteristic features that are specifically due to Fe doping in Ga 2 O 3 . The spreading factor and relaxation time, calculated using Cole-Cole plots, are in the ranges of 0.65-0.76 and 10 -4 s, respectively. The results demonstrate that densification and control over the microstructure and properties of GFO can be achieved by optimizing T sint .

Authigenic magnetite formation from goethite and hematite and chemical remanent magnetization acquisition

NASA Astrophysics Data System (ADS)

Till, J. L.; Nowaczyk, N.

2018-06-01

The iron oxyhydroxide goethite is unstable at elevated temperatures and can transform to magnetite under reducing conditions. In this study, various heating experiments were conducted to simulate Fe-mineral transformations during pyrogenic or burial diagenesis alteration in the presence of organic matter. Thermomagnetic measurements, capsule heating experiments and thermochemical remanence acquisition measurements were performed to determine the effect of organic carbon additions on samples containing synthetic microcrystalline goethite, microcrystalline hematite or nanocrystalline goethite. Changes in magnetic properties with heating were monitored to characterize the magnetic behaviour of secondary magnetite and hematite formed during the experiments. Authigenic magnetite formed in all samples containing organic C, while goethite heated without organic C altered to poorly crystalline pseudomorphic hematite. The concentration of organic matter was found to have little influence on the rate or extent of reaction or on the characteristics of the secondary phases. Authigenic magnetite formed from microcrystalline goethite and hematite dominantly behaves as interacting single-domain particles, while nanophase goethite alters to a mixture of small single-domain and superparamagnetic magnetite. Authigenic magnetite and hematite both acquire a stable thermochemical remanence on heating to temperatures between 350 and 600 °C, although the remanence intensity acquired below 500 °C is much weaker than that at higher temperatures. Reductive transformation of fine-grained goethite or hematite is therefore a potential pathway for the production of authigenic magnetite and the generation of stable chemical remanence that may be responsible for remagnetization in organic-matter-bearing sedimentary rocks.

Limestone calcination under calcium-looping conditions for CO2 capture and thermochemical energy storage in the presence of H2O: an in situ XRD analysis.

PubMed

Valverde, Jose Manuel; Medina, Santiago

2017-03-15

This work reports an in situ XRD analysis of whether the calcination/carbonation behavior of natural limestone (CaCO 3 ) is affected by the addition of H 2 O to the calciner at a very low concentration under relevant Calcium-Looping (CaL) conditions for CO 2 capture in coal fired power plants (CFPP) and Thermochemical Energy Storage (TCES) in Concentrated Solar Power plants (CSP). Previous studies have demonstrated that the presence of steam in the calciner at a high concentration yields a significant increase in the reaction rate. However, a further undesired consequence is the serious deterioration of the CaO mechanical strength, which would lead to particle attrition and mass loss in any CaL process based on the use of circulating fluidized beds. The results presented in this manuscript on the time evolution of the wt% and crystallite size of the phases involved in the calcination/carbonation reactions indicate that the calcination rate is still notably increased by the presence of H 2 O at very low concentrations whereas the reactivity toward carbonation and crystal structure of the formed CaO are not essentially affected, which suggests that the CaO mechanical strength is not impaired. Thus, the benefit of using steam for calcination in the CaL process could be still retained while at the same time particle attrition would not be promoted.

Interfacial Reaction Studies Using ONIOM

NASA Technical Reports Server (NTRS)

Cardelino, Beatriz H.

2003-01-01

In this report, we focus on the calculations of the energetics and chemical kinetics of heterogeneous reactions for Organometallic vapor phase epitaxy (OMVPE). The work described in this report builds upon our own previous thermochemical and chemical kinetics studies. The first of these articles refers to the prediction of thermochemical properties, and the latter one deals with the prediction of rate constants for gaseous homolytic dissociation reactions. The calculations of this investigation are at the microscopic level. The systems chosen consisted of a gallium nitride (GaN) substrate, and molecular nitrogen (N2) and ammonia (NH3) as adsorbants. The energetics for the adsorption and the adsorbant dissociation processes were estimated, and reaction rate constants for the dissociation reactions of free and adsorbed molecules were predicted. The energetics for substrate decomposition was also computed. The ONIOM method, implemented in the Gaussian98 program, was used to perform the calculations. This approach has been selected since it allows dividing the system into two layers that can be treated at different levels of accuracy. The atoms of the substrate were modeled using molecular mechanics6 with universal force fields, whereas the adsorbed molecules were approximated using quantum mechanics, based on density functional theory methods with B3LYP functionals and 6-311G(d,p) basis sets. Calculations for the substrate were performed in slabs of several unit cells in each direction. The N2 and NH3 adsorbates were attached to a central location at the Ga-lined surface.

Agro-industrial waste to solid biofuel through hydrothermal carbonization.

PubMed

Basso, Daniele; Patuzzi, Francesco; Castello, Daniele; Baratieri, Marco; Rada, Elena Cristina; Weiss-Hortala, Elsa; Fiori, Luca

2016-01-01

In this paper, the use of grape marc for energy purposes was investigated. Grape marc is a residual lignocellulosic by-product from the winery industry, which is present in every world region where vine-making is addressed. Among the others, hydrothermal carbonization was chosen as a promising alternative thermochemical process, suitable for the treatment of this high moisture substrate. Through a 50 mL experimental apparatus, hydrothermal carbonization tests were performed at several temperatures (namely: 180, 220 and 250 °C) and residence times (1, 3, 8 h). Analyses on both the solid and the gaseous phases obtained downstream of the process were performed. In particular, solid and gas yields versus the process operational conditions were studied and the obtained hydrochar was evaluated in terms of calorific value, elemental analysis, and thermal stability. Data testify that hydrochar form grape marc presents interesting values of HHV (in the range 19.8-24.1 MJ/kg) and physical-chemical characteristics which make hydrochar exploitable as a solid biofuel. In the meanwhile, the amount of gases produced is very small, if compared to other thermochemical processes. This represents an interesting result when considering environmental issues. Statistical analysis of data allows to affirm that, in the chosen range of operational conditions, the process is influenced more by temperature than residence time. These preliminary results support the option of upgrading grape marc toward its energetic valorisation through hydrothermal carbonization. Copyright © 2015 Elsevier Ltd. All rights reserved.

Laboratory simulations of acid-sulfate weathering under volcanic hydrothermal conditions: Implications for early Mars.

PubMed

Marcucci, Emma C; Hynek, Brian M

2014-03-01

We have completed laboratory experiments and thermochemical equilibrium models to investigate secondary mineral formation under conditions akin to volcanic, hydrothermal acid-sulfate weathering systems. Our research used the basaltic mineralogy at Cerro Negro Volcano, Nicaragua, characterized by plagioclase, pyroxene, olivine, and volcanic glass. These individual minerals and whole-rock field samples were reacted in the laboratory with 1 molal sulfuric acid at varying temperatures (65, 150, and 200°C), fluid:rock weight ratios (1:1, 4:1, and 10:1), and durations (1-60 days). Thermochemical equilibrium models were developed using Geochemist's Workbench. To understand the reaction products and fluids, we employed scanning electron microscopy/energy dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma-atomic emission spectroscopy. The results of our experiments and models yielded major alteration minerals that include anhydrite, natroalunite, minor iron oxide, and amorphous Al-Si gel. We found that variations in experimental parameters did not drastically change the suite of minerals produced; instead, abundance, size, and crystallographic shape changed. Our results also suggest that it is essential to separate phases formed during experiments from those formed during fluid evaporation to fully understand the reaction processes. Our laboratory reacted and model predicted products are consistent with the mineralogy observed at places on Mars. However, our results indicate that determination of the formation conditions requires microscopic imagery and regional context, as well as a thorough understanding of contributions from both experiment precipitation and fluid evaporation minerals.

Insecticidal activity of bio-oil from the pyrolysis of straw from Brassica spp.

PubMed

Suqi, Liu; Cáceres, Luis A; Caceres, Luis; Schieck, Katie; McGarvey, Brian D; Booker, Christina J; McGarvey, Brian M; Yeung, Ken K-C; Pariente, Stephane; Briens, Cedric; Berruti, Franco; Scott, Ian M

2014-04-23

Agricultural crop residues can be converted through thermochemical pyrolysis to bio-oil, a sustainable source of biofuel and biochemicals. The pyrolysis bio-oil is known to contain many chemicals, some of which have insecticidal activity and can be a potential source of value-added pest control products. Brassicacae crops, cabbage, broccoli, and mustards, contain glucosinolates and isocyanates, compounds with recognized anti-herbivore activity. In Canada, canola Brassica napus straw is available from over 6 000 000 ha and mustard Brassica carinata and Brassica juncea straw is available from 200 000 ha. The straw can be converted by microbial lignocellulosic enzymes as a substrate for bioethanol production but can also be converted to bio-oil by thermochemical means. Straw from all three species was pyrolyzed, and the insecticidal components in the bio-oil were isolated by bioassay-guided solvent fractionation. Of particular interest were the mustard straw bio-oil aqueous fractions with insecticidal and feeding repellent activity to Colorado potato beetle larvae. Aqueous fractions further analyzed for active compounds were found not to contain many of the undesirable phenol compounds, which were previously found in other bio-oils seen in the dichloromethane (DCM) and ethyl acetate (EA) solvent phases of the present study. Identified within the most polar fractions were hexadecanoic and octadecanoic fatty acids, indicating that separation of these compounds during bio-oil production may provide a source of effective insecticidal compounds.

Laboratory simulations of acid-sulfate weathering under volcanic hydrothermal conditions: Implications for early Mars

PubMed Central

Marcucci, Emma C; Hynek, Brian M

2014-01-01

We have completed laboratory experiments and thermochemical equilibrium models to investigate secondary mineral formation under conditions akin to volcanic, hydrothermal acid-sulfate weathering systems. Our research used the basaltic mineralogy at Cerro Negro Volcano, Nicaragua, characterized by plagioclase, pyroxene, olivine, and volcanic glass. These individual minerals and whole-rock field samples were reacted in the laboratory with 1 molal sulfuric acid at varying temperatures (65, 150, and 200°C), fluid:rock weight ratios (1:1, 4:1, and 10:1), and durations (1–60 days). Thermochemical equilibrium models were developed using Geochemist's Workbench. To understand the reaction products and fluids, we employed scanning electron microscopy/energy dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma-atomic emission spectroscopy. The results of our experiments and models yielded major alteration minerals that include anhydrite, natroalunite, minor iron oxide, and amorphous Al-Si gel. We found that variations in experimental parameters did not drastically change the suite of minerals produced; instead, abundance, size, and crystallographic shape changed. Our results also suggest that it is essential to separate phases formed during experiments from those formed during fluid evaporation to fully understand the reaction processes. Our laboratory reacted and model predicted products are consistent with the mineralogy observed at places on Mars. However, our results indicate that determination of the formation conditions requires microscopic imagery and regional context, as well as a thorough understanding of contributions from both experiment precipitation and fluid evaporation minerals. PMID:26213665

The Forest Inventory and Analysis Database: Database description and users manual version 4.0 for Phase 2

Treesearch

Sharon W. Woudenberg; Barbara L. Conkling; Barbara M. O' Connell; Elizabeth B. LaPoint; Jeffery A. Turner; Karen L. Waddell

2010-01-01

This document is based on previous documentation of the nationally standardized Forest Inventory and Analysis database (Hansen and others 1992; Woudenberg and Farrenkopf 1995; Miles and others 2001). Documentation of the structure of the Forest Inventory and Analysis database (FIADB) for Phase 2 data, as well as codes and definitions, is provided. Examples for...

Equilibrium chemistry down to 100 K. Impact of silicates and phyllosilicates on the carbon to oxygen ratio

NASA Astrophysics Data System (ADS)

Woitke, P.; Helling, Ch.; Hunter, G. H.; Millard, J. D.; Turner, G. E.; Worters, M.; Blecic, J.; Stock, J. W.

2018-06-01

We have introduced a fast and versatile computer code, GGCHEM, to determine the chemical composition of gases in thermo-chemical equilibrium down to 100 K, with or without equilibrium condensation. We have reviewed the data for molecular equilibrium constants, kp(T), from several sources and discussed which functional fits are most suitable for low temperatures. We benchmarked our results against another chemical equilibrium code. We collected Gibbs free energies, ΔGf⊖, for about 200 solid and liquid species from the NIST-JANAF database and the geophysical database SUPCRTBL. We discussed the condensation sequence of the elements with solar abundances in phase equilibrium down to 100 K. Once the major magnesium silicates Mg2SiO4[s] and MgSiO3[s] have formed, the dust to gas mass ratio jumps to a value of about 0.0045 which is significantly lower than the often assumed value of 0.01. Silicate condensation is found to increase the carbon to oxygen ratio (C/O) in the gas from its solar value of 0.55 up to 0.71, and, by the additional intake of water and hydroxyl into the solid matrix, the formation of phyllosilicates at temperatures below 400 K increases the gaseous C/O further to about 0.83. Metallic tungsten (W) is the first condensate found to become thermodynamically stable around 1600-2200 K (depending on pressure), several hundreds of Kelvin before subsequent materials such as zirconium dioxide (ZrO2) or corundum (Al2O3) can condense. We briefly discuss whether tungsten, despite its low abundance of 2 × 10-7 times the silicon abundance, could provide the first seed particles for astrophysical dust formation. GGCHEM code is publicly available at http://https://github.com/pw31/GGchemTable D.1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/614/A1

Additional and revised thermochemical data and computer code for WATEQ2: a computerized chemical model for trace and major element speciation and mineral equilibria of natural waters

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; Jenne, Everett A.

1980-01-01

A computerized chemical model, WATEQ2, has resulted from extensive additions to and revision of the WATEQ model of Truesdell and Jones (Truesdell, A. H., and Jones, B. F., 1974, WATEQ, a computer program for calculating chemical equilibria of natural waters: J. Res. U. S. Geol, Survey, v. 2, p. 233-274). The model building effort has necessitated searching the literature and selecting thermochemical data pertinent to the reactions added to the model. This supplementary report manes available the details of the reactions added to the model together with the selected thermochemical data and their sources. Also listed are details of program operation and a brief description of the output of the model. Appendices-contain a glossary of identifiers used in the PL/1 computer code, the complete PL/1 listing, and sample output from three water analyses used as test cases.

TEA: A Code Calculating Thermochemical Equilibrium Abundances

NASA Astrophysics Data System (ADS)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver

2016-07-01

We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. We tested the code against the method of Burrows & Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows & Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but with higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.

Evaluation energy efficiency of bioconversion knot rejects to ethanol in comparison to other thermochemically pretreated biomass.

PubMed

Wang, Zhaojiang; Qin, Menghua; Zhu, J Y; Tian, Guoyu; Li, Zongquan

2013-02-01

Rejects from sulfite pulp mill that otherwise would be disposed of by incineration were converted to ethanol by a combined physical-biological process that was comprised of physical refining and simultaneous saccharification and fermentation (SSF). The energy efficiency was evaluated with comparison to thermochemically pretreated biomass, such as those pretreated by dilute acid (DA) and sulfite pretreatment to overcome recalcitrance of lignocelluloses (SPORL). It was observed that the structure deconstruction of rejects by physical refining was indispensable to effective bioconversion but more energy intensive than that of thermochemically pretreated biomass. Fortunately, the energy consumption was compensated by the reduced enzyme dosage and the elevated ethanol yield. Furthermore, adjustment of disk-plates gap led to reduction in energy consumption with negligible influence on ethanol yield. In this context, energy efficiency up to 717.7% was achieved for rejects, much higher than that of SPORL sample (283.7%) and DA sample (152.8%). Copyright © 2012 Elsevier Ltd. All rights reserved.

Solar hydrogen production with cerium oxides thermochemical cycle

NASA Astrophysics Data System (ADS)

Binotti, Marco; Di Marcoberardino, Gioele; Biassoni, Mauro; Manzolini, Giampaolo

2017-06-01

This paper discusses the hydrogen production using a solar driven thermochemical cycle. The thermochemical cycle is based on nonstoichiometric cerium oxides redox and the solar concentration system is a solar dish. Detailed optical and redox models were developed to optimize the hydrogen production performance as function of several design parameters (i.e. concentration ratio, reactor pressures and temperatures) The efficiency of the considered technology is compared against two commercially available technologies namely PV + electrolyzer and Dish Stirling + electrolyzer. Results show that solar-to-fuel efficiency of 21.2% can be achieved at design condition assuming a concentration ratio around 5000, reduction and oxidation temperatures of 1500°C and 1275 °C. When moving to annual performance, the annual yield of the considered approach can be as high as 16.7% which is about 43% higher than the best competitive technology. The higher performance implies that higher installation costs around 40% can be accepted for the innovative concept to achieve the same cost of hydrogen.

Thermochemical hydrogen production based on magnetic fusion

NASA Astrophysics Data System (ADS)

Krikorian, O. H.; Brown, L. C.

Preliminary results of a DoE study to define the configuration and production costs for a Tandem Mirror Reactor (TMR) heat source H2 fuel production plant are presented. The TMR uses the D-T reaction to produce thermal energy and dc electrical current, with an Li blanket employed to breed more H-3 for fuel. Various blanket designs are being considered, and the coupling of two of them, a heat pipe blanket to a Joule-boosted decomposer, and a two-temperature zone blanket to a fluidized bed decomposer, are discussed. The thermal energy would be used in an H2SO4 thermochemical cycler to produce the H2. The Joule-boosted decomposer, involving the use of electrically heated commercial SiC furnace elements to transfer process heat to the thermochemical H2 cycle, is found to yield H2 fuel at a cost of $12-14/GJ, which is the projected cost of fossil fuels in 30-40 yr, when the TMR H2 production facility would be operable.

TEA: A CODE CALCULATING THERMOCHEMICAL EQUILIBRIUM ABUNDANCES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver, E-mail: jasmina@physics.ucf.edu

2016-07-01

We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature–pressure pairs. We tested the code against the method of Burrows and Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows and Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but withmore » higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.« less

Potential for thermochemical conversion of biomass residues from the integrated sugar-ethanol process - Fate of ash and ash-forming elements.

PubMed

Dirbeba, Meheretu Jaleta; Brink, Anders; DeMartini, Nikolai; Zevenhoven, Maria; Hupa, Mikko

2017-06-01

In this work, potential for thermochemical conversion of biomass residues from an integrated sugar-ethanol process and the fate of ash and ash-forming elements in the process are presented. Ash, ash-forming elements, and energy flows in the process were determined using mass balances and analyses of eight different biomass samples for ash contents, elemental compositions, and heating values. The results show that the ash content increases from the sugarcane to the final residue, vinasse. The cane straw, which is left in the field, contains one-third of the energy and 25% of the K and Cl while the vinasse contains 2% of the energy and 40% of the K and Cl in the cane. K and Cl in biomass fuels cause corrosion and fouling problems in boilers and gasifiers. Over 85% of these elements in the straw are water soluble indicating that water leaching would improve it for utilization in thermochemical conversion. Copyright © 2017 Elsevier Ltd. All rights reserved.

Exploring a Multiphysics Resolution Approach for Additive Manufacturing

NASA Astrophysics Data System (ADS)

Estupinan Donoso, Alvaro Antonio; Peters, Bernhard

2018-06-01

Metal additive manufacturing (AM) is a fast-evolving technology aiming to efficiently produce complex parts while saving resources. Worldwide, active research is being performed to solve the existing challenges of this growing technique. Constant computational advances have enabled multiscale and multiphysics numerical tools that complement the traditional physical experimentation. In this contribution, an advanced discrete-continuous concept is proposed to address the physical phenomena involved during laser powder bed fusion. The concept treats powder as discrete by the extended discrete element method, which predicts the thermodynamic state and phase change for each particle. The fluid surrounding is solved with multiphase computational fluid dynamics techniques to determine momentum, heat, gas and liquid transfer. Thus, results track the positions and thermochemical history of individual particles in conjunction with the prevailing fluid phases' temperature and composition. It is believed that this methodology can be employed to complement experimental research by analysis of the comprehensive results, which can be extracted from it to enable AM processes optimization for parts qualification.

Equations of state of anhydrous AlF3 and AlI3: Modeling of extreme condition halide chemistry

NASA Astrophysics Data System (ADS)

Stavrou, Elissaios; Zaug, Joseph M.; Bastea, Sorin; Crowhurst, Jonathan C.; Goncharov, Alexander F.; Radousky, Harry B.; Armstrong, Michael R.; Roberts, Sarah K.; Plaue, Jonathan W.

2015-06-01

Pressure dependent angle-dispersive x-ray powder diffraction measurements of alpha-phase aluminum trifluoride (α-AlF3) and separately, aluminum triiodide (AlI3) were conducted using a diamond-anvil cell. Results at 295 K extend to 50 GPa. The equations of state of AlF3 and AlI3 were determined through refinements of collected x-ray diffraction patterns. The respective bulk moduli and corresponding pressure derivatives are reported for multiple orders of the Birch-Murnaghan (B-M), finite-strain (F-f), and higher pressure finite-strain (G-g) EOS analysis models. Aluminum trifluoride exhibits an apparent isostructural phase transition at approximately 12 GPa. Aluminum triiodide also undergoes a second-order atomic rearrangement: applied stress transformed a monoclinically distorted face centered cubic (fcc) structure into a standard fcc structural arrangement of iodine atoms. Results from semi-empirical thermochemical computations of energetic materials formulated with fluorine containing reactants were obtained with the aim of predicting the yield of halogenated products.

Modeling of Fine-Particle Formation in Turbulent Flames

NASA Astrophysics Data System (ADS)

Raman, Venkat; Fox, Rodney O.

2016-01-01

The generation of nanostructured particles in high-temperature flames is important both for the control of emissions from combustion devices and for the synthesis of high-value chemicals for a variety of applications. The physiochemical processes that lead to the production of fine particles in turbulent flames are highly sensitive to the flow physics and, in particular, the history of thermochemical compositions and turbulent features they encounter. Consequently, it is possible to change the characteristic size, structure, composition, and yield of the fine particles by altering the flow configuration. This review describes the complex multiscale interactions among turbulent fluid flow, gas-phase chemical reactions, and solid-phase particle evolution. The focus is on modeling the generation of soot particles, an unwanted pollutant from automobile and aircraft engines, as well as metal oxides, a class of high-value chemicals sought for specialized applications, including emissions control. Issues arising due to the numerical methods used to approximate the particle number density function, the modeling of turbulence-chemistry interactions, and model validation are also discussed.

Effect of hydrothermal liquefaction aqueous phase recycling on bio-crude yields and composition.

PubMed

Biller, Patrick; Madsen, René B; Klemmer, Maika; Becker, Jacob; Iversen, Bo B; Glasius, Marianne

2016-11-01

Hydrothermal liquefaction (HTL) is a promising thermo-chemical processing technology for the production of biofuels but produces large amounts of process water. Therefore recirculation of process water from HTL of dried distillers grains with solubles (DDGS) is investigated. Two sets of recirculation on a continuous reactor system using K2CO3 as catalyst were carried out. Following this, the process water was recirculated in batch experiments for a total of 10 rounds. To assess the effect of alkali catalyst, non-catalytic HTL process water recycling was performed with 9 recycle rounds. Both sets of experiments showed a large increase in bio-crude yields from approximately 35 to 55wt%. The water phase and bio-crude samples from all experiments were analysed via quantitative gas chromatography-mass spectrometry (GC-MS) to investigate their composition and build-up of organic compounds. Overall the results show an increase in HTL conversion efficiency and a lower volume, more concentrated aqueous by-product following recycling. Copyright © 2016 Elsevier Ltd. All rights reserved.

Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

USGS Publications Warehouse

Meshoulam, Alexander; Ellis, Geoffrey S.; Ahmad, Ward Said; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

2016-01-01

Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and provide important mechanistic details about the overall TSR process.

Structure-activity relationships for novel drug precursor N-substituted-6-acylbenzothiazolon derivatives: A theoretical approach

NASA Astrophysics Data System (ADS)

Sıdır, Yadigar Gülseven; Sıdır, İsa

2013-08-01

In this study, the twelve new modeled N-substituted-6-acylbenzothiazolon derivatives having analgesic analog structure have been investigated by quantum chemical methods using a lot of electronic parameters and structure-activity properties; such as molecular polarizability (α), dipole moment (μ), EHOMO, ELUMO, q-, qH+, molecular volume (Vm), ionization potential (IP), electron affinity (EA), electronegativity (χ), molecular hardness (η), molecular softness (S), electrophilic index (ω), heat of formation (HOF), molar refractivity (MR), octanol-water partition coefficient (log P), thermochemical properties (entropy (S), capacity of heat (Cv)); as to investigate activity relationships with molecular structure. The correlations of log P with Vm, MR, ω, EA, EHOMO - ELUMO (ΔE), HOF in aqueous phase, χ, μ, S, η parameters, respectively are obtained, while the linear relation of log P with IP, Cv, HOF in gas phase are not observed. The log P parameter is obtained to be depending on different properties of compounds due to their complexity.

The Corrosion Behavior of Ni3(Si,Nb) Alloys in Boiling 70 wt.% Sulfuric Acid

NASA Astrophysics Data System (ADS)

Hsu, Jen-Hsien; Larson, Christopher M.; Newkirk, Joseph W.; Brow, Richard K.; Zhang, San-Hong

2016-02-01

Corrosion-resistant Ni3(Si,Nb) alloys are promising materials of construction for hydrogen-production systems based on the sulfur-iodine thermochemical cycle. In this work, the corrosion rates of three different Ni3(Si,Nb) alloys were measured in boiling 70 wt.% sulfuric acid and a three-stage corrosion mechanism was identified, based on the composition and morphology of surface scale that developed. The α(Ni) + β(Ni3Si) eutectic constituent of the alloy microstructure was selectively attacked by acid and, when present, is detrimental to corrosion resistance. The G-phase (Ni16Si17Nb6) is more passive than the β-matrix and seems to contribute to a lower steady-state corrosion rate.

An experimental test plan for the characterization of molten salt thermochemical properties in heat transport systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pattrick Calderoni

2010-09-01

Molten salts are considered within the Very High Temperature Reactor program as heat transfer media because of their intrinsically favorable thermo-physical properties at temperatures starting from 300 C and extending up to 1200 C. In this context two main applications of molten salt are considered, both involving fluoride-based materials: as primary coolants for a heterogeneous fuel reactor core and as secondary heat transport medium to a helium power cycle for electricity generation or other processing plants, such as hydrogen production. The reference design concept here considered is the Advanced High Temperature Reactor (AHTR), which is a large passively safe reactormore » that uses solid graphite-matrix coated-particle fuel (similar to that used in gas-cooled reactors) and a molten salt primary and secondary coolant with peak temperatures between 700 and 1000 C, depending upon the application. However, the considerations included in this report apply to any high temperature system employing fluoride salts as heat transfer fluid, including intermediate heat exchangers for gas-cooled reactor concepts and homogenous molten salt concepts, and extending also to fast reactors, accelerator-driven systems and fusion energy systems. The purpose of this report is to identify the technical issues related to the thermo-physical and thermo-chemical properties of the molten salts that would require experimental characterization in order to proceed with a credible design of heat transfer systems and their subsequent safety evaluation and licensing. In particular, the report outlines an experimental R&D test plan that would have to be incorporated as part of the design and operation of an engineering scaled facility aimed at validating molten salt heat transfer components, such as Intermediate Heat Exchangers. This report builds on a previous review of thermo-physical properties and thermo-chemical characteristics of candidate molten salt coolants that was generated as part of the same project [1]. However, this work focuses on two materials: the LiF-BeF2 eutectic (67 and 33 mol%, respectively, also known as flibe) as primary coolant and the LiF-NaF-KF eutectic (46.5, 11.5, and 52 mol%, respectively, also known as flinak) as secondary heat transport fluid. At first common issues are identified, involving the preparation and purification of the materials as well as the development of suitable diagnostics. Than issues specific to each material and its application are considered, with focus on the compatibility with structural materials and the extension of the existing properties database.« less

Mathematical Models of Human Hematopoiesis Following Acute Radiation Exposure

DTIC Science & Technology

2014-05-01

Agency 8725 John J . Kingman Road, MS 6201 Fort Belvoir, VA 22060-6201 T E C H N IC A L R E P O R T DTRA...eV) 1.602 177 × 10–19 joule ( J ) erg 1 × 10–7 joule ( J ) kiloton (kT) (TNT equivalent) 4.184 × 1012 joule ( J ) British thermal unit (Btu...thermochemical) 1.054 350 × 103 joule ( J ) foot-pound-force (ft lbf) 1.355 818 joule ( J ) calorie (cal) (thermochemical) 4.184 joule ( J ) Pressure

Thermochemical energy storage for a lunar base

NASA Technical Reports Server (NTRS)

Perez-Davis, Marla E.; Mckissock, Barbara I.; Difilippo, Frank

1992-01-01

A thermochemical solar energy storage concept involving the reversible reaction CaO + H2O yields Ca(OH)2 is proposed as a power system element for a lunar base. The operation and components of such a system are described. The CaO/H2O system is capable of generating electric power during both the day and night. Mass of the required amount of CaO is neglected since it is obtained from lunar soil. Potential technical problems, such as reactor design and lunar soil processing, are reviewed.

The applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research

NASA Technical Reports Server (NTRS)

Fegley, Bruce, Jr.

1990-01-01

A review of the applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research during the past four decades is presented with an emphasis on chemical equilibrium models and thermochemical kinetics. Several current problems in planetary atmospheres research such as the origin of the atmospheres of the terrestrial planets, atmosphere-surface interactions on Venus and Mars, deep mixing in the atmospheres of the gas giant planets, and the origin of the atmospheres of outer planet satellites all require laboratory data on the kinetics of thermochemical reactions for their solution.

Thermochemical water decomposition processes

NASA Technical Reports Server (NTRS)

Chao, R. E.

1974-01-01

Thermochemical processes which lead to the production of hydrogen and oxygen from water without the consumption of any other material have a number of advantages when compared to other processes such as water electrolysis. It is possible to operate a sequence of chemical steps with net work requirements equal to zero at temperatures well below the temperature required for water dissociation in a single step. Various types of procedures are discussed, giving attention to halide processes, reverse Deacon processes, iron oxide and carbon oxide processes, and metal and alkali metal processes. Economical questions are also considered.

Methane-methanol cycle for the thermochemical production of hydrogen

DOEpatents

Dreyfuss, Robert M.; Hickman, Robert G.

1976-01-01

A thermochemical reaction cycle for the generation of hydrogen from water comprising the following sequence of reactions wherein M represents a metal: CH.sub.4 + H.sub.2 O .fwdarw. CO + 3H.sub.2 (1) co + 2h.sub.2 .fwdarw. ch.sub.3 oh (2) ch.sub.3 oh + so.sub.2 + mo .fwdarw. mso.sub.4 + ch.sub.4 (3) mso.sub.4 .fwdarw. mo + so.sub.2 + 1/2o.sub.2 (4) the net reaction is the decomposition of water into hydrogen and oxygen.

Solar thermochemical processing system and method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wegeng, Robert S.; Humble, Paul H.; Krishnan, Shankar

A solar thermochemical processing system is disclosed. The system includes a first unit operation for receiving concentrated solar energy. Heat from the solar energy is used to drive the first unit operation. The first unit operation also receives a first set of reactants and produces a first set of products. A second unit operation receives the first set of products from the first unit operation and produces a second set of products. A third unit operation receives heat from the second unit operation to produce a portion of the first set of reactants.

Development and testing of a numerical simulation method for thermally nonequilibrium dissociating flows in ANSYS Fluent

NASA Astrophysics Data System (ADS)

Shoev, G. V.; Bondar, Ye. A.; Oblapenko, G. P.; Kustova, E. V.

2016-03-01

Various issues of numerical simulation of supersonic gas flows with allowance for thermochemical nonequilibrium on the basis of fluid dynamic equations in the two-temperature approximation are discussed. The computational tool for modeling flows with thermochemical nonequilibrium is the commercial software package ANSYS Fluent with an additional userdefined open-code module. A comparative analysis of results obtained by various models of vibration-dissociation coupling in binary gas mixtures of nitrogen and oxygen is performed. Results of numerical simulations are compared with available experimental data.

Tuning the Thermochemical Properties of Oxonol Dyes for Digital Versatile Disc Recordable: Reduction of Thermal Interference in High-Speed Recording

NASA Astrophysics Data System (ADS)

Morishima, Shin-Ichi; Wariishi, Koji; Mikoshiba, Hisashi; Inagaki, Yoshio; Shibata, Michihiro; Hashimoto, Hirokazu; Kubo, Hiroshi

To reduce thermal interference between adjacent recording marks on a recordable digital versatile disc, we examined the thermochemical behavior of oxonol dyes for digital versatile disc recordable (DVD-R). We found that oxonol dyes with Meldrum's acid skeleton exhibited an abrupt reduction in weight with increasing temperature without generating excessive heat that is the fundamental cause of thermal interference. DVD-R with the oxonol dyes suppressed fluctuation in the shapes of recorded marks, thereby attaining compatibility with high-speed recording.

An adaptive Bayesian inversion for upper-mantle structure using surface waves and scattered body waves

NASA Astrophysics Data System (ADS)

Eilon, Zachary; Fischer, Karen M.; Dalton, Colleen A.

2018-07-01

We present a methodology for 1-D imaging of upper-mantle structure using a Bayesian approach that incorporates a novel combination of seismic data types and an adaptive parametrization based on piecewise discontinuous splines. Our inversion algorithm lays the groundwork for improved seismic velocity models of the lithosphere and asthenosphere by harnessing the recent expansion of large seismic arrays and computational power alongside sophisticated data analysis. Careful processing of P- and S-wave arrivals isolates converted phases generated at velocity gradients between the mid-crust and 300 km depth. This data is allied with ambient noise and earthquake Rayleigh wave phase velocities to obtain detailed VS and VP velocity models. Synthetic tests demonstrate that converted phases are necessary to accurately constrain velocity gradients, and S-p phases are particularly important for resolving mantle structure, while surface waves are necessary for capturing absolute velocities. We apply the method to several stations in the northwest and north-central United States, finding that the imaged structure improves upon existing models by sharpening the vertical resolution of absolute velocity profiles, offering robust uncertainty estimates, and revealing mid-lithospheric velocity gradients indicative of thermochemical cratonic layering. This flexible method holds promise for increasingly detailed understanding of the upper mantle.

An adaptive Bayesian inversion for upper mantle structure using surface waves and scattered body waves

NASA Astrophysics Data System (ADS)

Eilon, Zachary; Fischer, Karen M.; Dalton, Colleen A.

2018-04-01

We present a methodology for 1-D imaging of upper mantle structure using a Bayesian approach that incorporates a novel combination of seismic data types and an adaptive parameterisation based on piecewise discontinuous splines. Our inversion algorithm lays the groundwork for improved seismic velocity models of the lithosphere and asthenosphere by harnessing the recent expansion of large seismic arrays and computational power alongside sophisticated data analysis. Careful processing of P- and S-wave arrivals isolates converted phases generated at velocity gradients between the mid-crust and 300 km depth. This data is allied with ambient noise and earthquake Rayleigh wave phase velocities to obtain detailed VS and VP velocity models. Synthetic tests demonstrate that converted phases are necessary to accurately constrain velocity gradients, and S-p phases are particularly important for resolving mantle structure, while surface waves are necessary for capturing absolute velocities. We apply the method to several stations in the northwest and north-central United States, finding that the imaged structure improves upon existing models by sharpening the vertical resolution of absolute velocity profiles, offering robust uncertainty estimates, and revealing mid-lithospheric velocity gradients indicative of thermochemical cratonic layering. This flexible method holds promise for increasingly detailed understanding of the upper mantle.

Optimization of the thermodynamic properties and phase diagrams of P2O5-containing systems

NASA Astrophysics Data System (ADS)

Hudon, Pierre; Jung, In-Ho

2014-05-01

P2O5 is an important oxide component in the late stage products of numerous igneous rocks such as granites and pegmatites. Typically, P2O5 combines with CaO and crystallizes in the form of apatite, while in volatile-free conditions, Ca-whitlockite is formed. In spite of their interest, the thermodynamic properties and phase diagrams of P2O5-containg systems are not well known yet. In the case of the pure P2O5 for example, no experimental thermodynamic data are available for the liquid and the O and O' solid phases. As a result, we re-evaluated all the thermodynamic and phase diagram data of the P2O5 unary system [1]. Optimization of the thermodynamic properties and phase diagrams of the binary P2O5 systems was then performed including the Li2O-, Na2O-, MgO-, CaO-, BaO-, MnO-, FeO-, Fe2O3-, ZnO-, Al2O3-, and SiO2-P2O5 [2] systems. All available thermodynamic and phase equilibrium data were simultaneously reproduced in order to obtain a set of model equations for the Gibbs energies of all phases as functions of temperature and composition. In particular, the Gibbs energy of the liquid solution was described using the Modified Quasichemical Model [3-5] implemented in the FactSage software [6]. Thermodynamic modeling of the Li2O-Na2O-K2O-MgO-CaO-FeO-Fe2O3-Al2O3-SiO2 system, which include many granite-forming minerals such as nepheline, leucite, pyroxene, melilite, feldspar and spinel is currently in progress. [1] Jung, I.-H., Hudon, P. (2012) Thermodynamic assessment of P2O5. J. Am. Ceram. Soc., 95 (11), 3665-3672. [2] Rahman, M., Hudon, P. and Jung, I.-H. (2013) A coupled experimental study and thermodynamic modeling of the SiO2-P2O5 system. Metall. Mater. Trans. B, 44 (4), 837-852. [3] Pelton, A.D. and Blander, M. (1984) Computer-assisted analysis of the thermodynamic properties and phase diagrams of slags. Proc. AIME Symp. Metall. Slags Fluxes, TMS-AIME, 281-294. [4] Pelton, A.D. and Blander, M. (1986) Thermodynamic analysis of ordered liquid solutions by a modified quasichemical approach application to silicate slags. Metall. Trans. B, 17, 805-815. [5] A.D. Pelton, S.A. Decterov, G. Eriksson, C. Robelin and Y. Dessureault (2000) The modified quasichemical model - I Binary solutions. Metall. Mater. Trans. B, 31, 651-660. [6] C.W. Bale, P. Chartrand, S.A. Decterov, G. Eriksson, K. Hack, R. Ben Mahfoud, J. Melançon, A.D. Pelton and S. Petersen. (2002) FactSage Thermochemical Software and Databases. Calphad, 26, 189-228.

The Forest Inventory and Analysis Database Version 4.0: Database Description and Users Manual for Phase 3

Treesearch

Christopher W. Woodall; Barbara L. Conkling; Michael C. Amacher; John W. Coulston; Sarah Jovan; Charles H. Perry; Beth Schulz; Gretchen C. Smith; Susan Will Wolf

2010-01-01

Describes the structure of the Forest Inventory and Analysis Database (FIADB) 4.0 for phase 3 indicators. The FIADB structure provides a consistent framework for storing forest health monitoring data across all ownerships for the entire United States. These data are available to the public.

Modeling of Blast Furnace with Layered Cohesive Zone

NASA Astrophysics Data System (ADS)

Dong, X. F.; Yu, A. B.; Chew, S. J.; Zulli, P.

2010-04-01

An ironmaking blast furnace (BF) is a moving bed reactor involving counter-, co-, and cross-current flows of gas, powder, liquids, and solids, coupled with heat exchange and chemical reactions. The behavior of multiple phases directly affects the stability and productivity of the furnace. In the present study, a mathematical model is proposed to describe the behavior of fluid flow, heat and mass transfer, as well as chemical reactions in a BF, in which gas, solid, and liquid phases affect each other through interaction forces, and their flows are competing for the space available. Process variables that characterize the internal furnace state, such as reduction degree, reducing gas and burden concentrations, as well as gas and condensed phase temperatures, have been described quantitatively. In particular, different treatments of the cohesive zone (CZ), i.e., layered, isotropic, and anisotropic nonlayered, are discussed, and their influence on simulation results is compared. The results show that predicted fluid flow and thermochemical phenomena within and around the CZ and in the lower part of the BF are different for different treatments. The layered CZ treatment corresponds to the layered charging of burden and naturally can predict the CZ as a gas distributor and liquid generator.

A thermodynamic description for water, hydrogen fluoride and hydrogen dissolutions in cryolite-base molten salts.

PubMed

Wang, Kun; Chartrand, Patrice

2018-06-15

This paper presents a quantitative thermodynamic description for water, hydrogen fluoride and hydrogen dissolutions in cryolite-base molten salts, which is of technological importance to the Hall-Héroult electrolytic aluminum extraction cell. The Modified Quasichemical Model in the Quadruplet Approximation (MQMQA), as used to treat a large variety of molten salt systems, was adopted to thermodynamically describe the present liquid phase; all solid solutions were modeled using the Compound Energy Formalism (CEF); the gas phase was thermodynamically treated as an ideal mixture of all possible species. The model parameters were mainly obtained by critical evaluations and optimizations of thermodynamic and phase equilibrium data available from relative experimental measurements and theoretical predictions (first-principles calculations and empirical estimations) for the lower-order subsystems. These optimized model parameters were thereafter merged within the Kohler/Toop interpolation scheme, facilitating the prediction of gas solubility (H2O, HF and H2) in multicomponent cryolite-base molten salts using the FactSage thermochemical software. Several interesting diagrams were finally obtained in order to provide useful information for the industrial partners dedicated to the Hall-Héroult electrolytic aluminum production or other molten-salt technologies (the purification process and electroslag refining).

Laser beam heat method reported

NASA Astrophysics Data System (ADS)

Tsuchiya, Hachiro; Goto, Hidekazu

1988-07-01

An outline of research involving the processing method utilizing laser-induced thermochemistry was presented, with the CO2 laser processing of ceramics in CF4 gas used as a practical processing example. It has become clear that it will be possible to conduct laser proccessing of ceramics with high efficiency and high precision by utilizing the thermochemical processes, but it is not believed that the present method is the best one and it is not clear that it can be applied to commercial processing. It is thought that the processing characteristics of this method will be greatly changed by the combination of the atmospheric gas and the material, and it is important to conduct tests on various combinations. However, it is believed that the improvement and development will become possible by theoretically confirming the basic process of the processing, especially of the the thermochemical process between the solid surface and the atmospheric gas molecule. Actually, it is believed that the thermochemical process on the solid surface is quite complicated. For example, it was confirmed that when thermochemical processing the Si monocrystal in the CF4 gas, the processing speed would change by at least 10 times through changing the gas pressure and the mixing O2 gas density. However, conversely speaking, it is believed that the fact that this method is complicated, with many unexplained points and room for research, conceals the possibility of its being applied to various fields, and also, in this sense, the quantitative confirmation of its basic process in an important problem to be solved in the future.

Copper(II)-mediated thermolysis of alginates: a model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae

PubMed Central

Rowbotham, J. S.; Dyer, P. W.; Greenwell, H. C.; Selby, D.; Theodorou, M. K.

2013-01-01

Thermochemical processing methods such as pyrolysis are of growing interest as a means of converting biomass into fuels and commodity chemicals in a sustainable manner. Macroalgae, or seaweed, represent a novel class of feedstock for pyrolysis that, owing to the nature of the environments in which they grow coupled with their biochemistry, naturally possess high metal contents. Although the impact of metals upon the pyrolysis of terrestrial biomass is well documented, their influence on the thermochemical conversion of marine-derived feeds is largely unknown. Furthermore, these effects are inherently difficult to study, owing to the heterogeneous character of natural seaweed samples. The work described in this paper uses copper(II) alginate, together with alginic acid and sodium alginate as model compounds for exploring the effects of metals upon macroalgae thermolysis. A thermogravimetric analysis–Fourier transform infrared spectroscopic study revealed that, unusually, Cu2+ ions promote the onset of pyrolysis in the alginate polymer, with copper(II) alginate initiating rapid devolatilization at 143°C, 14°C lower than alginic acid and 61°C below the equivalent point for sodium alginate. Moreover, this effect was mirrored in a sample of wild Laminaria digitata that had been doped with Cu2+ ions prior to pyrolysis, thus validating the use of alginates as model compounds with which to study the thermolysis of macroalgae. These observations indicate the varying impact of different metal species on thermochemical behaviour of seaweeds and offer an insight into the pyrolysis of brown macroalgae used in phytoremediation of metal-containing waste streams. PMID:24427515

PHASE I MATERIALS PROPERTY DATABASE DEVELOPMENT FOR ASME CODES AND STANDARDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ren, Weiju; Lin, Lianshan

2013-01-01

To support the ASME Boiler and Pressure Vessel Codes and Standard (BPVC) in modern information era, development of a web-based materials property database is initiated under the supervision of ASME Committee on Materials. To achieve efficiency, the project heavily draws upon experience from development of the Gen IV Materials Handbook and the Nuclear System Materials Handbook. The effort is divided into two phases. Phase I is planned to deliver a materials data file warehouse that offers a depository for various files containing raw data and background information, and Phase II will provide a relational digital database that provides advanced featuresmore » facilitating digital data processing and management. Population of the database will start with materials property data for nuclear applications and expand to data covering the entire ASME Code and Standards including the piping codes as the database structure is continuously optimized. The ultimate goal of the effort is to establish a sound cyber infrastructure that support ASME Codes and Standards development and maintenance.« less

The thermochemical structure and evolution of Earth's mantle: constraints and numerical models.

PubMed

Tackley, Paul J; Xie, Shunxing

2002-11-15

Geochemical observations place several constraints on geophysical processes in the mantle, including a requirement to maintain several distinct reservoirs. Geophysical constraints limit plausible physical locations of these reservoirs to a thin basal layer, isolated deep 'piles' of material under large-scale mantle upwellings, high-viscosity blobs/plums or thin strips throughout the mantle, or some combination of these. A numerical model capable of simulating the thermochemical evolution of the mantle is introduced. Preliminary simulations are more differentiated than Earth but display some of the proposed thermochemical processes, including the generation of a high-mu mantle reservoir by recycling of crust, and the generation of a high-(3)He/(4)He reservoir by recycling of residuum, although the resulting high-(3)He/(4)He material tends to aggregate near the top, where mid-ocean-ridge melting should sample it. If primitive material exists as a dense basal layer, it must be much denser than subducted crust in order to retain its primitive (e.g. high-(3)He) signature. Much progress is expected in the near future.

Comparison of seven types of thermo-chemical pretreatments on the structural features and anaerobic digestion of sunflower stalks.

PubMed

Monlau, F; Barakat, A; Steyer, J P; Carrere, H

2012-09-01

Sunflower stalks can be used for the production of methane, but their recalcitrant structure requires the use of thermo-chemical pretreatments. Two thermal (55 and 170°C) and five thermo-chemical pretreatments (NaOH, H(2)O(2), Ca(OH)(2), HCl and FeCl(3)) were carried out, followed by anaerobic digestion. The highest methane production (259 ± 6 mL CH(4)g(-1) VS) was achieved after pretreatment at 55°C with 4% NaOH for 24h. Acidic pretreatments at 170°C removed more than 90% of hemicelluloses and uronic acids whereas alkaline and oxidative pretreatments were more effective in dissolving lignin. However, no pretreatment was effective in reducing the crystallinity of cellulose. Methane production rate was positively correlated with the amount of solubilized matter whereas methane potential was negatively correlated with the amount of lignin. Considering that the major challenge is obtaining increased methane potential, alkaline pretreatments can be recommended in order to optimize the anaerobic digestion of lignocellulosic substrates. Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermochemistry and vertical mixing in the tropospheres of Uranus and Neptune: How convection inhibition can affect the derivation of deep oxygen abundances

NASA Astrophysics Data System (ADS)

Cavalié, T.; Venot, O.; Selsis, F.; Hersant, F.; Hartogh, P.; Leconte, J.

2017-07-01

Thermochemical models have been used in the past to constrain the deep oxygen abundance in the gas and ice giant planets from tropospheric CO spectroscopic measurements. Knowing the oxygen abundance of these planets is a key to better understand their formation. These models have widely used dry and/or moist adiabats to extrapolate temperatures from the measured values in the upper troposphere down to the level where the thermochemical equilibrium between H2O and CO is established. The mean molecular mass gradient produced by the condensation of H2O stabilizes the atmosphere against convection and results in a vertical thermal profile and H2O distribution that departs significantly from previous estimates. We revisit O/H estimates using an atmospheric structure that accounts for the inhibition of the convection by condensation. We use a thermochemical network and the latest observations of CO in Uranus and Neptune to calculate the internal oxygen enrichment required to satisfy both these new estimates of the thermal profile and the observations. We also present the current limitations of such modeling.

Biochar potential evaluation of palm oil wastes through slow pyrolysis: Thermochemical characterization and pyrolytic kinetic studies.

PubMed

Lee, Xin Jiat; Lee, Lai Yee; Gan, Suyin; Thangalazhy-Gopakumar, Suchithra; Ng, Hoon Kiat

2017-07-01

This research investigated the potential of palm kernel shell (PKS), empty fruit bunch (EFB) and palm oil sludge (POS), abundantly available agricultural wastes, as feedstock for biochar production by slow pyrolysis (50mLmin -1 N 2 at 500°C). Various characterization tests were performed to establish the thermochemical properties of the feedstocks and obtained biochars. PKS and EFB had higher lignin, volatiles, carbon and HHV, and lower ash than POS. The thermochemical conversion had enhanced the biofuel quality of PKS-char and EFB-char exhibiting increased HHV (26.18-27.50MJkg -1 ) and fixed carbon (53.78-59.92%), and decreased moisture (1.03-2.26%). The kinetics of pyrolysis were evaluated by thermogravimetry at different heating rates (10-40°C). The activation energies determined by Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa models were similar, and comparable with literature data. The findings implied that PKS and EFB are very promising sources for biochars synthesis, and the obtained chars possessed significant biofuel potential. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solar Thermochemical Energy Storage Through Carbonation Cycles of SrCO3/SrO Supported on SrZrO3.

PubMed

Rhodes, Nathan R; Barde, Amey; Randhir, Kelvin; Li, Like; Hahn, David W; Mei, Renwei; Klausner, James F; AuYeung, Nick

2015-11-01

Solar thermochemical energy storage has enormous potential for enabling cost-effective concentrated solar power (CSP). A thermochemical storage system based on a SrO/SrCO3 carbonation cycle offers the ability to store and release high temperature (≈1200 °C) heat. The energy density of SrCO3/SrO systems supported by zirconia-based sintering inhibitors was investigated for 15 cycles of exothermic carbonation at 1150 °C followed by decomposition at 1235 °C. A sample with 40 wt % of SrO supported by yttria-stabilized zirconia (YSZ) shows good energy storage stability at 1450 MJ m(-3) over fifteen cycles at the same cycling temperatures. After further testing over 45 cycles, a decrease in energy storage capacity to 1260 MJ m(-3) is observed during the final cycle. The decrease is due to slowing carbonation kinetics, and the original value of energy density may be obtained by lengthening the carbonation steps. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ability of thermochemical calculation to treat organic peroxides

NASA Astrophysics Data System (ADS)

Osmont, Antoine; Baudin, Gérard; Genetier, Marc

2017-06-01

Since 3 years, the CEA Gramat is developing a new thermochemical code, called SIAME, funded by DGA to help French defense industry at conceiving new explosives compositions. It enables the calculation of CJ detonation and deflagration points and combustion of explosives. The accuracy of the code has been checked on several compositions containing PETN, RDX, HMX, TNT, NTO. The error on the velocity of detonation is 3%. To enlarge the domain of validity of the code, organic peroxides have been considered. It is known that thermochemical simulation is in failure regarding compounds as simple as hydrogen peroxide. The computed velocity of detonation is 5720 m/s when shock planar impact gives 6150 m/s. The same discrepancy is found for TATP, with a calculated value at 5870 m/s when 5290 has been measured. Detonation velocity of TATP has been measured at two different densities. These velocities agree with other published values. A closer look at the enthalpy of formation of TATP has revealed that it comes from an article of 1932. Ab initio computations have given a totally different value, leading to better agreement with experiment.

Uncertainty quantification of crustal scale thermo-chemical properties in Southeast Australia

NASA Astrophysics Data System (ADS)

Mather, B.; Moresi, L. N.; Rayner, P. J.

2017-12-01

The thermo-chemical properties of the crust are essential to understanding the mechanical and thermal state of the lithosphere. The uncertainties associated with these parameters are connected to the available geophysical observations and a priori information to constrain the objective function. Often, it is computationally efficient to reduce the parameter space by mapping large portions of the crust into lithologies that have assumed homogeneity. However, the boundaries of these lithologies are, in themselves, uncertain and should also be included in the inverse problem. We assimilate geological uncertainties from an a priori geological model of Southeast Australia with geophysical uncertainties from S-wave tomography and 174 heat flow observations within an adjoint inversion framework. This reduces the computational cost of inverting high dimensional probability spaces, compared to probabilistic inversion techniques that operate in the `forward' mode, but at the sacrifice of uncertainty and covariance information. We overcome this restriction using a sensitivity analysis, that perturbs our observations and a priori information within their probability distributions, to estimate the posterior uncertainty of thermo-chemical parameters in the crust.

Melting and reactive flow of a volatilized mantle beneath mid-ocean ridges: theory and numerical models

NASA Astrophysics Data System (ADS)

Keller, Tobias; Katz, Richard F.

2015-04-01

Laboratory experiments indicate that even small concentrations volatiles (H2O or CO2) in the upper mantle significantly affect the silicate melting behavior [HK96,DH06]. The presence of volatiles stabilizes volatile-rich melt at high pressure, thus vastly increasing the volume of the upper mantle expected to be partially molten [H10,DH10]. These small-degree melts have important consequences for chemical differentiation and could affect the dynamics of mantle flow. We have developed theory and numerical implementation to simulate thermo-chemically coupled magma/mantle dynamics in terms of a two-phase (rock+melt), three component (dunite+MORB+volatilized MORB) physical model. The fluid dynamics is based on McKenzie's equations [McK84], while the thermo-chemical formulation of the system is represented by a novel disequilibrium multi-component melting model based on thermo-dynamic theory [RBS11]. This physical model is implemented as a parallel, two-dimensional, finite-volume code that leverages tools from the PETSc toolkit. Application of this simulation code to a mid-ocean ridge system suggests that the methodology captures the leading-order features of both hydrated and carbonated mantle melting, including deep, low-degree, volatile-rich melt formation. Melt segregation leads to continuous dynamic thermo-chemical dis-equilibration, while phenomenological reaction rates are applied to continually move the system towards re-equilibration. The simulations will be used first to characterize volatile extraction from the MOR system assuming a chemically homogeneous mantle. Subsequently, simulations will be extended to investigate the consequences of heterogeneity in lithology [KW12] and volatile content. These studies will advance our understanding of the role of volatiles in the dynamic and chemical evolution of the upper mantle. Moreover, they will help to gauge the significance of the coupling between the deep carbon cycle and the ocean/atmosphere system. REFERENCES HK96 Hirth & Kohlstedt (1996), Earth Planet Sci Lett DH06 Dasgupta & Hirschmann (2006), doi:10.1038/nature04612. H10 Hirschmann (2010), doi:10.1016/j.pepi.2009.12.003. DH10 Dasgupta & Hirschmann (2010), doi:10.1016/j.epsl.2010.06.039. McK84 McKenzie (1984), J Pet KW12 Katz & Weatherley (2012), doi: 10.1016/j.epsl.2012.04.042. RBS11 Rudge, Bercovici & Spiegelman (2011), doi: 10.1111/j.1365-246X.2010.04870.x

Life cycle assessment of nuclear-based hydrogen production via thermochemical water splitting using a copper-chlorine (Cu-Cl) cycle

NASA Astrophysics Data System (ADS)

Ozbilen, Ahmet Ziyaettin

The energy carrier hydrogen is expected to solve some energy challenges. Since its oxidation does not emit greenhouse gases (GHGs), its use does not contribute to climate change, provided that it is derived from clean energy sources. Thermochemical water splitting using a Cu-Cl cycle, linked with a nuclear super-critical water cooled reactor (SCWR), which is being considered as a Generation IV nuclear reactor, is a promising option for hydrogen production. In this thesis, a comparative environmental study is reported of the three-, four- and five-step Cu-Cl thermochemical water splitting cycles with various other hydrogen production methods. The investigation uses life cycle assessment (LCA), which is an analytical tool to identify and quantify environmentally critical phases during the life cycle of a system or a product and/or to evaluate and decrease the overall environmental impact of the system or product. The LCA results for the hydrogen production processes indicate that the four-step Cu-Cl cycle has lower environmental impacts than the three- and five-step Cu-Cl cycles due to its lower thermal energy requirement. Parametric studies show that acidification potentials (APs) and global warming potentials (GWPs) for the four-step Cu-Cl cycle can be reduced from 0.0031 to 0.0028 kg SO2-eq and from 0.63 to 0.55 kg CO2-eq, respectively, if the lifetime of the system increases from 10 to 100 years. Moreover, the comparative study shows that the nuclear-based S-I and the four-step Cu-Cl cycles are the most environmentally benign hydrogen production methods in terms of AP and GWP. GWPs of the S-I and the four-step Cu-Cl cycles are 0.412 and 0.559 kg CO2-eq for reference case which has a lifetime of 60 years. Also, the corresponding APs of these cycles are 0.00241 and 0.00284 kg SO2-eq. It is also found that an increase in hydrogen plant efficiency from 0.36 to 0.65 decreases the GWP from 0.902 to 0.412 kg CO 2-eq and the AP from 0.00459 to 0.00209 kg SO2-eq for the four-step Cu-Cl cycle. Keywords: Hydrogen production, nuclear energy, Cu-Cl cycle, environmental impact, LCA.

Chemsheet as a Simulation Platform for Pyrometallurgical Processes

NASA Astrophysics Data System (ADS)

Penttilä, Karri; Salminen, Justin; Tripathi, Nagendra; Koukkari, Pertti

ChemSheet is a thermodynamic multi-phase multi-component simulation software, which is used as an Add-in in Microsoft Excel. In ChemSheet, the unique Constrained Gibbs free energy method can be used to include dynamic constraints and reaction rates of kinetically slow reactions, yet retaining full consistency of the multiphase thermodynamic model. With appropriate data, ChemSheet models can be used to simulate reactors and processes in all fields of thermochemistry. The presentation will cover off-line modeling of Cu-flash smelters and advanced thermochemical simulation coupled with on-line process control of Cu-Ni smelting. The presentation will describe an off-line model of Cu-smelter based on critically assessed properties of the Al-Ca-Cu-Fe-O-S-Si -system (slag, matte and liquid metal) by using the quasichemical model. A four-stage reactor model (shaft, settler, uptake and bath) is used for optimizing process parameters and feed particle distribution. As a second example, an advanced thermochemical model of a Ni-Cu sulphide smelting plant will be given. The on-line model covers the operation of treating Ni-Cu-S concentrate via roasters, electric furnace and converters, producing a high grade Bessemer matte product for further refining. The model integrates the thermochemistry of the roasters and electric furnace, and predicts important process parameters such as degree of sulphur elimination in the fluid-bed roasters, matte grade, iron metallization, slag losses and the iron to silica ratio in the electric furnace slag. Both models can be used to assist process engineers and operators in calculating the addition rates of coke, flux and air for different feed scenarios.

Analysis of medium-BTU gasification condensates, June 1985-June 1986

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elliott, D.C.

1987-05-01

This report provides the final results of chemical and physical analysis of condensates from biomass gasification systems which are part of the US Department of Energy Biomass Thermochemical Conversion Program. The work described in detail in this report involves extensive analysis of condensates from four medium-BTU gasifiers. The analyses include elemental analysis, ash, moisture, heating value, density, specific chemical analysis, ash, moisture, heating value, density, specific chemical analysis (gas chromatography/mass spectrometry, infrared spectrophotometry, Carbon-13 nuclear magnetic resonance spectrometry) and Ames Assay. This work was an extension of a broader study earlier completed of the condensates of all the gasifers andmore » pyrolyzers in the Biomass Thermochemical Conversion Program. The analytical data demonstrates the wide range of chemical composition of the organics recoverd in the condensates and suggests a direct relationship between operating temperature and chemical composition of the condensates. A continuous pathway of thermal degradation of the tar components as a function of temperature is proposed. Variations in the chemical composition of the organic in the tars are reflected in the physical properties of tars and phase stability in relation to water in the condensate. The biological activity appears to be limited to the tars produced at high temperatures as a result of formation of polycyclic aromatic hydrocarbons in high concentrations. Future studies of the time/temperature relationship to tar composition and the effect of processing atmosphere should be undertaken. Further processing of the condensates either as wastewater treatment or upgrading of the organics to useful products is also recommended. 15 refs., 4 figs., 4 tabs.« less

Bioactive macroporous titanium implants highly interconnected.

PubMed

Caparrós, Cristina; Ortiz-Hernandez, Mónica; Molmeneu, Meritxell; Punset, Miguel; Calero, José Antonio; Aparicio, Conrado; Fernández-Fairén, Mariano; Perez, Román; Gil, Francisco Javier

2016-10-01

Intervertebral implants should be designed with low load requirements, high friction coefficient and low elastic modulus in order to avoid the stress shielding effect on bone. Furthermore, the presence of a highly interconnected porous structure allows stimulating bone in-growth and enhancing implant-bone fixation. The aim of this study was to obtain bioactive porous titanium implants with highly interconnected pores with a total porosity of approximately 57 %. Porous Titanium implants were produced by powder sintering route using the space holder technique with a binder phase and were then evaluated in an in vivo study. The size of the interconnection diameter between the macropores was about 210 μm in order to guarantee bone in-growth through osteblastic cell penetration. Surface roughness and mechanical properties were analyzed. Stiffness was reduced as a result of the powder sintering technique which allowed the formation of a porous network. Compression and fatigue tests exhibited suitable properties in order to guarantee a proper compromise between mechanical properties and pore interconnectivity. Bioactivity treatment effect in novel sintered porous titanium materials was studied by thermo-chemical treatments and were compared with the same material that had undergone different bioactive treatments. Bioactive thermo-chemical treatment was confirmed by the presence of sodium titanates on the surface of the implants as well as inside the porous network. Raman spectroscopy results suggested that the identified titanate structures would enhance in vivo apatite formation by promoting ion exchange for the apatite formation process. In vivo results demonstrated that the bioactive titanium achieved over 75 % tissue colonization compared to the 40 % value for the untreated titanium.

Toward Phase IV, Populating the WOVOdat Database

NASA Astrophysics Data System (ADS)

Ratdomopurbo, A.; Newhall, C. G.; Schwandner, F. M.; Selva, J.; Ueda, H.

2009-12-01

One of challenges for volcanologists is the fact that more and more people are likely to live on volcanic slopes. Information about volcanic activity during unrest should be accurate and rapidly distributed. As unrest may lead to eruption, evacuation may be necessary to minimize damage and casualties. The decision to evacuate people is usually based on the interpretation of monitoring data. Over the past several decades, monitoring volcanoes has used more and more sophisticated instruments. A huge volume of data is collected in order to understand the state of activity and behaviour of a volcano. WOVOdat, The World Organization of Volcano Observatories (WOVO) Database of Volcanic Unrest, will provide context within which scientists can interpret the state of their own volcano, during and between crises. After a decision during the 2000 IAVCEI General Assembly to create WOVOdat, development has passed through several phases, from Concept Development (Phase-I in 2000-2002), Database Design (Phase-II, 2003-2006) and Pilot Testing (Phase-III in 2007-2008). For WOVOdat to be operational, there are still two (2) steps to complete, which are: Database Population (Phase-IV) and Enhancement and Maintenance (Phase-V). Since January 2009, the WOVOdat project is hosted by Earth Observatory of Singapore for at least a 5-year period. According to the original planning in 2002, this 5-year period will be used for completing the Phase-IV. As the WOVOdat design is not yet tested for all types of data, 2009 is still reserved for building the back-end relational database management system (RDBMS) of WOVOdat and testing it with more complex data. Fine-tuning of the WOVOdat’s RDBMS design is being done with each new upload of observatory data. The next and main phase of WOVOdat development will be data population, managing data transfer from multiple observatory formats to WOVOdat format. Data population will depend on two important things, the availability of SQL database in volcano observatories and their data sharing policy. Hence, a strong collaboration with every WOVO observatory is important. For some volcanoes where the data are not in an SQL system, the WOVOdat project will help scientists working on the volcano to start building an SQL database.

The modelling routes for the chemical vapour deposition process: application to Si 1- xGe x deposition

NASA Astrophysics Data System (ADS)

Pons, M.; Bernard, C.; Rouch, H.; Madar, R.

1995-10-01

The purpose of this article is to present the modelling routes for the chemical vapour deposition process with a special emphasis on mass transport models with near local thermochemical equilibrium imposed in the gas-phase and at the deposition surface. The theoretical problems arising from the linking of the two selected approaches, thermodynamics and mass transport, are shown and a solution procedure is proposed. As an illustration, selected results of thermodynamic and mass transport analysis and of the coupled approach showed that, for the deposition of Si 1- xGe x solid solution at 1300 K (system SiGeClHAr), the thermodynamic heterogeneous stability of the reactive gases and the thermal diffusion led to the germanium depletion of the deposit.

Thermochemical and Physical Properties of Fluids, Lubricants and Related Materials. Delivery Order 0001 : Improved Methods Development for Determining Thermophysical and Thermochemical Properties of Fluids, Lubricants and Related Materials

DTIC Science & Technology

2008-07-01

PRF-5606H, ...................76 FTM 791C, method 36003) 168 hrs. @ 70ºC using NBR -L (AMS3217/2B Rubber specimens. 42. MLO-06...0275: Rubber Swell Test (MIL-PRF-5606H, .................77 FTM 791C, method 3603) 168 hrs. @ 70ºC using NBR -L...NUMBER MLO-05-421 Rubber Swell Test (MIL-PRF-5606H, FTM 791C, method 36003) 168 Hours @ 70°C (158°F) using NBR -L(AMS 3217/2B) rubber specimens

General Model for Multicomponent Ablation Thermochemistry

NASA Technical Reports Server (NTRS)

Milos, Frank S.; Marschall, Jochen; Rasky, Daniel J. (Technical Monitor)

1994-01-01

A previous paper (AIAA 94-2042) presented equations and numerical procedures for modeling the thermochemical ablation and pyrolysis of thermal protection materials which contain multiple surface species. This work describes modifications and enhancements to the Multicomponent Ablation Thermochemistry (MAT) theory and code for application to the general case which includes surface area constraints, rate limited surface reactions, and non-thermochemical mass loss (failure). Detailed results and comparisons with data are presented for the Shuttle Orbiter reinforced carbon-carbon oxidation protection system which contains a mixture of sodium silicate (Na2SiO3), silica (SiO2), silicon carbide (SiC), and carbon (C).

Corn fiber hulls as a food additive or animal feed

DOEpatents

Abbas, Charles; Beery, Kyle E.; Cecava, Michael J.; Doane, Perry H.

2010-12-21

The present invention provides a novel animal feed or food additive that may be made from thermochemically hydrolyzed, solvent-extracted corn fiber hulls. The animal feed or food additive may be made, for instance, by thermochemically treating corn fiber hulls to hydrolyze and solubilize the hemicellulose and starch present in the corn fiber hulls to oligosaccharides. The residue may be extracted with a solvent to separate the oil from the corn fiber, leaving a solid residue that may be prepared, for instance by aggolmerating, and sold as a food additive or an animal feed.

Predicting radiative heat transfer in thermochemical nonequilibrium flow fields. Theory and user's manual for the LORAN code

NASA Technical Reports Server (NTRS)

Chambers, Lin Hartung

1994-01-01

The theory for radiation emission, absorption, and transfer in a thermochemical nonequilibrium flow is presented. The expressions developed reduce correctly to the limit at equilibrium. To implement the theory in a practical computer code, some approximations are used, particularly the smearing of molecular radiation. Details of these approximations are presented and helpful information is included concerning the use of the computer code. This user's manual should benefit both occasional users of the Langley Optimized Radiative Nonequilibrium (LORAN) code and those who wish to use it to experiment with improved models or properties.

Oxidative vaporization kinetics of chromium (III) oxide in oxygen from 1270 to 1570 K

NASA Technical Reports Server (NTRS)

Stearns, C. A.; Kohl, F. J.; Fryburg, G. C.

1974-01-01

Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at 0.115 torr for temperatures from 1270 to 1570 K. Reaction controlled rates were obtained from experimental rates by a gold calibration technique. These rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporation reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data by using boundary layer theory.

System for thermochemical hydrogen production

DOEpatents

Werner, R.W.; Galloway, T.R.; Krikorian, O.H.

1981-05-22

Method and apparatus are described for joule boosting a SO/sub 3/ decomposer using electrical instead of thermal energy to heat the reactants of the high temperature SO/sub 3/ decomposition step of a thermochemical hydrogen production process driven by a tandem mirror reactor. Joule boosting the decomposer to a sufficiently high temperature from a lower temperature heat source eliminates the need for expensive catalysts and reduces the temperature and consequent materials requirements for the reactor blanket. A particular decomposer design utilizes electrically heated silicon carbide rods, at a temperature of 1250/sup 0/K, to decompose a cross flow of SO/sub 3/ gas.

Generation of metallic plasmon nanostructures in a thin transparent photosensitive copper oxide film by femtosecond thermochemical decomposition

NASA Astrophysics Data System (ADS)

Danilov, P. A.; Zayarny, D. A.; Ionin, A. A.; Kudryashov, S. I.; Litovko, E. P.; Mel'nik, N. N.; Rudenko, A. A.; Saraeva, I. N.; Umanskaya, S. P.; Khmelnitskii, R. A.

2017-09-01

Irradiation of optically transparent copper (I) oxide film covering a glass substrate with a tightly focused femtosecond laser pulses in the pre-ablation regime leads to film reduction to a metallic colloidal state via a single-photon absorption and its subsequent thermochemical decomposition. This effect was demonstrated by the corresponding measurement of the extinction spectrum in visible spectral range. The laser-induced formation of metallic copper nanoparticles in the focal region inside the bulk oxide film allows direct recording of individual thin-film plasmon nanostructures and optical-range metasurfaces.

Study of TLIPSS formation on different metals and alloys and their selective etching

NASA Astrophysics Data System (ADS)

Dostovalov, Alexandr V.; Korolkov, Victor P.; Terentiev, Vadim S.; Okotrub, Konstantin A.; Dultsev, Fedor N.; Nemykin, Anton; Babin, Sergey A.

2017-02-01

Experimental investigation of thermochemical laser-induced periodic surface structures (TLIPSS) formation on metal films (Ti, Cr, Ni, NiCr) at different processing conditions is presented. The hypothesis that the TLIPSS formation depends significantly on parabolic rate constant for oxide thin film growth is discussed. Evidently, low value of this parameter for Ni is the reason of TLIPSS absence on Ni and NiCr film with low Cr content. The effect of simultaneous ablative (with period ≍λ) and thermochemical (with period ≍λ) LIPSS formation was observed. The formation of structures after TLIPSS selective etching was demonstrated.

Thermochemical generation of hydrogen

NASA Technical Reports Server (NTRS)

Lawson, D. D.; Petersen, G. R. (Inventor)

1982-01-01

The direct fluid contact heat exchange with H2SO4 at about 330 C prior to high temperature decomposition at about 830 C in the oxygen release step of several thermochemical cycles for splitting water into hydrogen and oxygen provides higher heat transfer rates, savings in energy and permits use of cast vessels rather than expensive forged alloy indirect heat exchangers. Among several candidate perfluorocarbon liquids tested, only perfluoropropylene oxide polymers having a degree of polymerization from about 10 to 60 were chemically stable, had low miscibility and vapor pressure when tested with sulfuric acid at temperatures from 300 C to 400 C.

Oxidative vaporization kinetics of Cr2O3 in oxygen from 1000 to 1300 C

NASA Technical Reports Server (NTRS)

Stearns, C. A.; Kohl, F. J.; Fryburg, G. C.

1974-01-01

Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at a pressure of 0.115 Torr for temperatures from 1000 to 1300 C. Reaction controlled rates were obtained from experimental rates by a gold calibration technique, and these rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporization reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data using boundary-layer theory.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao, C.N.R., E-mail: cnrrao@jncasr.ac.in; Dey, Sunita

Generation of H{sub 2} and CO by splitting H{sub 2}O and CO{sub 2} respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H{sub 2}O or CO{sub 2} over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H{sub 2}O or CO{sub 2}. While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites ofmore » the type Ln{sub 1−x}A{sub x}Mn{sub 1−y}M{sub y}O{sub 3} (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H{sub 2} and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y{sub 0.5}Sr{sub 0.5}MnO{sub 3} which releases 483 µmol/g of O{sub 2} at 1673 K and produces 757 µmol/g of CO from CO{sub 2} at 1173 K. The production of H{sub 2} from H{sub 2}O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H{sub 2} based on the Mn{sub 3}O{sub 4}/NaMnO{sub 2} cycle briefly. - Graphical abstract: Ln{sub 0.5}A{sub 0.5}Mn{sub 1−x}M{sub x}O{sub 3} (Ln=lanthanide; A=Ca, Sr; M=Al, Ga, Sc, Mg, Cr, Fe, Co) perovskites are employed for the two step thermochemical splitting of CO{sub 2} and H{sub 2}O for the generation of CO and H{sub 2}. - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO{sub 2} and H{sub 2}O. • In Ln{sub 1−x}A{sub x}MnO{sub 3} perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major roles in the thermochemical process. • H{sub 2}O splitting is also achieved by the use of the Mn{sub 3}O{sub 4}-sodium carbonate system. • Thermochemical splitting of CO{sub 2} and H{sub 2}O using perovskite oxides is explained. • Mn based perovskites.« less

The StarLite Project Prototyping Real-Time Software

DTIC Science & Technology

1991-10-01

multiversion data objects using the prototyping environment. Section 5 concludes the paper. 2. Message-Based Simulation When prototyping distributed...phase locking and priority-based synchronization algorithms, and between a multiversion database and its corresponding single-version database, through...its deadline, since the transaction is only aborted in the validation phase. 4.5. A Multiversion Database System To illustrate the effctivcness of the

Thermal decomposition of sewage sludge under N2, CO2 and air: Gas characterization and kinetic analysis.

PubMed

Hernández, Ana Belén; Okonta, Felix; Freeman, Ntuli

2017-07-01

Thermochemical valorisation processes that allow energy to be recovered from sewage sludge, such as pyrolysis and gasification, have demonstrated great potential as convenient alternatives to conventional sewage sludge disposal technologies. Moreover, these processes may benefit from CO 2 recycling. Today, the scaling up of these technologies requires an advanced knowledge of the reactivity of sewage sludge and the characteristics of the products, specific to the thermochemical process. In this study the behaviour of sewage sludge during thermochemical conversion, under different atmospheres (N 2 , CO 2 and air), was studied, using TGA-FTIR, in order to understand the effects of different atmospheric gases on the kinetics of degradation and on the gaseous products. The different steps observed during the solid degradation were related with the production of different gaseous compounds. A higher oxidative degree of the atmosphere surrounding the sample resulted in higher reaction rates and a shift of the degradation mechanisms to lower temperatures, especially for the mechanisms taking place at temperatures above 400 °C. Finally, a multiple first-order reaction model was proposed to compare the kinetic parameters obtained under different atmospheres. Overall, the highest activation energies were obtained for combustion. This work proves that CO 2 , an intermediate oxidative atmosphere between N 2 and air, results in an intermediate behaviour (intermediate peaks in the derivative thermogravimetric curves and intermediate activation energies) during the thermochemical decomposition of sewage sludge. Overall, it can be concluded that the kinetics of these different processes require a different approach for their scaling up and specific consideration of their characteristic reaction temperatures and rates should be evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lifecycle assessment of microalgae to biofuel: Comparison of thermochemical processing pathways

DOE PAGES

Bennion, Edward P.; Ginosar, Daniel M.; Moses, John; ...

2015-01-16

Microalgae are currently being investigated as a renewable transportation fuel feedstock based on various advantages that include high annual yields, utilization of poor quality land, does not compete with food, and can be integrated with various waste streams. This study focuses on directly assessing the impact of two different thermochemical conversion technologies on the microalgae to biofuel process through life cycle assessment. A system boundary of a “well to pump” (WTP) is defined and includes sub-process models of the growth, dewatering, thermochemical bio-oil recovery, bio-oil stabilization, conversion to renewable diesel, and transport to the pump. Models were validated with experimentalmore » and literature data and are representative of an industrial-scale microalgae to biofuel process. Two different thermochemical bio-oil conversion systems are modeled and compared on a systems level, hydrothermal liquefaction (HTL) and pyrolysis. The environmental impact of the two pathways were quantified on the metrics of net energy ratio (NER), defined here as energy consumed over energy produced, and greenhouse gas (GHG) emissions. Results for WTP biofuel production through the HTL pathway were determined to be 1.23 for the NER and GHG emissions of -11.4 g CO 2-eq (MJ renewable diesel) -1. WTP biofuel production through the pyrolysis pathway results in a NER of 2.27 and GHG emissions of 210 g CO2 eq (MJ renewable diesel)-1. The large environmental impact associated with the pyrolysis pathway is attributed to feedstock drying requirements and combustion of co-products to improve system energetics. Discussion focuses on a detailed breakdown of the overall process energetics and GHGs, impact of modeling at laboratory- scale compared to industrial-scale, environmental impact sensitivity to engineering systems input parameters for future focused research and development and a comparison of results to literature.« less

Life cycle assessment of microalgae to biofuel: Thermochemical processing through hydrothermal liquefaction or pyrolysis

NASA Astrophysics Data System (ADS)

Bennion, Edward P.

Microalgae are currently being investigated as a renewable transportation fuel feedstock based on various advantages that include high annual yields, utilization of poor quality land, does not compete with food, and can be integrated with various waste streams. This study focuses on directly assessing the impact of two different thermochemical conversion technologies on the microalgae-to-biofuel process through life cycle assessment. A system boundary of a "well to pump" (WTP) is defined and includes sub-process models of the growth, dewatering, thermochemical bio-oil recovery, bio-oil stabilization, conversion to renewable diesel, and transport to the pump. Models were validated with experimental and literature data and are representative of an industrial-scale microalgae-to-biofuel process. Two different thermochemical bio-oil conversion systems are modeled and compared on a systems level, hydrothermal liquefaction (HTL) and pyrolysis. The environmental impact of the two pathways were quantified on the metrics of net energy ratio (NER), defined here as energy consumed over energy produced, and greenhouse gas (GHG) emissions. Results for WTP biofuel production through the HTL pathway were determined to be 1.23 for the NER and GHG emissions of -11.4 g CO2 eq (MJ renewable diesel)-1. WTP biofuel production through the pyrolysis pathway results in a NER of 2.27 and GHG emissions of 210 g CO2 eq (MJ renewable diesel)-1. The large environmental impact associated with the pyrolysis pathway is attributed to feedstock drying requirements and combustion of co-products to improve system energetics. Discussion focuses on a detailed breakdown of the overall process energetics and GHGs, impact of modeling at laboratory-scale compared to industrial-scale, environmental impact sensitivity to engineering systems input parameters for future focused research and development, and a comparison of results to literature.

Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

NASA Astrophysics Data System (ADS)

Meshoulam, Alexander; Ellis, Geoffrey S.; Said Ahmad, Ward; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

2016-09-01

The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰). Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4 dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and provide important mechanistic details about the overall TSR process.

Thermal storage/discharge performances of Cu-Si alloy for solar thermochemical process

NASA Astrophysics Data System (ADS)

Gokon, Nobuyuki; Yamaguchi, Tomoya; Cho, Hyun-seok; Bellan, Selvan; Hatamachi, Tsuyoshi; Kodama, Tatsuya

2017-06-01

The present authors (Niigata University, Japan) have developed a tubular reactor system using novel "double-walled" reactor/receiver tubes with carbonate molten-salt thermal storage as a phase change material (PCM) for solar reforming of natural gas and with Al-Si alloy thermal storage as a PCM for solar air receiver to produce high-temperature air. For both of the cases, the high heat capacity and large latent heat (heat of solidification) of the PCM phase circumvents the rapid temperature change of the reactor/receiver tubes at high temperatures under variable and uncontinuous characteristics of solar radiation. In this study, we examined cyclic properties of thermal storage/discharge for Cu-Si alloy in air stream in order to evaluate a potentiality of Cu-Si alloy as a PCM thermal storage material. Temperature-increasing performances of Cu-Si alloy are measured during thermal storage (or heat-charge) mode and during cooling (or heat-discharge) mode. A oxidation state of the Cu-Si alloy after the cyclic reaction was evaluated by using electron probe micro analyzer (EPMA).

Anthracene + Pyrene Solid Mixtures: Eutectic and Azeotropic Character

PubMed Central

Rice, James W.; Fu, Jinxia; Suuberg, Eric M.

2010-01-01

To better characterize the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the anthracene (1) + pyrene (2) system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at 404 K at x1 = 0.22. A model based on eutectic formation can be used to predict the enthalpy of fusion associated with the mixture. For mixtures that contain x1 < 0.90, the enthalpy of fusion is near that of pure pyrene. This and X-ray diffraction results indicate that mixtures of anthracene and pyrene have pyrene-like crystal structures and energetics until the composition nears that of pure anthracene. Solid-vapor equilibrium studies show that mixtures of anthracene and pyrene form solid azeotropes at x1 of 0.03 and 0.14. Additionally, mixtures at x1 = 0.99 sublime at the vapor pressure of pure anthracene, suggesting that anthracene behavior is not significantly influenced by x2 = 0.01 in the crystal structure. PMID:21116474

Principles and applications of laser-induced liquid-phase jet-chemical etching

NASA Astrophysics Data System (ADS)

Stephen, Andreas; Metev, Simeon; Vollertsen, Frank

2003-11-01

In this treatment method laser radiation, which is guided from a coaxially expanding liquid jet-stream, locally initiates a thermochemical etching reaction on a metal surface, which leads to selective material removal at high resolution and quality of the treated surface as well as low thermal influence on the workpiece. Electrochemical investigations were performed under focused laser irradiation using a cw-Nd:YAG laser with a maximum power of 15 W and a simultaneous impact of the liquid jet-stream consisting of phosphoric acid with a maximum flow rate of 20 m/s. The time resolved measurements of the electrical potential difference against an electrochemical reference electrode were correlated with the specific processing parameters and corresponding etch rates to identify processing conditions for temporally stable and enhanced chemical etching reactions. Applications of laser-induced liquid-phase jet-chemical etching in the field of sensor technology, micromechanics and micrmoulding technology are presented. This includes the microstructuring of thin film systems, cutting of foils of shape memory alloys or the generation of structures with defined shape in bulk material.

Equations of state of anhydrous AlF 3 and AlI 3 : Modeling of extreme condition halide chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stavrou, Elissaios; Zaug, Joseph M.; Bastea, Sorin

Pressure dependent angle-dispersive x-ray powder diffraction measurements of alpha-phase aluminum trifluoride (α-AlF 3) and separately, aluminum triiodide (AlI 3) were conducted using a diamond-anvil cell. Results at 295 K extend to 50 GPa. The equations of state of AlF 3 and AlI 3 were determined through refinements of collected x-ray diffraction patterns. The respective bulk moduli and corresponding pressure derivatives are reported for multiple orders of the Birch-Murnaghan (B-M), finite-strain (F-f), and higher pressure finite-strain (G-g) EOS analysis models. Aluminum trifluoride exhibits an apparent isostructural phase transition at approximately 12 GPa. Aluminum triiodide also undergoes a second-order atomic rearrangement: appliedmore » stress transformed a monoclinically distorted face centered cubic (fcc) structure into a standard fcc structural arrangement of iodine atoms. In conclusion, results from semi-empirical thermochemical computations of energetic materials formulated with fluorine containing reactants were obtained with the aim of predicting the yield of halogenated products.« less

Equations of state of anhydrous AlF{sub 3} and AlI{sub 3}: Modeling of extreme condition halide chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stavrou, Elissaios, E-mail: stavrou1@llnl.gov; Lawrence Livermore National Laboratory, Physical and Life Sciences Directorate, P.O. Box 808 L-350, Livermore, California 94550; Zaug, Joseph M., E-mail: zaug1@llnl.gov

Pressure dependent angle-dispersive x-ray powder diffraction measurements of alpha-phase aluminum trifluoride (α-AlF{sub 3}) and separately, aluminum triiodide (AlI{sub 3}) were conducted using a diamond-anvil cell. Results at 295 K extend to 50 GPa. The equations of state of AlF{sub 3} and AlI{sub 3} were determined through refinements of collected x-ray diffraction patterns. The respective bulk moduli and corresponding pressure derivatives are reported for multiple orders of the Birch-Murnaghan (B-M), finite-strain (F-f), and higher pressure finite-strain (G-g) EOS analysis models. Aluminum trifluoride exhibits an apparent isostructural phase transition at approximately 12 GPa. Aluminum triiodide also undergoes a second-order atomic rearrangement: appliedmore » stress transformed a monoclinically distorted face centered cubic (fcc) structure into a standard fcc structural arrangement of iodine atoms. Results from semi-empirical thermochemical computations of energetic materials formulated with fluorine containing reactants were obtained with the aim of predicting the yield of halogenated products.« less

Equations of state of anhydrous AlF 3 and AlI 3 : Modeling of extreme condition halide chemistry

DOE PAGES

Stavrou, Elissaios; Zaug, Joseph M.; Bastea, Sorin; ...

2015-06-04

Pressure dependent angle-dispersive x-ray powder diffraction measurements of alpha-phase aluminum trifluoride (α-AlF 3) and separately, aluminum triiodide (AlI 3) were conducted using a diamond-anvil cell. Results at 295 K extend to 50 GPa. The equations of state of AlF 3 and AlI 3 were determined through refinements of collected x-ray diffraction patterns. The respective bulk moduli and corresponding pressure derivatives are reported for multiple orders of the Birch-Murnaghan (B-M), finite-strain (F-f), and higher pressure finite-strain (G-g) EOS analysis models. Aluminum trifluoride exhibits an apparent isostructural phase transition at approximately 12 GPa. Aluminum triiodide also undergoes a second-order atomic rearrangement: appliedmore » stress transformed a monoclinically distorted face centered cubic (fcc) structure into a standard fcc structural arrangement of iodine atoms. In conclusion, results from semi-empirical thermochemical computations of energetic materials formulated with fluorine containing reactants were obtained with the aim of predicting the yield of halogenated products.« less

Thermochemistry of dense hydrous magnesium silicates

NASA Technical Reports Server (NTRS)

Bose, Kunal; Burnley, Pamela; Navrotsky, Alexandra

1994-01-01

Recent experimental investigations under mantle conditions have identified a suite of dense hydrous magnesium silicate (DHMS) phases that could be conduits to transport water to at least the 660 km discontinuity via mature, relatively cold, subducting slabs. Water released from successive dehydration of these phases during subduction could be responsible for deep focus earthquakes, mantle metasomatism and a host of other physico-chemical processes central to our understanding of the earth's deep interior. In order to construct a thermodynamic data base that can delineate and predict the stability ranges for DHMS phases, reliable thermochemical and thermophysical data are required. One of the major obstacles in calorimetric studies of phases synthesized under high pressure conditions has been limitation due to the small (less than 5 mg) sample mass. Our refinement of calorimeter techniques now allow precise determination of enthalpies of solution of less than 5 mg samples of hydrous magnesium silicates. For example, high temperature solution calorimetry of natural talc (Mg(0.99) Fe(0.01)Si4O10(OH)2), periclase (MgO) and quartz (SiO2) yield enthalpies of drop solution at 1044 K to be 592.2 (2.2), 52.01 (0.12) and 45.76 (0.4) kJ/mol respectively. The corresponding enthalpy of formation from oxides at 298 K for talc is minus 5908.2 kJ/mol agreeing within 0.1 percent to literature values.

Absolute Standard Hydrogen Electrode Potential Measured by Reduction of Aqueous Nanodrops in the Gas Phase

PubMed Central

Donald, William A.; Leib, Ryan D.; O'Brien, Jeremy T.; Bush, Matthew F.; Williams, Evan R.

2008-01-01

In solution, half-cell potentials are measured relative to those of other half cells, thereby establishing a ladder of thermochemical values that are referenced to the standard hydrogen electrode (SHE), which is arbitrarily assigned a value of exactly 0 V. Although there has been considerable interest in, and efforts toward, establishing an absolute electrochemical half-cell potential in solution, there is no general consensus regarding the best approach to obtain this value. Here, ion-electron recombination energies resulting from electron capture by gas-phase nanodrops containing individual [M(NH3)6]3+, M = Ru, Co, Os, Cr, and Ir, and Cu2+ ions are obtained from the number of water molecules that are lost from the reduced precursors. These experimental data combined with nanodrop solvation energies estimated from Born theory and solution-phase entropies estimated from limited experimental data provide absolute reduction energies for these redox couples in bulk aqueous solution. A key advantage of this approach is that solvent effects well past two solvent shells, that are difficult to model accurately, are included in these experimental measurements. By evaluating these data relative to known solution-phase reduction potentials, an absolute value for the SHE of 4.2 ± 0.4 V versus a free electron is obtained. Although not achieved here, the uncertainty of this method could potentially be reduced to below 0.1 V, making this an attractive method for establishing an absolute electrochemical scale that bridges solution and gas-phase redox chemistry. PMID:18288835

The equation of state of predominant detonation products

NASA Astrophysics Data System (ADS)

Zaug, Joseph; Crowhurst, Jonathan; Bastea, Sorin; Fried, Laurence

2009-06-01

The equation of state of detonation products, when incorporated into an experimentally grounded thermochemical reaction algorithm can be used to predict the performance of explosives. Here we report laser based Impulsive Stimulated Light Scattering measurements of the speed of sound from a variety of polar and nonpolar detonation product supercritical fluids and mixtures. The speed of sound data are used to improve the exponential-six potentials employed within the Cheetah thermochemical code. We will discuss the improvements made to Cheetah in terms of predictions vs. measured performance data for common polymer blended explosives. Accurately computing the chemistry that occurs from reacted binder materials is one important step forward in our efforts.

Thermochemical study of the system Fe-As-S

USGS Publications Warehouse

Barton, P.B.

1969-01-01

The results of Toulmin and Barton (1964) for the Fe-S system have been combined with a series of new measurements on As-bearing assemblages in the 500??-850??C temperature range to derive data on the free energies, enthalpies, and entropies of formation for arsenopyrite, loellingite, orpiment, realgar, FeAs, and Fe2As. The enthalpies and free energies of formation of orpiment and realgar are only approximately one-half as large as indicated in recent compilations of thermochemical data (Wagman et al., 1965). Data are also presented for the covariation of activity of S2(g) with temperature and composition of the sulfur-arsenic liquid. ?? 1969.

Solar thermochemical process interface study

NASA Technical Reports Server (NTRS)

1984-01-01

The design and analyses of a subsystem of a hydrogen production process are described. The process is based on solar driven thermochemical reactions. The subject subsystem receives sulfuric acid of 60% concentration at 100 C, 1 atm pressure. The acid is further concentrated, vaporized, and decomposed (at a rate of 122 g moles/sec H2SO4) into SO2, O2, and water. The produce stream is cooled to 100 C. Three subsystem options, each being driven by direct solar energy, were designed and analyzed. The results are compared with a prior study case in which solar energy was provided indirectly through a helium loop.

Thermochemical generation of hydrogen and oxygen from water

DOEpatents

Robinson, Paul R.; Bamberger, Carlos E.

1981-01-01

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Thermochemical generation of hydrogen and oxygen from water

DOEpatents

Robinson, Paul R.; Bamberger, Carlos E.

1982-01-01

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Thermo-Chemical Conversion of Microwave Activated Biomass Mixtures

NASA Astrophysics Data System (ADS)

Barmina, I.; Kolmickovs, A.; Valdmanis, R.; Vostrikovs, S.; Zake, M.

2018-05-01

Thermo-chemical conversion of microwave activated wheat straw mixtures with wood or peat pellets is studied experimentally with the aim to provide more effective application of wheat straw for heat energy production. Microwave pre-processing of straw pellets is used to provide a partial decomposition of the main constituents of straw and to activate the thermo-chemical conversion of wheat straw mixtures with wood or peat pellets. The experimental study includes complex measurements of the elemental composition of biomass pellets (wheat straw, wood, peat), DTG analysis of their thermal degradation, FTIR analysis of the composition of combustible volatiles entering the combustor, the flame temperature, the heat output of the device and composition of the products by comparing these characteristics for mixtures with unprocessed and mw pre-treated straw pellets. The results of experimental study confirm that mw pre-processing of straw activates the thermal decomposition of mixtures providing enhanced formation of combustible volatiles. This leads to improvement of the combustion conditions in the flame reaction zone, completing thus the combustion of volatiles, increasing the flame temperature, the heat output from the device, the produced heat energy per mass of burned mixture and decreasing at the same time the mass fraction of unburned volatiles in the products.

Thermal tests of a multi-tubular reactor for hydrogen production by using mixed ferrites thermochemical cycle

NASA Astrophysics Data System (ADS)

Gonzalez-Pardo, Aurelio; Denk, Thorsten; Vidal, Alfonso

2017-06-01

The SolH2 project is an INNPACTO initiative of the Spanish Ministry of Economy and Competitiveness, with the main goal to demonstrate the technological feasibility of solar thermochemical water splitting cycles as one of the most promising options to produce H2 from renewable sources in an emission-free way. A multi-tubular solar reactor was designed and build to evaluate a ferrite thermochemical cycle. At the end of this project, the ownership of this plant was transferred to CIEMAT. This paper reviews some additional tests with this pilot plant performed in the Plataforma Solar de Almería with the main goal to assess the thermal behavior of the reactor, evaluating the evolution of the temperatures inside the cavity and the relation between supplied power and reached temperatures. Previous experience with alumina tubes showed that they are very sensitive to temperature and flux gradients, what leads to elaborate an aiming strategy for the heliostat field to achieve a uniform distribution of the radiation inside the cavity. Additionally, the passing of clouds is a phenomenon that importantly affects all the CSP facilities by reducing their efficiency. The behavior of the reactor under these conditions has been studied.

Characterisation of agroindustrial solid residues as biofuels and potential application in thermochemical processes.

PubMed

Virmond, Elaine; De Sena, Rennio F; Albrecht, Waldir; Althoff, Christine A; Moreira, Regina F P M; José, Humberto J

2012-10-01

In the present work, selected agroindustrial solid residues from Brazil - biosolids from meat processing wastewater treatment and mixture of sawdust with these biosolids; residues from apple and orange juice industries; sugarcane bagasse; açaí kernels (Euterpe oleracea) and rice husk - were characterised as solid fuels and an evaluation of their properties, including proximate and ultimate composition, energy content, thermal behaviour, composition and fusibility of the ashes was performed. The lower heating value of the biomasses ranged from 14.31 MJkg(-1) to 29.14 MJkg(-1), on a dry and ash free basis (daf), all presenting high volatile matter content, varying between 70.57 wt.% and 85.36 wt.% (daf) what improves the thermochemical conversion of the solids. The fouling and slagging tendency of the ashes was predicted based on the fuel ash composition and on the ash fusibility correlations proposed in the literature, which is important to the project and operation of biomass conversion systems. The potential for application of the Brazilian agroindustrial solid residues studied as alternative energy sources in thermochemical processes has been identified, especially concerning direct combustion for steam generation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Giant onsite electronic entropy enhances the performance of ceria for water splitting.

PubMed

Naghavi, S Shahab; Emery, Antoine A; Hansen, Heine A; Zhou, Fei; Ozolins, Vidvuds; Wolverton, Chris

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce 4+ /Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

Improvement of medication event interventions through use of an electronic database.

PubMed

Merandi, Jenna; Morvay, Shelly; Lewe, Dorcas; Stewart, Barb; Catt, Char; Chanthasene, Phillip P; McClead, Richard; Kappeler, Karl; Mirtallo, Jay M

2013-10-01

Patient safety enhancements achieved through the use of an electronic Web-based system for responding to adverse drug events (ADEs) are described. A two-phase initiative was carried out at an academic pediatric hospital to improve processes related to "medication event huddles" (interdisciplinary meetings focused on ADE interventions). Phase 1 of the initiative entailed a review of huddles and interventions over a 16-month baseline period during which multiple databases were used to manage the huddle process and staff interventions were assigned via manually generated e-mail reminders. Phase 1 data collection included ADE details (e.g., medications and staff involved, location and date of event) and the types and frequencies of interventions. Based on the phase 1 analysis, an electronic database was created to eliminate the use of multiple systems for huddle scheduling and documentation and to automatically generate e-mail reminders on assigned interventions. In phase 2 of the initiative, the impact of the database during a 5-month period was evaluated; the primary outcome was the percentage of interventions documented as completed after database implementation. During the postimplementation period, 44.7% of assigned interventions were completed, compared with a completion rate of 21% during the preimplementation period, and interventions documented as incomplete decreased from 77% to 43.7% (p < 0.0001). Process changes, education, and medication order improvements were the most frequently documented categories of interventions. Implementation of a user-friendly electronic database improved intervention completion and documentation after medication event huddles.

Shockwave Processing of Composite Boron and Titanium Nitride Powders

NASA Astrophysics Data System (ADS)

Beason, Matthew T.; Gunduz, I. Emre; Mukasyan, Alexander S.; Son, Steven F.

2015-06-01

Shockwave processing of powders has been shown to initiate reactions between condensed phase reactants. It has been observed that these reactions can occur at very short timescales, resulting in chemical reactions occurring at a high pressure state. These reactions have the potential to produce metastable phases. Kinetic limitations prevent gaseous reactants from being used in this type of synthesis reaction. To overcome this limitation, a solid source of gaseous reactants must be used. An example of this type of reaction is the nitrogen exchange reaction (e.g. B + TiN, B + Si3N4 etc.). In these reactions nitrogen is ``carried'' by a material that can be then reduced by the second reactant. This work explores the possibility of using nitrogen exchange reactions to synthesize the cubic phase of boron nitride (c-BN) through shockwave processing of ball milled mixtures of boron and titanium nitride. The heating from the passage of the shock wave (pore collapse, plastic work, etc.) combined with thermochemical energy from the reaction may provide a means to synthesize c-BN. This material is based upon work supported by the Department of Energy, National Nuclear Security Administration, under Award Number(s) DE-NA0002377. National Defense Science & Engineering Graduate Fellowship (NDSEG), 32 CFR 168a.

Silicon Materials Task of the Low Cost Solar Array Project, Phase 3. Effect of Impurities and Processing on Silicon Solar Cells

NASA Technical Reports Server (NTRS)

Hopkins, R. H.; Davis, J. R.; Blais, P. D.; Rohatgi, A.; Campbell, R. B.; Rai-Choudhury, P.; Stapleton, R. E.; Mollenkopf, H. C.; Mccormick, J. R.

1979-01-01

The effects of impurities, various thermochemical processes, and any impurity process interactions on the performance of terrestrial silicon solar cells are defined. Determinations of the segregation coefficients of tungsten, tantalum, and cobalt for the Czochralski pulling of silicon single crystals are reported. Sensitive neutron activation analysis was used to determine the metal impurity content of the silicon while atomic absorption was used to measure the metal content of the residual liquid from which the doped crystals were grown. Gettering of Ti doped silicon wafers improved cell performance by one to two percent for the highest temperatures and longest times. The HCl is more effective than POCl3 treatments for deactivating Ti but POCl3 and HCl produced essentially identical results for Mo or Fe.

Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

DOE PAGES

Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.; ...

2016-09-05

Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, heremore » we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective valorization strategies for these waste streams.« less

Finite element calculations of the time dependent thermal fluxes in the laser-heated diamond anvil cell

NASA Astrophysics Data System (ADS)

Montoya, Javier A.; Goncharov, Alexander F.

2012-06-01

The time-dependent temperature distribution in the laser-heated diamond anvil cell (DAC) is examined using finite element simulations. Calculations are carried out for the practically important case of a surface-absorbing metallic plate (coupler) surrounded by a thermally insulating transparent medium. The time scales of the heat transfer in the DAC cavity are found to be typically on the order of tens of microseconds depending on the geometrical and thermochemical parameters of the constituent materials. The use of much shorter laser pulses (e.g., on the order of tens of nanoseconds) creates sharp radial temperature gradients, which result in a very intense and abrupt axial conductive heat transfer that exceeds the radiative heat transfer by several orders of magnitude in the practically usable temperature range (<12 000 K). In contrast, the use of laser pulses with several μs duration provides sufficiently uniform spatial heating conditions suitable for studying the bulk sample. The effect of the latent heat of melting on the temperature distribution has been examined in the case of iron and hydrogen for both pulsed and continuous laser heating. The observed anomalies in temperature-laser power dependencies cannot be due to latent heat effects only. Finally, we examine the applicability of a modification to the plate geometry Ångström method for measurements of the thermal diffusivity in the DAC. The calculations show substantial effects of the thermochemical parameters of the insulating medium on the amplitude change and phase shift between the surface temperature variations of the front and back of the sample, which makes this method dependent on the precise knowledge of the properties of the medium.

Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.

Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, heremore » we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective valorization strategies for these waste streams.« less

Parallel database search and prime factorization with magnonic holographic memory devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khitun, Alexander

In this work, we describe the capabilities of Magnonic Holographic Memory (MHM) for parallel database search and prime factorization. MHM is a type of holographic device, which utilizes spin waves for data transfer and processing. Its operation is based on the correlation between the phases and the amplitudes of the input spin waves and the output inductive voltage. The input of MHM is provided by the phased array of spin wave generating elements allowing the producing of phase patterns of an arbitrary form. The latter makes it possible to code logic states into the phases of propagating waves and exploitmore » wave superposition for parallel data processing. We present the results of numerical modeling illustrating parallel database search and prime factorization. The results of numerical simulations on the database search are in agreement with the available experimental data. The use of classical wave interference may results in a significant speedup over the conventional digital logic circuits in special task data processing (e.g., √n in database search). Potentially, magnonic holographic devices can be implemented as complementary logic units to digital processors. Physical limitations and technological constrains of the spin wave approach are also discussed.« less

Parallel database search and prime factorization with magnonic holographic memory devices

NASA Astrophysics Data System (ADS)

Khitun, Alexander

2015-12-01

In this work, we describe the capabilities of Magnonic Holographic Memory (MHM) for parallel database search and prime factorization. MHM is a type of holographic device, which utilizes spin waves for data transfer and processing. Its operation is based on the correlation between the phases and the amplitudes of the input spin waves and the output inductive voltage. The input of MHM is provided by the phased array of spin wave generating elements allowing the producing of phase patterns of an arbitrary form. The latter makes it possible to code logic states into the phases of propagating waves and exploit wave superposition for parallel data processing. We present the results of numerical modeling illustrating parallel database search and prime factorization. The results of numerical simulations on the database search are in agreement with the available experimental data. The use of classical wave interference may results in a significant speedup over the conventional digital logic circuits in special task data processing (e.g., √n in database search). Potentially, magnonic holographic devices can be implemented as complementary logic units to digital processors. Physical limitations and technological constrains of the spin wave approach are also discussed.

Early ICU Standardized Rehabilitation Therapy for the Critically Injured Burn Patient

DTIC Science & Technology

2017-10-01

phase proposed to examine medical records within a large national hospital database to identify optimal care delivery patters. Minimizing the...The original study was deemed phase I and closed. The second phase proposed to examine medical records within a large national hospital database to...engineering, and the academic world on areas such as: • improving public knowledge, attitudes, skills, and abilities; • changing behavior, practices

Modelling the combustion of charcoal in a model blast furnace

NASA Astrophysics Data System (ADS)

Shen, Yansong; Shiozawa, Tomo; Yu, Aibing; Austin, Peter

2013-07-01

The pulverized charcoal (PCH) combustion in ironmaking blast furnaces is abstracting remarkable attention due to various benefits such as lowering CO2 emission. In this study, a three-dimensional CFD model is used to simulate the flow and thermo-chemical behaviours in this process. The model is validated against the experimental results from a pilot-scale combustion test rig for a range of conditions. The typical flow and thermo-chemical phenomena is simulated. The effect of charcoal type, i.e. VM content is examined, showing that the burnout increases with VM content in a linear relationship. This model provides an effective way for designing and optimizing PCH operation in blast furnace practice.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nexant, Inc., San Francisco, California

The first section (Task 1) of this report by Nexant includes a survey and screening of various acid gas removal processes in order to evaluate their capability to meet the specific design requirements for thermochemical ethanol synthesis in NREL's thermochemical ethanol design report (Phillips et al. 2007, NREL/TP-510-41168). MDEA and selexol were short-listed as the most promising acid-gas removal agents based on work described in Task 1. The second report section (Task 2) describes a detailed design of an MDEA (methyl diethanol amine) based acid gas removal system for removing CO2 and H2S from biomass-derived syngas. Only MDEA was chosenmore » for detailed study because of the available resources.« less

Estimating Equivalency of Explosives Through A Thermochemical Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maienschein, J L

2002-07-08

The Cheetah thermochemical computer code provides an accurate method for estimating the TNT equivalency of any explosive, evaluated either with respect to peak pressure or the quasi-static pressure at long time in a confined volume. Cheetah calculates the detonation energy and heat of combustion for virtually any explosive (pure or formulation). Comparing the detonation energy for an explosive with that of TNT allows estimation of the TNT equivalency with respect to peak pressure, while comparison of the heat of combustion allows estimation of TNT equivalency with respect to quasi-static pressure. We discuss the methodology, present results for many explosives, andmore » show comparisons with equivalency data from other sources.« less

A thermochemical model of radiation damage and annealing applied to GaAs solar cells

NASA Technical Reports Server (NTRS)

Conway, E. J.; Walker, G. H.; Heinbockel, J. H.

1981-01-01

Calculations of the equilibrium conditions for continuous radiation damage and thermal annealing are reported. The calculations are based on a thermochemical model developed to analyze the incorporation of point imperfections in GaAs, and modified by introducing the radiation to produce native lattice defects rather than high-temperature and arsenic atmospheric pressure. The concentration of a set of defects, including vacancies, divacancies, and impurity vacancy complexes, are calculated as a function of temperature. Minority carrier lifetimes, short circuit current, and efficiency are deduced for a range of equilibrium temperatures. The results indicate that GaAs solar cells could have a mission life which is not greatly limited by radiation damage.

A theoretical study of the structure and thermochemical properties of alkali metal fluoroplumbates MPbF3.

PubMed

Boltalin, A I; Korenev, Yu M; Sipachev, V A

2007-07-19

Molecular constants of MPbF3 (M=Li, Na, K, Rb, and Cs) were calculated theoretically at the MP2(full) and B3LYP levels with the SDD (Pb, K, Rb, and Cs) and cc-aug-pVQZ (F, Li, and Na) basis sets to determine the thermochemical characteristics of the substances. Satisfactory agreement with experiment was obtained, including the unexpected nonmonotonic dependence of substance dissociation energies on the alkali metal atomic number. The bond lengths of the theoretical CsPbF3 model were substantially elongated compared with experimental estimates, likely because of errors in both theoretical calculations and electron diffraction data processing.

The SERI solar energy storage program

NASA Technical Reports Server (NTRS)

Copeland, R. J.; Wright, J. D.; Wyman, C. E.

1980-01-01

In support of the DOE thermal and chemical energy storage program, the solar energy storage program (SERI) provides research on advanced technologies, systems analyses, and assessments of thermal energy storage for solar applications in support of the Thermal and Chemical Energy Storage Program of the DOE Division of Energy Storage Systems. Currently, research is in progress on direct contact latent heat storage and thermochemical energy storage and transport. Systems analyses are being performed of thermal energy storage for solar thermal applications, and surveys and assessments are being prepared of thermal energy storage in solar applications. A ranking methodology for comparing thermal storage systems (performance and cost) is presented. Research in latent heat storage and thermochemical storage and transport is reported.

Particle kinetic simulation of high altitude hypervelocity flight

NASA Technical Reports Server (NTRS)

Heinemann, Klaus; Boyd, Iain D.; Haas, Brian L.

1993-01-01

In this grant period, the focus has been on the effects of thermo-chemical nonequilibrium in low-density gases, and on interactions between such gases and solid surfaces. Such conditions apply to hypersonic flows of re-entry vehicles, and to the expansion plumes of small rockets. Due to the nonequilibrium nature of these flows, a particle approach has been adopted. The method continues to undergo refinement and application to typical flows of interest. A number of studies have been performed for flows in thermo-chemical nonequilibrium. The effects of vibrational nonequilibrium on the rate of dissociation were studied for diatomic nitrogen. It was found that a new model reproduced the nonequilibrium behavior observed experimentally.

Thermochemical characterization of pigeon pea stalk for its efficient utilization as an energy source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katyal, S.K.; Iyer, P.V.R.

2000-05-01

Pigeon pea stalk is a widely available biomass species in India. In this article the potential use of pigeon pea stalk as a fuel source through thermochemical conversion methods such as combustion, gasification, and pyrolysis has been investigated through experimentation using a thermogravimetric analyzer and pilot-plant-scale equipment. It has been proposed that pigeon pea stalks can be effectively utilized in two ways. The first is to pyrolyze the material to produce value-added products such as char, tar, and fuel gas. The second alternative is to partially pyrolyze the material to remove tar-forming volatiles, followed by gasification of reactive char tomore » generate producer gas.« less

Thermochemical generation of hydrogen and oxygen from water. [NaMnO/sub 2/ and TiO/sub 2/

DOEpatents

Robinson, P.R.; Bamberger, C.E.

1980-02-08

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO/sub 2/) and titanium dioxide (TiO/sub 2/) to form sodium titanate (Na/sub 2/TiO/sub 3/), manganese (II) titanate (MnTiO/sub 3/) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Hydrogen as an energy medium

NASA Technical Reports Server (NTRS)

Cox, K. E.

1976-01-01

Coal, though abundant in certain geographical locations of the USA poses environmental problems associated with its mining and combustion. Also, nuclear fission energy appears to have problems regarding safety and radioactive waste disposal that are as yet unresolved. The paper discusses hydrogen use and market projection along with energy sources for hydrogen production. Particular attention is given to hydrogen production technology as related to electrolysis and thermochemical water decomposition. Economics of hydrogen will ultimately be determined by the price and availability of future energy carriers such as electricity and synthetic natural gas. Thermochemical methods of hydrogen production appear to offer promise largely in the efficiency of energy conversion and in capital costs over electrolytic methods.

Radiation Transport Around Axisymmetric Blunt Body Vehicles Using a Modified Differential Approximation

NASA Technical Reports Server (NTRS)

Hartung, Lin C.; Hassan, H. A.

1992-01-01

A moment method for computing 3-D radiative transport is applied to axisymmetric flows in thermochemical nonequilibrium. Such flows are representative of proposed aerobrake missions. The method uses the P-1 approximation to reduce the governing system of integro-di erential equations to a coupled set of partial di erential equations. A numerical solution method for these equations given actual variations of the radiation properties in thermochemical nonequilibrium blunt body flows is developed. Initial results from the method are shown and compared to tangent slab calculations. The agreement between the transport methods is found to be about 10 percent in the stagnation region, with the difference increasing along the flank of the vehicle.

Nonequilibrium shock-heated nitrogen flows using a rovibrational state-to-state method

NASA Astrophysics Data System (ADS)

Panesi, M.; Munafò, A.; Magin, T. E.; Jaffe, R. L.

2014-07-01

A rovibrational collisional model is developed to study the internal energy excitation and dissociation processes behind a strong shock wave in a nitrogen flow. The reaction rate coefficients are obtained from the ab initio database of the NASA Ames Research Center. The master equation is coupled with a one-dimensional flow solver to study the nonequilibrium phenomena encountered in the gas during a hyperbolic reentry into Earth's atmosphere. The analysis of the populations of the rovibrational levels demonstrates how rotational and vibrational relaxation proceed at the same rate. This contrasts with the common misconception that translational and rotational relaxation occur concurrently. A significant part of the relaxation process occurs in non-quasi-steady-state conditions. Exchange processes are found to have a significant impact on the relaxation of the gas, while predissociation has a negligible effect. The results obtained by means of the full rovibrational collisional model are used to assess the validity of reduced order models (vibrational collisional and multitemperature) which are based on the same kinetic database. It is found that thermalization and dissociation are drastically overestimated by the reduced order models. The reasons of the failure differ in the two cases. In the vibrational collisional model the overestimation of the dissociation is a consequence of the assumption of equilibrium between the rotational energy and the translational energy. The multitemperature model fails to predict the correct thermochemical relaxation due to the failure of the quasi-steady-state assumption, used to derive the phenomenological rate coefficient for dissociation.

The life story of hydrogen peroxide II: a periodic pH and thermochemical drive for the RNA world

PubMed Central

Ball, Rowena; Brindley, John

2015-01-01

It is now accepted that primordial non-cellular RNA communities must have been subject to a periodic drive in order to replicate and prosper. We have proposed the oxidation of thiosulfate by hydrogen peroxide as this drive. This reaction system behaves as (i) a thermochemical and (ii) a pH oscillator, and in this work, we unify (i) and (ii) for the first time. We report thermally self-consistent, dynamical simulations in which the system transitions smoothly from nearly isothermal pH to fully developed thermo-pH oscillatory regimes. We use this oscillator to drive simulated replication of a 39-bp RNA species. Production of replicated duplex under thermo-pH drive was significantly enhanced compared with that under purely thermochemical drive, effectively allowing longer strands to replicate. Longer strands are fitter, with more potential to evolve enzyme activity and resist degradation. We affirm that concern over the alleged toxicity of hydrogen peroxide to life is largely misplaced in the current context, we survey its occurrence in the solar system to motivate its inclusion as a biosignature in the search for life on other worlds and highlight that pH oscillations in a spatially extended, bounded system manifest as the fundamental driving force of life: a proton gradient. PMID:26202683

Thermochemical hydrolysis of macroalgae Ulva for biorefinery: Taguchi robust design method

PubMed Central

Jiang, Rui; Linzon, Yoav; Vitkin, Edward; Yakhini, Zohar; Chudnovsky, Alexandra; Golberg, Alexander

2016-01-01

Understanding the impact of all process parameters on the efficiency of biomass hydrolysis and on the final yield of products is critical to biorefinery design. Using Taguchi orthogonal arrays experimental design and Partial Least Square Regression, we investigated the impact of change and the comparative significance of thermochemical process temperature, treatment time, %Acid and %Solid load on carbohydrates release from green macroalgae from Ulva genus, a promising biorefinery feedstock. The average density of hydrolysate was determined using a new microelectromechanical optical resonator mass sensor. In addition, using Flux Balance Analysis techniques, we compared the potential fermentation yields of these hydrolysate products using metabolic models of Escherichia coli, Saccharomyces cerevisiae wild type, Saccharomyces cerevisiae RN1016 with xylose isomerase and Clostridium acetobutylicum. We found that %Acid plays the most significant role and treatment time the least significant role in affecting the monosaccharaides released from Ulva biomass. We also found that within the tested range of parameters, hydrolysis with 121 °C, 30 min 2% Acid, 15% Solids could lead to the highest yields of conversion: 54.134–57.500 gr ethanol kg−1 Ulva dry weight by S. cerevisiae RN1016 with xylose isomerase. Our results support optimized marine algae utilization process design and will enable smart energy harvesting by thermochemical hydrolysis. PMID:27291594

Climate Impact and Economic Feasibility of Solar Thermochemical Jet Fuel Production.

PubMed

Falter, Christoph; Batteiger, Valentin; Sizmann, Andreas

2016-01-05

Solar thermochemistry presents a promising option for the efficient conversion of H2O and CO2 into liquid hydrocarbon fuels using concentrated solar energy. To explore the potential of this fuel production pathway, the climate impact and economic performance are analyzed. Key drivers for the economic and ecological performance are thermochemical energy conversion efficiency, the level of solar irradiation, operation and maintenance, and the initial investment in the fuel production plant. For the baseline case of a solar tower concentrator with CO2 capture from air, jet fuel production costs of 2.23 €/L and life cycle greenhouse gas (LC GHG) emissions of 0.49 kgCO2-equiv/L are estimated. Capturing CO2 from a natural gas combined cycle power plant instead of the air reduces the production costs by 15% but leads to LC GHG emissions higher than that of conventional jet fuel. Favorable assumptions for all involved process steps (30% thermochemical energy conversion efficiency, 3000 kWh/(m(2) a) solar irradiation, low CO2 and heliostat costs) result in jet fuel production costs of 1.28 €/L at LC GHG emissions close to zero. Even lower production costs may be achieved if the commercial value of oxygen as a byproduct is considered.

Development and application of computational aerothermodynamics flowfield computer codes

NASA Technical Reports Server (NTRS)

Venkatapathy, Ethiraj

1994-01-01

Research was performed in the area of computational modeling and application of hypersonic, high-enthalpy, thermo-chemical nonequilibrium flow (Aerothermodynamics) problems. A number of computational fluid dynamic (CFD) codes were developed and applied to simulate high altitude rocket-plume, the Aeroassist Flight Experiment (AFE), hypersonic base flow for planetary probes, the single expansion ramp model (SERN) connected with the National Aerospace Plane, hypersonic drag devices, hypersonic ramp flows, ballistic range models, shock tunnel facility nozzles, transient and steady flows in the shock tunnel facility, arc-jet flows, thermochemical nonequilibrium flows around simple and complex bodies, axisymmetric ionized flows of interest to re-entry, unsteady shock induced combustion phenomena, high enthalpy pulsed facility simulations, and unsteady shock boundary layer interactions in shock tunnels. Computational modeling involved developing appropriate numerical schemes for the flows on interest and developing, applying, and validating appropriate thermochemical processes. As part of improving the accuracy of the numerical predictions, adaptive grid algorithms were explored, and a user-friendly, self-adaptive code (SAGE) was developed. Aerothermodynamic flows of interest included energy transfer due to strong radiation, and a significant level of effort was spent in developing computational codes for calculating radiation and radiation modeling. In addition, computational tools were developed and applied to predict the radiative heat flux and spectra that reach the model surface.

Thermochemical hydrolysis of macroalgae Ulva for biorefinery: Taguchi robust design method

NASA Astrophysics Data System (ADS)

Jiang, Rui; Linzon, Yoav; Vitkin, Edward; Yakhini, Zohar; Chudnovsky, Alexandra; Golberg, Alexander

2016-06-01

Understanding the impact of all process parameters on the efficiency of biomass hydrolysis and on the final yield of products is critical to biorefinery design. Using Taguchi orthogonal arrays experimental design and Partial Least Square Regression, we investigated the impact of change and the comparative significance of thermochemical process temperature, treatment time, %Acid and %Solid load on carbohydrates release from green macroalgae from Ulva genus, a promising biorefinery feedstock. The average density of hydrolysate was determined using a new microelectromechanical optical resonator mass sensor. In addition, using Flux Balance Analysis techniques, we compared the potential fermentation yields of these hydrolysate products using metabolic models of Escherichia coli, Saccharomyces cerevisiae wild type, Saccharomyces cerevisiae RN1016 with xylose isomerase and Clostridium acetobutylicum. We found that %Acid plays the most significant role and treatment time the least significant role in affecting the monosaccharaides released from Ulva biomass. We also found that within the tested range of parameters, hydrolysis with 121 °C, 30 min 2% Acid, 15% Solids could lead to the highest yields of conversion: 54.134-57.500 gr ethanol kg-1 Ulva dry weight by S. cerevisiae RN1016 with xylose isomerase. Our results support optimized marine algae utilization process design and will enable smart energy harvesting by thermochemical hydrolysis.

Effect of various types of thermochemical processing of sewage sludges on phosphorus speciation, solubility, and fertilization performance.

PubMed

Steckenmesser, Daniel; Vogel, Christian; Adam, Christian; Steffens, Diedrich

2017-04-01

Sewage sludge has one of the highest phosphorus (P) recovery potentials of all waste materials. Therefore, P-recycling from sewage sludge could contribute to closing the P-cycle. Recently, various thermal processes for P-recovery have been developed, but there is still a demand for information on the effect of different process parameters (e.g. additives and temperature) on P-speciation and especially on the fertilization performance. In the present study, two common methods (low-temperature conversion at 400-500°C and thermochemical treatment at 950°C) were investigated and combined to produce highly bioavailable P-fertilizers from two different types of sewage sludge based on chemical phosphorus precipitation (Chem-P) and enhanced biological phosphorus removal (Bio-P). The results of P-fractionation, X-ray diffraction analysis, and pot experiments with maize showed that Bio-P sludges attain high P-plant-availability after treatment at low temperatures (400°C). In contrast, Chem-P sludges can adequately be treated at higher temperatures under reductive conditions with sodium additives to form highly bioavailable calcium-sodium-phosphate. Additionally, also highly heavy-metal contaminated sludges can be thermochemically treated at high temperatures to achieve the legal requirements for fertilizers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Tungsten - Yttrium Based Nuclear Structural Materials

NASA Astrophysics Data System (ADS)

Ramana, Chintalapalle; Chessa, Jack; Martinenz, Gustavo

2013-04-01

The challenging problem currently facing the nuclear science community in this 21st century is design and development of novel structural materials, which will have an impact on the next-generation nuclear reactors. The materials available at present include reduced activation ferritic/martensitic steels, dispersion strengthened reduced activation ferritic steels, and vanadium- or tungsten-based alloys. These materials exhibit one or more specific problems, which are either intrinsic or caused by reactors. This work is focussed towards tungsten-yttrium (W-Y) based alloys and oxide ceramics, which can be utilized in nuclear applications. The goal is to derive a fundamental scientific understanding of W-Y-based materials. In collaboration with University of Califonia -- Davis, the project is designated to demonstrate the W-Y based alloys, ceramics and composites with enhanced physical, mechanical, thermo-chemical properties and higher radiation resistance. Efforts are focussed on understanding the microstructure, manipulating materials behavior under charged-particle and neutron irradiation, and create a knowledge database of defects, elemental diffusion/segregation, and defect trapping along grain boundaries and interfaces. Preliminary results will be discussed.

Kinetics and mechanism of solid decompositions — From basic discoveries by atomic absorption spectrometry and quadrupole mass spectroscopy to thorough thermogravimetric analysis

NASA Astrophysics Data System (ADS)

L'vov, Boris V.

2008-02-01

This paper sums up the evolution of thermochemical approach to the interpretation of solid decompositions for the past 25 years. This period includes two stages related to decomposition studies by different techniques: by ET AAS and QMS in 1981-2001 and by TG in 2002-2007. As a result of ET AAS and QMS investigations, the method for determination of absolute rates of solid decompositions was developed and the mechanism of decompositions through the congruent dissociative vaporization was discovered. On this basis, in the period from 1997 to 2001, the decomposition mechanisms of several classes of reactants were interpreted and some unusual effects observed in TA were explained. However, the thermochemical approach has not received any support by other TA researchers. One of the potential reasons of this distrust was the unreliability of the E values measured by the traditional Arrhenius plot method. The theoretical analysis and comparison of metrological features of different methods used in the determinations of thermochemical quantities permitted to conclude that in comparison with the Arrhenius plot and second-law methods, the third-law method is to be very much preferred. However, this method cannot be used in the kinetic studies by the Arrhenius approach because its use suggests the measuring of the equilibrium pressures of decomposition products. On the contrary, the method of absolute rates is ideally suitable for this purpose. As a result of much higher precision of the third-law method, some quantitative conclusions that follow from the theory were confirmed, and several new effects, which were invisible in the framework of the Arrhenius approach, have been revealed. In spite of great progress reached in the development of reliable methodology, based on the third-law method, the thermochemical approach remains unclaimed as before.

Biomass thermochemical gasification: Experimental studies and modeling

NASA Astrophysics Data System (ADS)

Kumar, Ajay

The overall goals of this research were to study the biomass thermochemical gasification using experimental and modeling techniques, and to evaluate the cost of industrial gas production and combined heat and power generation. This dissertation includes an extensive review of progresses in biomass thermochemical gasification. Product gases from biomass gasification can be converted to biopower, biofuels and chemicals. However, for its viable commercial applications, the study summarizes the technical challenges in the gasification and downstream processing of product gas. Corn stover and dried distillers grains with solubles (DDGS), a non-fermentable byproduct of ethanol production, were used as the biomass feedstocks. One of the objectives was to determine selected physical and chemical properties of corn stover related to thermochemical conversion. The parameters of the reaction kinetics for weight loss were obtained. The next objective was to investigate the effects of temperature, steam to biomass ratio and equivalence ratio on gas composition and efficiencies. DDGS gasification was performed on a lab-scale fluidized-bed gasifier with steam and air as fluidizing and oxidizing agents. Increasing the temperature resulted in increases in hydrogen and methane contents and efficiencies. A model was developed to simulate the performance of a lab-scale gasifier using Aspen Plus(TM) software. Mass balance, energy balance and minimization of Gibbs free energy were applied for the gasification to determine the product gas composition. The final objective was to optimize the process by maximizing the net energy efficiency, and to estimate the cost of industrial gas, and combined heat and power (CHP) at a biomass feedrate of 2000 kg/h. The selling price of gas was estimated to be 11.49/GJ for corn stover, and 13.08/GJ for DDGS. For CHP generation, the electrical and net efficiencies were 37 and 86%, respectively for corn stover, and 34 and 78%, respectively for DDGS. For corn stover, the selling price of electricity was 0.1351/kWh. For DDGS, the selling price of electricity was 0.1287/kWh.

Coupled thermo-chemical boundary conditions in double-diffusive geodynamo models at arbitrary Lewis numbers.

NASA Astrophysics Data System (ADS)

Bouffard, M.

2016-12-01

Convection in the Earth's outer core is driven by the combination of two buoyancy sources: a thermal source directly related to the Earth's secular cooling, the release of latent heat and possibly the heat generated by radioactive decay, and a compositional source due to the crystallization of the growing inner core which releases light elements into the liquid outer core. The dynamics of fusion/crystallization being dependent on the heat flux distribution, the thermochemical boundary conditions are coupled at the inner core boundary which may affect the dynamo in various ways, particularly if heterogeneous conditions are imposed at one boundary. In addition, the thermal and compositional molecular diffusivities differ by three orders of magnitude. This can produce significant differences in the convective dynamics compared to pure thermal or compositional convection due to the potential occurence of double-diffusive phenomena. Traditionally, temperature and composition have been combined into one single variable called codensity under the assumption that turbulence mixes all physical properties at an "eddy-diffusion" rate. This description does not allow for a proper treatment of the thermochemical coupling and is certainly incorrect within stratified layers in which double-diffusive phenomena can be expected. For a more general and rigorous approach, two distinct transport equations should therefore be solved for temperature and composition. However, the weak compositional diffusivity is technically difficult to handle in current geodynamo codes and requires the use of a semi-Lagrangian description to minimize numerical diffusion. We implemented a "particle-in-cell" method into a geodynamo code to properly describe the compositional field. The code is suitable for High Parallel Computing architectures and was successfully tested on two benchmarks. Following the work by Aubert et al. (2008) we use this new tool to perform dynamo simulations including thermochemical coupling at the inner core boundary as well as exploration of the infinite Lewis number limit to study the effect of a heterogeneous core mantle boundary heat flow on the inner core growth.

Thermodynamic Analysis of the Use a Chemical Heat Pump to Link a Supercritical Water-Cooled Nuclear Reactor and a Thermochemical Water-Splitting Cycle for Hydrogen Production

NASA Astrophysics Data System (ADS)

Granovskii, Mikhail; Dincer, Ibrahim; Rosen, Marc A.; Pioro, Igor

Increases in the power generation efficiency of nuclear power plants (NPPs) are mainly limited by the permissible temperatures in nuclear reactors and the corresponding temperatures and pressures of the coolants in reactors. Coolant parameters are limited by the corrosion rates of materials and nuclear-reactor safety constraints. The advanced construction materials for the next generation of CANDU reactors, which employ supercritical water (SCW) as a coolant and heat carrier, permit improved “steam” parameters (outlet temperatures up to 625°C and pressures of about 25 MPa). An increase in the temperature of steam allows it to be utilized in thermochemical water splitting cycles to produce hydrogen. These methods are considered by many to be among the most efficient ways to produce hydrogen from water and to have advantages over traditional low-temperature water electrolysis. However, even lower temperature water splitting cycles (Cu-Cl, UT-3, etc.) require an intensive heat supply at temperatures higher than 550-600°C. A sufficient increase in the heat transfer from the nuclear reactor to a thermochemical water splitting cycle, without jeopardizing nuclear reactor safety, might be effectively achieved by application of a heat pump, which increases the temperature of the heat supplied by virtue of a cyclic process driven by mechanical or electrical work. Here, a high-temperature chemical heat pump, which employs the reversible catalytic methane conversion reaction, is proposed. The reaction shift from exothermic to endothermic and back is achieved by a change of the steam concentration in the reaction mixture. This heat pump, coupled with the second steam cycle of a SCW nuclear power generation plant on one side and a thermochemical water splitting cycle on the other, increases the temperature of the “nuclear” heat and, consequently, the intensity of heat transfer into the water splitting cycle. A comparative preliminary thermodynamic analysis is conducted of the combined system comprising a SCW nuclear power generation plant and a chemical heat pump, which provides high-temperature heat to a thermochemical water splitting cycle for hydrogen production. It is concluded that the proposed chemical heat pump permits the utilization efficiency of nuclear energy to be improved by at least 2% without jeopardizing nuclear reactor safety. Based on this analysis, further research appears to be merited on the proposed advanced design of a nuclear power generation plant combined with a chemical heat pump, and implementation in appropriate applications seems worthwhile.

The Effect of Boronizing on Metallic Alloys for Automotive Applications

NASA Astrophysics Data System (ADS)

Petrova, Roumiana S.; Suwattananont, Naruemon; Samardzic, Veljko

2008-06-01

In this study the wear resistance, corrosion resistance, and oxidation resistance of boronized metallic alloys were investigated. Thermochemical treatment was performed by powder pack boronizing process at temperature 850-950 °C for 4 h. Saw-tooth morphology and smooth interface microstructures were observed with an optical microscope; microhardness was measured across the coating depth. The phases present in the boron coatings depend on the substrate material. High-temperature oxidation resistance was investigated and it was found that boron coating on ferrous alloys can resist temperatures up to 800 °C. The corrosion resistance of the boronized samples was improved and the corrosion rate was calculated for boronized and plain specimens. Wear testing was conducted by following the procedures of ASTM G99, ASTM D2526, and ASTM D4060. The obtained experimental results revealed that boronizing significantly improves the wear-resistance, corrosion-resistance, and oxidation resistance of metallic alloys.

Critical Evaluation of Kinetic Method Measurements: Possible Origins of Nonlinear Effects

NASA Astrophysics Data System (ADS)

Bourgoin-Voillard, Sandrine; Afonso, Carlos; Lesage, Denis; Zins, Emilie-Laure; Tabet, Jean-Claude; Armentrout, P. B.

2013-03-01

The kinetic method is a widely used approach for the determination of thermochemical data such as proton affinities (PA) and gas-phase acidities ( ΔH° acid ). These data are easily obtained from decompositions of noncovalent heterodimers if care is taken in the choice of the method, references used, and experimental conditions. Previously, several papers have focused on theoretical considerations concerning the nature of the references. Few investigations have been devoted to conditions required to validate the quality of the experimental results. In the present work, we are interested in rationalizing the origin of nonlinear effects that can be obtained with the kinetic method. It is shown that such deviations result from intrinsic properties of the systems investigated but can also be enhanced by artifacts resulting from experimental issues. Overall, it is shown that orthogonal distance regression (ODR) analysis of kinetic method data provides the optimum way of acquiring accurate thermodynamic information.

Computational Aerothermodynamics in Aeroassist Applications

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.

2001-01-01

Aeroassisted planetary entry uses atmospheric drag to decelerate spacecraft from super-orbital to orbital or suborbital velocities. Numerical simulation of flow fields surrounding these spacecraft during hypersonic atmospheric entry is required to define aerothermal loads. The severe compression in the shock layer in front of the vehicle and subsequent, rapid expansion into the wake are characterized by high temperature, thermo-chemical nonequilibrium processes. Implicit algorithms required for efficient, stable computation of the governing equations involving disparate time scales of convection, diffusion, chemical reactions, and thermal relaxation are discussed. Robust point-implicit strategies are utilized in the initialization phase; less robust but more efficient line-implicit strategies are applied in the endgame. Applications to ballutes (balloon-like decelerators) in the atmospheres of Venus, Mars, Titan, Saturn, and Neptune and a Mars Sample Return Orbiter (MSRO) are featured. Examples are discussed where time-accurate simulation is required to achieve a steady-state solution.

Space exploration and the history of solar-system volatiles

NASA Technical Reports Server (NTRS)

Fanale, F. P.

1976-01-01

The thermochemical history of volatile substances in all solar-system planets, satellites, and planetoids is discussed extensively. The volatiles are viewed as an interface between the abiotic and biotic worlds and as a key to the history of bodies of the solar system. A flowsheet of processes and states is exhibited. Differences in bulk volatiles distribution between the planetary bodies and between the interior, surface, and atmosphere of each body are considered, as well as sinks for volatiles in degassing. The volatiles-rich Jovian and Saturnian satellites, the effect of large-planet magnetosphere sweeps on nearby satellites, volatiles of asteroids and comets, and the crucial importance of seismic, gravity, and libration data are treated. A research program encompassing analysis of the elemental and isotopic composition of rare gas in atmospheres, assay of volatiles-containing phases in regoliths, and examination of present or past atmospheric escape/accretion processes is recommended.

JAGUAR Procedures for Detonation Behavior of Silicon Containing Explosives

NASA Astrophysics Data System (ADS)

Stiel, Leonard; Baker, Ernest; Capellos, Christos; Poulos, William; Pincay, Jack

2007-06-01

Improved relationships for the thermodynamic properties of solid and liquid silicon and silicon oxide for use with JAGUAR thermo-chemical equation of state routines were developed in this study. Analyses of experimental melting temperature curves for silicon and silicon oxide indicated complex phase behavior and that improved coefficients were required for solid and liquid thermodynamic properties. Advanced optimization routines were utilized in conjunction with the experimental melting point data to establish volumetric coefficients for these substances. The new property libraries resulted in agreement with available experimental values, including Hugoniot data at elevated pressures. Detonation properties were calculated with JAGUAR using the revised property libraries for silicon containing explosives. Constants of the JWLB equation of state were established for varying extent of silicon reaction. Supporting thermal heat transfer analyses were conducted for varying silicon particle sizes to establish characteristic times for melting and silicon reaction.

Detonation Velocity Calculations of Explosives with Slowly-Burning Constituents

NASA Astrophysics Data System (ADS)

Howard, W. Michael; Souers, P. Clark; Fried, Laurence E.

1997-07-01

The thermochemical code Equilbrium CHEETAH has been modified to allow partial reaction of constituents and partial flow of heat. Solid or liquid reactants are described by Einstein oscillators, whose temperatures can be changed to allow heat transfer. Hydroxy-terminated-poly-budadiene, mixed with RDX or HMX, does not react, as shown by the effect on the calculated detonation velocity. Aluminum and ammonium perchlorate in composites also do not react. Only partial heat flow also takes place in the unreacted materials. These results show that the usual assumption of total burn in a thermochemical code is probably incorrect, at least in the sonic reaction zone that drives the detonation velocity. A kinetic code would be the logical extension of this work.

The development of an explicit thermochemical nonequilibrium algorithm and its application to compute three dimensional AFE flowfields

NASA Technical Reports Server (NTRS)

Palmer, Grant

1989-01-01

This study presents a three-dimensional explicit, finite-difference, shock-capturing numerical algorithm applied to viscous hypersonic flows in thermochemical nonequilibrium. The algorithm employs a two-temperature physical model. Equations governing the finite-rate chemical reactions are fully-coupled to the gas dynamic equations using a novel coupling technique. The new coupling method maintains stability in the explicit, finite-rate formulation while allowing relatively large global time steps. The code uses flux-vector accuracy. Comparisons with experimental data and other numerical computations verify the accuracy of the present method. The code is used to compute the three-dimensional flowfield over the Aeroassist Flight Experiment (AFE) vehicle at one of its trajectory points.

Effective Heat and Mass Transport Properties of Anisotropic Porous Ceria for Solar Thermochemical Fuel Generation

PubMed Central

Haussener, Sophia; Steinfeld, Aldo

2012-01-01

High-resolution X-ray computed tomography is employed to obtain the exact 3D geometrical configuration of porous anisotropic ceria applied in solar-driven thermochemical cycles for splitting H2O and CO2. The tomography data are, in turn, used in direct pore-level numerical simulations for determining the morphological and effective heat/mass transport properties of porous ceria, namely: porosity, specific surface area, pore size distribution, extinction coefficient, thermal conductivity, convective heat transfer coefficient, permeability, Dupuit-Forchheimer coefficient, and tortuosity and residence time distributions. Tailored foam designs for enhanced transport properties are examined by means of adjusting morphologies of artificial ceria samples composed of bimodal distributed overlapping transparent spheres in an opaque medium. PMID:28817039

Thermochemical analysis of intermolecular interactions between N-acetylglycine and polyols in aqueous solutions

NASA Astrophysics Data System (ADS)

Mezhevoi, I. N.; Badelin, V. G.

2017-05-01

The integral enthalpies of dissolution Δsol H m for N-acetylglycine in aqueous solutions of glycerol, ethylene glycol and 1,2-propylene glycol are measured via solution calorimetry. The standard enthalpies of dissolution (Δsol H 0) and transfer (Δtr H 0) for N-acetylglycine from water to aqueous solutions of polyhydric alcohols are calculated from experimental data. Positive values of enthalpy coefficients of pair interactions h xy for amino acids and polyol molecules are calculated using the McMillan-Mayer theory. The results are discussed using an approach for evaluating different types of interactions in ternary systems and the effect the structural features of interacting biomolecules have on the thermochemical characteristics of N-acetylglycine dissolution.

Thermo-Chemical Convection in Europa's Icy Shell with Salinity

NASA Technical Reports Server (NTRS)

Han, L.; Showman, A. P.

2005-01-01

Europa's icy surface displays numerous pits, uplifts, and chaos terrains that have been suggested to result from solid-state thermal convection in the ice shell, perhaps aided by partial melting. However, numerical simulations of thermal convection show that plumes have insufficient buoyancy to produce surface deformation. Here we present numerical simulations of thermochemical convection to test the hypothesis that convection with salinity can produce Europa's pits and domes. Our simulations show that domes (200-300 m) and pits (300-400 m) comparable to the observations can be produced in an ice shell of 15 km thick with 5-10% compositional density variation if the maximum viscosity is less than 10(exp 18) Pa sec. Additional information is included in the original extended abstract.

Thermochemical production of hydrogen

DOEpatents

Dreyfuss, Robert M.

1976-07-13

A thermochemical reaction cycle for the generation of hydrogen from water comprising the following sequence of reactions wherein M represents a metal and Z represents a metalloid selected from the arsenic-antimony-bismuth and selenium-tellurium subgroups of the periodic system: 2MO + Z + SO.sub.2 .fwdarw. MZ + MSO.sub.4 (1) mz + h.sub.2 so.sub.4 .fwdarw. mso.sub.4 + h.sub.2 z (2) 2mso.sub.4 .fwdarw. 2mo + so.sub.2 + so.sub.3 + 1/20.sub.2 (3) h.sub.2 z .fwdarw. z + h.sub.2 (4) h.sub.2 o + so.sub.3 .fwdarw. h.sub.2 so.sub.4 (5) the net reaction is the decomposition of water into hydrogen and oxygen.

Method for thermochemical decomposition of water

DOEpatents

Abraham, Bernard M.; Schreiner, Felix

1977-01-11

Water is thermochemically decomposed to produce hydrogen by the following sequence of reactions: KI, NH.sub.3, CO.sub. 2 and water in an organic solvent such as ethyl or propyl alcohol are reacted to produce KHCO 3 and NH.sub.4 I. The KHCO.sub.3 is thermally decomposed to K.sub.2 CO.sub.3, H.sub.2 O and CO.sub.2, while the NH.sub.4 I is reacted with Hg to produce HgI.sub.2, NH.sub.3 and H.sub.2. The K.sub.2 CO.sub.3 obtained by calcining KHCO.sub.3 is then reacted with HgI.sub.2 to produce Hg, KI, CO and O.sub.2. All products of the reaction are recycled except hydrogen and oxygen.

Soot and Spectral Radiation Modeling in ECN Spray A and in Engines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haworth, Daniel C; Ferreyro-Fernandez, Sebastian; Paul, Chandan

The amount of soot formed in a turbulent combustion system is determined by a complex system of coupled nonlinear chemical and physical processes. Different physical subprocesses can dominate, depending on the hydrodynamic and thermochemical environments. Similarly, the relative importance of reabsorption, spectral radiation properties, and molecular gas radiation versus soot radiation varies with thermochemical conditions, and in ways that are difficult to predict for the highly nonhomogeneous in-cylinder mixtures in engines. Here it is shown that transport and mixing play relatively more important roles as rate-determining processes in soot formation at engine-relevant conditions. It is also shown that molecular gasmore » radiation and spectral radiation properties are important for engine-relevant conditions.« less

A thermochemical explanation for the stability of NaCl3 and NaCl7

NASA Astrophysics Data System (ADS)

Fernandes de Farias, Robson

2017-03-01

Thermodynamically stable cubic and orthorhombic NaCl3 as well as NaCl7 have been synthesized (Zhang et al., 2013). In the present work, a thermochemical explanation for the stability of such unusual sodium chlorides is provided, based on lattice energy values. Using the Glasser-Jenkins generalized equation (Glasser and Jenkins, 2000) lattice energies (kJ mol-1) of -162.5, -168.9 and -113.1 are calculated for Pm3n NaCl3, Pnma NaCl3 and NaCl7, respectively. It is postulated that any NaxCly compound could be synthesized, if the ionic character of the Nasbnd Cl bond in the prepared compound remains around 80%, and the sodium charge below unit.

Facile synthesis of iron oxides/reduced graphene oxide composites: application for electromagnetic wave absorption at high temperature.

PubMed

Zhang, Lili; Yu, Xinxin; Hu, Hongrui; Li, Yang; Wu, Mingzai; Wang, Zhongzhu; Li, Guang; Sun, Zhaoqi; Chen, Changle

2015-03-19

Iron oxides/reduced graphene oxide composites were synthesized by facile thermochemical reactions of graphite oxide and FeSO4 · 7H2O. By adjusting reaction temperature, α-Fe2O3/reduced graphene oxide and Fe3O4/reduced graphene oxide composites can be obtained conveniently. Graphene oxide and reduced graphene oxide sheets were demonstrated to regulate the phase transition from α-Fe2O3 to Fe3O4 via γ-Fe2O3, which was reported for the first time. The hydroxyl groups attached on the graphene oxide sheets and H2 gas generated during the annealing of graphene oxide are believed to play an important role during these phase transformations. These samples showed good electromagnetic wave absorption performance due to their electromagnetic complementary effect. These samples possess much better electromagnetic wave absorption properties than the mixture of separately prepared Fe3O4 with rGO, suggesting the crucial role of synthetic method in determining the product properties. Also, these samples perform much better than commercial absorbers. Most importantly, the great stability of these composites is highly advantageous for applications as electromagnetic wave absorption materials at high temperatures.

Hydrogen uptake characteristics of mischmetal based alloy

NASA Astrophysics Data System (ADS)

Jain, Ankur; Jain, R. K.; Jain, I. P.

Hydrogen storage properties of Mm 39.2Ni 42.1Mn 4.9Al 1.25Co 10.2Fe 2.35 alloy have been systematically studied in the present work. An attempt is made to relate the content of hydrogen with change in resistance. It is found that the resistance of material increases with the increase in value of H/ M due to hydrogen absorption. Pressure composition (P-C-T) isotherm using water displacement method has been investigated in the temperature and pressure ranges of 308 ≤ T ≤ 338 K and 0.5 ≤ P ≤ 10 bar, respectively. The P-C isotherms show the presence of two single α and β regions one mixed α + β phase. The maximum H (wt%) was found to be around 1.53 at 308 K and around 6 bar. Since enthalpy is an index of thermochemical stability of metal hydride the thermo dynamical parameters viz., the relative partial molar enthalpy (Δ H) and relative partial molar entropy (Δ S) of dissolved hydrogen have been calculated by plotting the Van't Hoff plot. The variation of Δ H and Δ S with the hydrogen concentration confirm the phase boundaries.

Facile synthesis of iron oxides/reduced graphene oxide composites: application for electromagnetic wave absorption at high temperature

PubMed Central

Zhang, Lili; Yu, Xinxin; Hu, Hongrui; Li, Yang; Wu, Mingzai; Wang, Zhongzhu; Li, Guang; Sun, Zhaoqi; Chen, Changle

2015-01-01

Iron oxides/reduced graphene oxide composites were synthesized by facile thermochemical reactions of graphite oxide and FeSO4·7H2O. By adjusting reaction temperature, α-Fe2O3/reduced graphene oxide and Fe3O4/reduced graphene oxide composites can be obtained conveniently. Graphene oxide and reduced graphene oxide sheets were demonstrated to regulate the phase transition from α-Fe2O3 to Fe3O4 via γ-Fe2O3, which was reported for the first time. The hydroxyl groups attached on the graphene oxide sheets and H2 gas generated during the annealing of graphene oxide are believed to play an important role during these phase transformations. These samples showed good electromagnetic wave absorption performance due to their electromagnetic complementary effect. These samples possess much better electromagnetic wave absorption properties than the mixture of separately prepared Fe3O4 with rGO, suggesting the crucial role of synthetic method in determining the product properties. Also, these samples perform much better than commercial absorbers. Most importantly, the great stability of these composites is highly advantageous for applications as electromagnetic wave absorption materials at high temperatures. PMID:25788158

Thermochemistry of Silicates

NASA Technical Reports Server (NTRS)

Costa, Gustavo; Jacobson, Nathan

2015-01-01

The thermodynamic properties of vapor and condensed phases of silicates are crucial in many fields of science. These quantities address fundamental questions on the formation, stability, transformation, and physical properties of silicate minerals and silicate coating compositions. Here the thermodynamic activities of silica and other species in solid solution have been measured by the analysis of the corresponding high temperature vapors using Knudsen Effusion Mass Spectrometry (KEMS). In first set of experiments KEMS has been used to examine the volatility sequence of species (Fe, SiO, Mg, O2 and O) present in the vapor phase during heating of fosterite-rich olivine (Fo93Fa7) up to 2400 C and to measure the Fe, SiO and Mg activities in its solid solution. The data of fosterite-rich olivine are essential for thermochemical equilibrium models to predict the atmospheric and surface composition of hot, rocky exoplanets (Lava Planets). In the second set of experiments the measured thermodynamic activities of the silica in Y2O3-SiO2 and Yb2O3-SiO2 systems are used to assess their reactivity and degradation recession as environmental barrier coatings (EBCs) in combustion environments (e.g. non-moveable parts of gas turbine engine).

The evolution of continental roots in numerical thermo-chemical mantle convection models including differentiation by partial melting

NASA Astrophysics Data System (ADS)

de Smet, J. H.; van den Berg, A. P.; Vlaar, N. J.

1999-09-01

Incorporating upper mantle differentiation through decompression melting in a numerical mantle convection model, we demonstrate that a compositionally distinct root consisting of depleted peridotite can grow and remain stable during a long period of secular cooling. Our modeling results show that in a hot convecting mantle partial melting will produce a compositional layering in a relatively short time of about 50 Ma. Due to secular cooling mantle differentiation finally stops before 1 Ga. The resulting continental root remains stable on a billion year time scale due to the combined effects of its intrinsically lower density and temperature-dependent rheology. Two different parameterizations of the melting phase-diagram are used in the models. The results indicate that during the Archaean melting occurred on a significant scale in the deep regions of the upper mantle, at pressures in excess of 15 GPa. The compositional depths of continental roots extend to 400 km depending on the potential temperature and the type of phase-diagram parameterization used in the model. The results reveal a strong correlation between lateral variations of temperature and the thickness of the continental root. This shows that cold regions in cratons are stabilized by a thick depleted root.

Influence of different propellant systems on ablation of EPDM insulators in overload state

NASA Astrophysics Data System (ADS)

Guan, Yiwen; Li, Jiang; Liu, Yang; Xu, Tuanwei

2018-04-01

This study examines the propellants used in full-scale solid rocket motors (SRM) and investigates how insulator ablation is affected by two propellant formulations (A and B) during flight overload conditions. An experimental study, theoretical analysis, and numerical simulations were performed to discover the intrinsic causes of insulator ablation rates from the perspective of lab-scaled ground-firing tests, the decoupling of thermochemical ablation, and particle erosion. In addition, the difference in propellant composition, and the insulator charring layer microstructure were analyzed. Results reveal that the degree of insulator ablation is positively correlated with the propellant burn rate, particle velocity, and aggregate concentrations during the condensed phase. A lower ratio of energetic additive material in the AP oxidizer of the propellant is promising for the reduction in particle size and increase in the burn rate and pressure index. However, the overall higher velocity of a two-phase flow causes severe erosion of the insulation material. While the higher ratio of energetic additive to the AP oxidizer imparts a smaller ablation rate to the insulator (under lab-scale test conditions), the slag deposition problem in the combustion chamber may cause catastrophic consequences for future large full-scale SRM flight experiments.

Scalable and Tunable Carbide-Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Regmi, Yagya; Rogers, Bridget; Labbe, Nicole

We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method comprised of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon increasing the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates usingmore » pyrolysis gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized to tune the composition of the bio-oil downstream.« less

Scalable and Tunable Carbide-Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

DOE PAGES

Regmi, Yagya; Rogers, Bridget; Labbe, Nicole; ...

2017-07-13

We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method comprised of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon increasing the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates usingmore » pyrolysis gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized to tune the composition of the bio-oil downstream.« less

Database for Regional Geology, Phase 1: A Tool for Informing Regional Evaluations of Alternative Geologic Media and Decision Making

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perry, Frank Vinton; Kelley, Richard E.; Birdsell, Suzanne M.

Reported is progress in the following areas: Phase 1 and 2 websites for the regional geology GIS database; terrane maps of crystalline basement rocks; inventory of shale formations in the US; and rock properties and in-situ conditions for shale estimated from sonic velocity measurements.

NHEXAS PHASE I ARIZONA STUDY--STANDARD OPERATING PROCEDURE FOR DATABASE TREE AND DATA SOURCES (UA-D-41.0)

EPA Science Inventory

The purpose of this SOP is to describe the database storage organization, as well as describe the sources of data for each database used during the Arizona NHEXAS project and the "Border" study. Keywords: data; database; organization.

The National Human Exposure Assessment Sur...

Analysis and comparison of biomass pyrolysis/gasification condensates: Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elliott, D.C.

1986-06-01

This report provides results of chemical and physical analysis of condensates from eleven biomass gasification and pyrolysis systems. The samples were representative of the various reactor configurations being researched within the Department of Energy, Biomass Thermochemical Conversion program. The condensates included tar phases and aqueous phases. The analyses included gross compositional analysis (elemental analysis, ash, moisture), physical characterization (pour point, viscosity, density, heat of combustion, distillation), specific chemical analysis (gas chromatography/mass spectrometry, infrared spectrophotometry, proton and carbon-13 nuclear magnetic resonance spectrometry) and biological activity (Ames assay and mouse skin tumorigenicity tests). These results are the first step of a longermore » term program to determine the properties, handling requirements, and utility of the condensates recovered from biomass gasification and pyrolysis. The analytical data demonstrates the wide range of chemical composition of the organics recovered in the condensates and suggests a direct relationship between operating temperature and chemical composition of the condensates. A continuous pathway of thermal degradation of the tar components as a function of temperature is proposed. Variations in the chemical composition of the organic components in the tars are reflected in the physical properties of tars and phase stability in relation to water in the condensate. The biological activity appears to be limited to the tars produced at high temperatures. 56 refs., 25 figs., 21 tabs.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rakshit, S.K.; Naik, Y.P.; Parida, S.C.

Three ternary oxides LiAl{sub 5}O{sub 8}(s), LiAlO{sub 2}(s) and Li{sub 5}AlO{sub 4}(s) in the system Li-Al-O were prepared by solid-state reaction route and characterized by X-ray powder diffraction method. Equilibrium partial pressure of CO{sub 2}(g) over the three-phase mixtures {l_brace}LiAl{sub 5}O{sub 8}(s)+Li{sub 2}CO{sub 3}(s)+5Al{sub 2}O{sub 3}(s){r_brace}, {l_brace}LiAl{sub 5}O{sub 8}(s)+5LiAlO{sub 2}(s)+2Li{sub 2}CO{sub 3}(s){r_brace} and {l_brace}LiAlO{sub 2}(s)+Li{sub 5}AlO{sub 4}(s)+2Li{sub 2}CO{sub 3}(s){r_brace} were measured using Knudsen effusion quadrupole mass spectrometry (KEQMS). Solid-state galvanic cell technique based on calcium fluoride electrolyte was used to determine the standard molar Gibbs energies of formations of these aluminates. The standard molar Gibbs energies of formation of thesemore » three aluminates calculated from KEQMS and galvanic cell measurements were in good agreement. Heat capacities of individual ternary oxides were measured from 127 to 868 K using differential scanning calorimetry. Thermodynamic tables representing the values of {delta}{sub f}H{sup 0}(298.15 K), S{sup 0}(298.15 K) S{sup 0}(T), C{sub p}{sup 0}(T), H{sup 0}(T), {l_brace}H{sup 0}(T)-H{sup 0}(298.15 K){r_brace}, G{sup 0}(T), {delta}{sub f}H{sup 0}(T), {delta}{sub f}G{sup 0}(T) and free energy function (fef) were constructed using second law analysis and FACTSAGE thermo-chemical database software. - Graphical abstract: Comparison of {delta}{sub f}G{sub m}{sup 0} of ternary oxides determined from KEQMS and solid-state galvanic cell techniques. (O) KEQMS, (9632;) solid-state galvanic cell and solid line: combined fit of both the experimental data.« less

Geodynamic modelling of low-buoyancy thermo-chemical plumes

NASA Astrophysics Data System (ADS)

Dannberg, Juliane; Sobolev, Stephan

2015-04-01

The Earth's biggest magmatic events that form Large Igneous Provinces are believed to originate from massive melting when hot mantle plumes rising from the lowermost mantle reach the base of the lithosphere. Classical models of thermal mantle plumes predict a flattening of the plume head to a disk-like structure, a kilometer-scale surface uplift just before the initiation of LIPs and thin plume tails. However, there are seismic observations and paleo-topography data that are difficult to explain with this classical approach. Here, using numerical models, we show that the issue can be resolved if major mantle plumes are thermo-chemical rather than purely thermal. It has been suggested a long time ago that subducted oceanic crust could be recycled by mantle plumes; and based on geochemical data, they may contain up to 15-20% of this recycled material in the form of dense eclogite, which drastically decreases their buoyancy and makes it depth-dependent. We perform numerical experiments in a 3D spherical shell geometry to investigate the dynamics of the plume ascent, the interaction between plume- and plate-driven flow and the dynamics of melting in a plume head. For this purpose, we use the finite-element code ASPECT, which allows for complex temperature-, pressure- and composition-dependent material properties. Moreover, our models incorporate phase transitions (including melting) with the accompanying rheological and density changes, Clapeyron slopes and latent heat effects for both peridotite and eclogite, mantle compressibility and a strong temperature- and depth-dependent viscosity. We demonstrate that despite their low buoyancy, such plumes can rise through the whole mantle causing only negligible surface uplift. Conditions for this ascent are high plume volume and moderate lower mantle subadiabaticity. While high plume buoyancy results in plumes directly advancing to the base of the lithosphere, plumes with slightly lower buoyancy pond in a depth of 300-400 km and form pools or a second layer of hot material. These structures are caused by phase transitions occurring in different depths in peridotite and eclogite; and they become asymmetric and finger-like channels begin to form when the plume gets entrained by a quickly moving overlying plate. We also show that the bulky tails of large and hot low-buoyancy plumes are stable for several tens of millions of years and that their shapes fit seismic tomography data much better than the narrow tails of thermal plumes.

Construction of a coarse-grain quasi-classical trajectory method. II. Comparison against the direct molecular simulation method

NASA Astrophysics Data System (ADS)

Macdonald, R. L.; Grover, M. S.; Schwartzentruber, T. E.; Panesi, M.

2018-02-01

This work presents the analysis of non-equilibrium energy transfer and dissociation of nitrogen molecules (N2(g+1Σ) ) using two different approaches: the direct molecular simulation (DMS) method and the coarse-grain quasi-classical trajectory (CG-QCT) method. The two methods are used to study thermochemical relaxation in a zero-dimensional isochoric and isothermal reactor in which the nitrogen molecules are heated to several thousand degrees Kelvin, forcing the system into strong non-equilibrium. The analysis considers thermochemical relaxation for temperatures ranging from 10 000 to 25 000 K. Both methods make use of the same potential energy surface for the N2(g+1Σ ) -N2(g+1Σ ) system taken from the NASA Ames quantum chemistry database. Within the CG-QCT method, the rovibrational energy levels of the electronic ground state of the nitrogen molecule are lumped into a reduced number of bins. Two different grouping strategies are used: the more conventional vibrational-based grouping, widely used in the literature, and energy-based grouping. The analysis of both the internal state populations and concentration profiles show excellent agreement between the energy-based grouping and the DMS solutions. During the energy transfer process, discrepancies arise between the energy-based grouping and DMS solution due to the increased importance of mode separation for low energy states. By contrast, the vibrational grouping, traditionally considered state-of-the-art, captures well the behavior of the energy relaxation but fails to consistently predict the dissociation process. The deficiency of the vibrational grouping model is due to the assumption of strict mode separation and equilibrium of rotational energy states. These assumptions result in errors predicting the energy contribution to dissociation from the rotational and vibrational modes, with rotational energy actually contributing 30%-40% of the energy required to dissociate a molecule. This work confirms the findings discussed in Paper I [R. L. Macdonald et al., J. Chem. Phys. 148, 054309 (2018)], which underlines the importance of rotational energy to the dissociation process, and demonstrates that an accurate non-equilibrium chemistry model must accurately predict the deviation of rovibrational distribution from equilibrium.

Construction of a coarse-grain quasi-classical trajectory method. II. Comparison against the direct molecular simulation method.

PubMed

Macdonald, R L; Grover, M S; Schwartzentruber, T E; Panesi, M

2018-02-07

This work presents the analysis of non-equilibrium energy transfer and dissociation of nitrogen molecules (N 2 (Σg+1)) using two different approaches: the direct molecular simulation (DMS) method and the coarse-grain quasi-classical trajectory (CG-QCT) method. The two methods are used to study thermochemical relaxation in a zero-dimensional isochoric and isothermal reactor in which the nitrogen molecules are heated to several thousand degrees Kelvin, forcing the system into strong non-equilibrium. The analysis considers thermochemical relaxation for temperatures ranging from 10 000 to 25 000 K. Both methods make use of the same potential energy surface for the N 2 (Σg+1)-N 2 (Σg+1) system taken from the NASA Ames quantum chemistry database. Within the CG-QCT method, the rovibrational energy levels of the electronic ground state of the nitrogen molecule are lumped into a reduced number of bins. Two different grouping strategies are used: the more conventional vibrational-based grouping, widely used in the literature, and energy-based grouping. The analysis of both the internal state populations and concentration profiles show excellent agreement between the energy-based grouping and the DMS solutions. During the energy transfer process, discrepancies arise between the energy-based grouping and DMS solution due to the increased importance of mode separation for low energy states. By contrast, the vibrational grouping, traditionally considered state-of-the-art, captures well the behavior of the energy relaxation but fails to consistently predict the dissociation process. The deficiency of the vibrational grouping model is due to the assumption of strict mode separation and equilibrium of rotational energy states. These assumptions result in errors predicting the energy contribution to dissociation from the rotational and vibrational modes, with rotational energy actually contributing 30%-40% of the energy required to dissociate a molecule. This work confirms the findings discussed in Paper I [R. L. Macdonald et al., J. Chem. Phys. 148, 054309 (2018)], which underlines the importance of rotational energy to the dissociation process, and demonstrates that an accurate non-equilibrium chemistry model must accurately predict the deviation of rovibrational distribution from equilibrium.

Multi-step approach for comparing the local air pollution contributions of conventional and innovative MSW thermo-chemical treatments.

PubMed

Ragazzi, M; Rada, E C

2012-10-01

In the sector of municipal solid waste management the debate on the performances of conventional and novel thermo-chemical technologies is still relevant. When a plant must be constructed, decision makers often select a technology prior to analyzing the local environmental impact of the available options, as this type of study is generally developed when the design of the plant has been carried out. Additionally, in the literature there is a lack of comparative analyses of the contributions to local air pollution from different technologies. The present study offers a multi-step approach, based on pollutant emission factors and atmospheric dilution coefficients, for a local comparative analysis. With this approach it is possible to check if some assumptions related to the advantages of the novel thermochemical technologies, in terms of local direct impact on air quality, can be applied to municipal solid waste treatment. The selected processes concern combustion, gasification and pyrolysis, alone or in combination. The pollutants considered are both carcinogenic and non-carcinogenic. A case study is presented concerning the location of a plant in an alpine region and its contribution to the local air pollution. Results show that differences among technologies are less than expected. Performances of each technology are discussed in details. Copyright © 2012 Elsevier Ltd. All rights reserved.

In situ flow cell for combined X-ray absorption spectroscopy, X-ray diffraction, and mass spectrometry at high photon energies under solar thermochemical looping conditions

NASA Astrophysics Data System (ADS)

Rothensteiner, Matthäus; Jenni, Joel; Emerich, Hermann; Bonk, Alexander; Vogt, Ulrich F.; van Bokhoven, Jeroen A.

2017-08-01

An in situ/operando flow cell for transmission mode X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), and combined XAS/XRD measurements in a single experiment under the extreme conditions of two-step solar thermochemical looping for the dissociation of water and/or carbon dioxide was developed. The apparatus exposes materials to relevant conditions of both the auto-reduction and the oxidation sub-steps of the thermochemical cycle at ambient temperature up to 1773 K and enables determination of the composition of the effluent gases by online quadrupole mass spectrometry. The cell is based on a tube-in-tube design and is heated by means of a focusing infrared furnace. It was tested successfully for carbon dioxide splitting. In combined XAS/XRD experiments with an unfocused beam, XAS measurements were performed at the Ce K edge (40.4 keV) and XRD measurements at 64.8 keV and 55.9 keV. Furthermore, XRD measurements with a focused beam at 41.5 keV were carried out. Equimolar ceria-hafnia was auto-reduced in a flow of argon and chemically reduced in a flow of hydrogen/helium. Under reducing conditions, all cerium(iv) was converted to cerium(iii) and a cation-ordered pyrochlore-type structure was formed, which was not stable upon oxidation in a flow of carbon dioxide.

In situ flow cell for combined X-ray absorption spectroscopy, X-ray diffraction, and mass spectrometry at high photon energies under solar thermochemical looping conditions.

PubMed

Rothensteiner, Matthäus; Jenni, Joel; Emerich, Hermann; Bonk, Alexander; Vogt, Ulrich F; van Bokhoven, Jeroen A

2017-08-01

An in situ/operando flow cell for transmission mode X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), and combined XAS/XRD measurements in a single experiment under the extreme conditions of two-step solar thermochemical looping for the dissociation of water and/or carbon dioxide was developed. The apparatus exposes materials to relevant conditions of both the auto-reduction and the oxidation sub-steps of the thermochemical cycle at ambient temperature up to 1773 K and enables determination of the composition of the effluent gases by online quadrupole mass spectrometry. The cell is based on a tube-in-tube design and is heated by means of a focusing infrared furnace. It was tested successfully for carbon dioxide splitting. In combined XAS/XRD experiments with an unfocused beam, XAS measurements were performed at the Ce K edge (40.4 keV) and XRD measurements at 64.8 keV and 55.9 keV. Furthermore, XRD measurements with a focused beam at 41.5 keV were carried out. Equimolar ceria-hafnia was auto-reduced in a flow of argon and chemically reduced in a flow of hydrogen/helium. Under reducing conditions, all cerium(iv) was converted to cerium(iii) and a cation-ordered pyrochlore-type structure was formed, which was not stable upon oxidation in a flow of carbon dioxide.

A rapid burst in hotspot motion through the interaction of tectonics and deep mantle flow.

PubMed

Hassan, Rakib; Müller, R Dietmar; Gurnis, Michael; Williams, Simon E; Flament, Nicolas

2016-05-12

Volcanic hotspot tracks featuring linear progressions in the age of volcanism are typical surface expressions of plate tectonic movement on top of narrow plumes of hot material within Earth's mantle. Seismic imaging reveals that these plumes can be of deep origin--probably rooted on thermochemical structures in the lower mantle. Although palaeomagnetic and radiometric age data suggest that mantle flow can advect plume conduits laterally, the flow dynamics underlying the formation of the sharp bend occurring only in the Hawaiian-Emperor hotspot track in the Pacific Ocean remains enigmatic. Here we present palaeogeographically constrained numerical models of thermochemical convection and demonstrate that flow in the deep lower mantle under the north Pacific was anomalously vigorous between 100 million years ago and 50 million years ago as a consequence of long-lasting subduction systems, unlike those in the south Pacific. These models show a sharp bend in the Hawaiian-Emperor hotspot track arising from the interplay of plume tilt and the lateral advection of plume sources. The different trajectories of the Hawaiian and Louisville hotspot tracks arise from asymmetric deformation of thermochemical structures under the Pacific between 100 million years ago and 50 million years ago. This asymmetric deformation waned just before the Hawaiian-Emperor bend developed, owing to flow in the deepest lower mantle associated with slab descent in the north and south Pacific.

Beneficial effects of substituting trivalent ions in the B-site of La0.5Sr0.5Mn1-xAxO3 (A = Al, Ga, Sc) on the thermochemical generation of CO and H2 from CO2 and H2O.

PubMed

Dey, Sunita; Naidu, B S; Rao, C N R

2016-02-14

The effect of substitution of Al(3+), Ga(3+) and Sc(3+) ions in the Mn(3+) site of La0.5Sr0.5MnO3 on the thermochemical splitting of CO2 to generate CO has been studied in detail. Both La0.5Sr0.5Mn1-xGaxO3 and La0.5Sr0.5Mn1-xScxO3 give high yields of O2 and generate CO more efficiently than La0.5Sr0.5Mn1-xAlxO3 or the parent La0.5Sr0.5MnO3. Substitution of even 5% Sc(3+) (x = 0.05) results in a remarkable improvement in performance. Thus La0.5Sr0.5Mn0.95Sc0.05O3 produces 417 μmol g(-1) of O2 and 545 μmol g(-1) of CO, respectively, i.e. 2 and 1.7 times more O2 and CO than La0.5Sr0.5MnO3. This manganite also generates H2 satisfactorily by the thermochemical splitting of H2O.

Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle

NASA Technical Reports Server (NTRS)

Fegley, Bruce, Jr.

1988-01-01

The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth.

Inertial effects on thermochemically driven convection and hydromagnetic dynamos in a spherical shell

NASA Astrophysics Data System (ADS)

Šimkanin, Ján; Kyselica, Juraj; Guba, Peter

2018-03-01

We investigate the thermochemical convection and hydromagnetic dynamos in a spherical shell using the so-called codensity formulation with different buoyancy sources: the secular cooling from the mantle, the buoyancy sources due to the solidification at the inner core boundary and the combination of the two sources. Numerical simulations of the fully non-linear problem are performed using the PARODY code. In the thermochemical regime, we find that when the Prandtl numbers are lower than Ekman numbers, inertial convection is preferred, while the large-scale columnar convection is preferred otherwise. Unlike the large-scale convection, the inertial convection is found to be almost independent of the nature of driving buoyancy source. Moreover, the codensity field evolves to a new, radially symmetric stationary state. At the Ekman numbers much smaller than the Prandtl numbers, we have obtained the westward equatorial zonal flow in the chemically driven regime, while for the other cases zonal flows are eastward near the equator. In the dynamo regime, inertial convection is preferred when the Prandtl numbers are lower than Ekman numbers and the generated dipolar magnetic fields oscillate from the polar region to the mid-latitudes and back. In this case, the generated magnetic fields are independent of the type of buoyancy source. At the Prandtl numbers greater than Ekman numbers, both dipolar and hemispherical dynamos are found.

Final Report - Enhanced LAW Glass Property - Composition Models - Phase 1 VSL-13R2940-1, Rev. 0, dated 9/27/2013

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kruger, Albert A.; Muller, I.; Gilbo, K.

2013-11-13

The objectives of this work are aimed at the development of enhanced LAW propertycomposition models that expand the composition region covered by the models. The models of interest include PCT, VHT, viscosity and electrical conductivity. This is planned as a multi-year effort that will be performed in phases with the objectives listed below for the current phase.  Incorporate property- composition data from the new glasses into the database.  Assess the database and identify composition spaces in the database that need augmentation.  Develop statistically-designed composition matrices to cover the composition regions identified in the above analysis.  Preparemore » crucible melts of glass compositions from the statistically-designed composition matrix and measure the properties of interest.  Incorporate the above property-composition data into the database.  Assess existing models against the complete dataset and, as necessary, start development of new models.« less

Nonmetallic materials handbook. Volume 1: Epoxy materials

NASA Technical Reports Server (NTRS)

Podlaseck, S. E.

1979-01-01

Thermochemical and other properties data is presented for the following types of epoxy materials: adhesives, coatings finishes, inks, electrical insulation, encapsulants, sealants, composite laminates, tapes, and thermal insulators.

Mechanisms Underpinning Degradation of Protective Oxides and Thermal Barrier Coatings in High Hydrogen Content (HHC) - Fueled Turbines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mumm, Daniel

2013-08-31

The overarching goal of this research program has been to evaluate the potential impacts of coal-derived syngas and high-hydrogen content fuels on the degradation of turbine hot-section components through attack of protective oxides and thermal barrier coatings. The primary focus of this research program has been to explore mechanisms underpinning the observed degradation processes, and connections to the combustion environments and characteristic non-combustible constituents. Based on the mechanistic understanding of how these emerging fuel streams affect materials degradation, the ultimate goal of the program is to advance the goals of the Advanced Turbine Program by developing materials design protocols leadingmore » to turbine hot-section components with improved resistance to service lifetime degradation under advanced fuels exposures. This research program has been focused on studying how: (1) differing combustion environments – relative to traditional natural gas fired systems – affect both the growth rate of thermally grown oxide (TGO) layers and the stability of these oxides and of protective thermal barrier coatings (TBCs); and (2) how low levels of fuel impurities and characteristic non-combustibles interact with surface oxides, for instance through the development of molten deposits that lead to hot corrosion of protective TBC coatings. The overall program has been comprised of six inter-related themes, each comprising a research thrust over the program period, including: (i) evaluating the role of syngas and high hydrogen content (HHC) combustion environments in modifying component surface temperatures, heat transfer to the TBC coatings, and thermal gradients within these coatings; (ii) understanding the instability of TBC coatings in the syngas and high hydrogen environment with regards to decomposition, phase changes and sintering; (iii) characterizing ash deposition, molten phase development and infiltration, and associated corrosive/thermo-chemical attack mechanisms; (iv) developing a mechanics-based analysis of the driving forces for crack growth and delamination, based on molten phase infiltration, misfit upon cooling, and loss of compliance; (v) understanding changes in TGO growth mechanisms associated with these emerging combustion product streams; and (vi) identifying degradation resistant alternative materials (including new compositions or bi-layer concepts) for use in mitigating the observed degradation modes. To address the materials stability concerns, this program integrated research thrusts aimed at: (1) Conducting tests in simulated syngas and HHC environments to evaluate materials evolution and degradation mechanisms; assessing thermally grown oxide development unique to HHC environmental exposures; carrying out high-resolution imaging and microanalysis to elucidate the evolution of surface deposits (molten phase formation and infiltration); exploring thermo-chemical instabilities; assessing thermo-mechanical drivers and thermal gradient effects on degradation; and quantitatively measuring stress evolution due to enhanced sintering and thermo-chemical instabilities induced in the coating. (2) Executing experiments to study the melting and infiltration of simulated ash deposits, and identifying reaction products and evolving phases associated with molten phase corrosion mechanisms; utilizing thermal spray techniques to fabricate test coupons with controlled microstructures to study mechanisms of instability and degradation; facilitating thermal gradient testing; and developing new materials systems for laboratory testing; (3) Correlating information on the resulting combustion environments to properly assess materials exposure conditions and guide the development of lab-scale simulations of material exposures; specification of representative syngas and high-hydrogen fuels with realistic levels of impurities and contaminants, to explore differences in heat transfer, surface degradation, and deposit formation; and facilitating combustion rig testing of materials test coupons.« less

Practical Quantum Private Database Queries Based on Passive Round-Robin Differential Phase-shift Quantum Key Distribution.

PubMed

Li, Jian; Yang, Yu-Guang; Chen, Xiu-Bo; Zhou, Yi-Hua; Shi, Wei-Min

2016-08-19

A novel quantum private database query protocol is proposed, based on passive round-robin differential phase-shift quantum key distribution. Compared with previous quantum private database query protocols, the present protocol has the following unique merits: (i) the user Alice can obtain one and only one key bit so that both the efficiency and security of the present protocol can be ensured, and (ii) it does not require to change the length difference of the two arms in a Mach-Zehnder interferometer and just chooses two pulses passively to interfere with so that it is much simpler and more practical. The present protocol is also proved to be secure in terms of the user security and database security.

Studies of thermochemical water-splitting cycles

NASA Technical Reports Server (NTRS)

Remick, R. J.; Foh, S. E.

1980-01-01

Higher temperatures and more isothermal heat profiles of solar heat sources are developed. The metal oxide metal sulfate class of cycles were suited for solar heat sources. Electrochemical oxidation of SO2 and thermochemical reactions are presented. Electrolytic oxidation of sulfur dioxide in dilute sulfuric acid solutions were appropriate for metal oxide metal sulfate cycles. The cell voltage at workable current densities required for the oxidation of SO2 was critical to the efficient operation of any metal oxide metal sulfate cycle. A sulfur dioxide depolarized electrolysis cell for the splitting of water via optimization of the anode reaction is discussed. Sulfuric acid concentrations of 30 to 35 weight percent are preferred. Platinized platinum or smooth platinum gave the best anode kinetics at a given potential of the five materials examined.

Hydrogen production from solar energy

NASA Technical Reports Server (NTRS)

Eisenstadt, M. M.; Cox, K. E.

1975-01-01

Three alternatives for hydrogen production from solar energy have been analyzed on both efficiency and economic grounds. The analysis shows that the alternative using solar energy followed by thermochemical decomposition of water to produce hydrogen is the optimum one. The other schemes considered were the direct conversion of solar energy to electricity by silicon cells and water electrolysis, and the use of solar energy to power a vapor cycle followed by electrical generation and electrolysis. The capital cost of hydrogen via the thermochemical alternative was estimated at $575/kW of hydrogen output or $3.15/million Btu. Although this cost appears high when compared with hydrogen from other primary energy sources or from fossil fuel, environmental and social costs which favor solar energy may prove this scheme feasible in the future.

Novel Fabrication of Biodegradable Superabsorbent Microspheres with Diffusion Barrier through Thermo-Chemical Modification and Their Potential Agriculture Applications for Water Holding and Sustained Release of Fertilizer.

PubMed

Feng, Diejing; Bai, Bo; Wang, Honglun; Suo, Yourui

2017-07-26

Synergistic utilization of water and fertilizer has vital contribution to the modern production of agriculture. This work reports on a simple and facile strategy to prepare biodegradable yeast/sodium alginate/poly(vinyl alcohol) superabsorbent microspheres with a diffusion barrier merit by thermo-chemical modification route. The integrated performances, including water absorbency, water retention, water evaporation ratio, leaching loss control, sustained-release behaviors, and degradation in soil, were systematically investigated. The results revealed that the modified microspheres were a triumphant water and fertilizer manager to effectively hold water and control the unexpected leakage of fertilizer for sustained release. Therefore, this work provides a promising approach to ameliorate the utilization efficiency of water and fertilizer in potential agriculture applications.

Supercritical Fluids Processing of Biomass to Chemicals and Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olson, Norman K.

2011-09-28

The main objective of this project is to develop and/or enhance cost-effective methodologies for converting biomass into a wide variety of chemicals, fuels, and products using supercritical fluids. Supercritical fluids will be used both to perform reactions of biomass to chemicals and products as well as to perform extractions/separations of bio-based chemicals from non-homogeneous mixtures. This work supports the Biomass Program’s Thermochemical Platform Goals. Supercritical fluids are a thermochemical approach to processing biomass that, while aligned with the Biomass Program’s interests in gasification and pyrolysis, offer the potential for more precise and controllable reactions. Indeed, the literature with respect tomore » the use of water as a supercritical fluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”« less

G3X-K theory: A composite theoretical method for thermochemical kinetics

NASA Astrophysics Data System (ADS)

da Silva, Gabriel

2013-02-01

A composite theoretical method for accurate thermochemical kinetics, G3X-K, is described. This method is accurate to around 0.5 kcal mol-1 for barrier heights and 0.8 kcal mol-1 for enthalpies of formation. G3X-K is a modification of G3SX theory using the M06-2X density functional for structures and zero-point energies and parameterized for a test set of 223 heats of formation and 23 barrier heights. A reduced perturbation-order variant, G3X(MP3)-K, is also developed, providing around 0.7 kcal mol-1 accuracy for barrier heights and 0.9 kcal mol-1 accuracy for enthalpies, at reduced computational cost. Some opportunities to further improve Gn composite methods are identified and briefly discussed.

Moving bed reactor for solar thermochemical fuel production

DOEpatents

Ermanoski, Ivan

2013-04-16

Reactors and methods for solar thermochemical reactions are disclosed. Embodiments of reactors include at least two distinct reactor chambers between which there is at least a pressure differential. In embodiments, reactive particles are exchanged between chambers during a reaction cycle to thermally reduce the particles at first conditions and oxidize the particles at second conditions to produce chemical work from heat. In embodiments, chambers of a reactor are coupled to a heat exchanger to pre-heat the reactive particles prior to direct exposure to thermal energy with heat transferred from reduced reactive particles as the particles are oppositely conveyed between the thermal reduction chamber and the fuel production chamber. In an embodiment, particle conveyance is in part provided by an elevator which may further function as a heat exchanger.

Computational aerothermodynamics

NASA Technical Reports Server (NTRS)

Deiwert, George S.

1989-01-01

Computational aerothermodynamics concerns the coupling of real gas effects with equations of motion to include thermochemical rate processes for chemical and energy exchange phenomena. These processes concern the creation and destruction of gas species by chemical reactions and the transfer of energy between the various species and between the various energy modes (e.g., translation, rotation, vibration, ionization, dissociation/recombination, etc.) of the species. To gain some insight into when such phenomena occur for current and future aerospace flight vehicles the author shows the flight regimes of some typical vehicles (e.g., Concord, aerospace plane, Space Shuttle, associated space transfer vehicles, Apollo entry vehicle, etc.) in terms of flight altitude and flight speed. Also indicated are regimes where chemical reactions such as dissociation and ionization are important and where nonequilibrium thermochemical phenomena are important.

Doped calcium manganites for advanced high-temperature thermochemical energy storage

DOE PAGES

Babiniec, Sean M.; Coker, Eric N.; Miller, James E.; ...

2015-12-16

Developing efficient thermal storage for concentrating solar power plants is essential to reducing the cost of generated electricity, extending or shifting the hours of operation, and facilitating renewable penetration into the grid. Perovskite materials of the CaB xMn 1-xO 3-δ family, where B = Al or Ti, promise improvements in cost and energy storage density over other perovskites currently under investigation. Thermogravimetric analysis of the thermal reduction and reoxidation of these materials was used to extract equilibrium thermodynamic parameters. Lastly, the results demonstrate that these novel thermochemical energy storage media display the highest reaction enthalpy capacity for perovskites reported tomore » date, with a reaction enthalpy of 390 kJ/kg, a 56% increase over previously reported compositions.« less

Report on phase 2 of 1990 OSSA data census

NASA Technical Reports Server (NTRS)

King, Joseph H.

1991-01-01

The 1990 NASA Office of Space Science and Applications (OSSA) data census contributed significantly to a database intended to identify and briefly describe all archived data and potentially archive-desirable data from active and inactive NASA/OSSA spaceflight investigations. This database is being created at the National Space Science Data Center (NSSDC) and will be more comprehensive than the databases describing data held at individual sites such as NSSDC. Active investigations are defined as those flying on currently operational spacecraft or those that flew on recently operational spacecraft for which project-coordinated data archiving is continuing. Inactive investigations are those that flew on spacecraft that are no longer operational, and for which systematic archiving has ended. The principal purpose of this report is to describe phase two of the 1990 census. The previously reported phase one of this census, as well as a relevant 1981 census, are briefly discussed. The phase two survey instrument is described, those surveyed and respondents/reponses are identified, and data sets from inactive OSSA investigations discovered during the 1990 census (phase two) are briefly discussed individually.

Critical evaluation and thermodynamic optimization of the Iron-Rare-Earth systems

NASA Astrophysics Data System (ADS)

Konar, Bikram

Rare-Earth elements by virtue of its typical magnetic, electronic and chemical properties are gaining importance in power, electronics, telecommunications and sustainable green technology related industries. The Magnets from RE-alloys are more powerful than conventional magnets which have more longevity and high temperature workability. The dis-equilibrium in the Rare-Earth element supply and demand has increased the importance of recycling and extraction of REE's from used permanent Magnets. However, lack of the thermodynamic data on RE alloys has made it difficult to design an effective extraction and recycling process. In this regard, Computational Thermodynamic calculations can serve as a cost effective and less time consuming tool to design a waste magnet recycling process. The most common RE permanent magnet is Nd magnet (Nd 2Fe14B). Various elements such as Dy, Tb, Pr, Cu, Co, Ni, etc. are also added to increase its magnetic and mechanical properties. In order to perform reliable thermodynamic calculations for the RE recycling process, accurate thermodynamic database for RE and related alloys are required. The thermodynamic database can be developed using the so-called CALPHAD method. The database development based on the CALPHAD method is essentially the critical evaluation and optimization of all available thermodynamic and phase diagram data. As a results, one set of self-consistent thermodynamic functions for all phases in the given system can be obtained, which can reproduce all reliable thermodynamic and phase diagram data. The database containing the optimized Gibbs energy functions can be used to calculate complex chemical reactions for any high temperature processes. Typically a Gibbs energy minimization routine, such as in FactSage software, can be used to obtain the accurate thermodynamic equilibrium in multicomponent systems. As part of a large thermodynamic database development for permanent magnet recycling and Mg alloy design, all thermodynamic and phase diagram data in the literature for the fourteen Fe-RE binary systems: Fe-La, Fe-Ce, Fe-Pr, Fe-Nd, Fe-Sm, Fe-Gd, Fe-Tb, Fe-Dy, Fe-Ho, Fe-Er, Fe-Tm, Fe-Lu, Fe-Sc and Fe-Y are critically evaluated and optimized to obtain thermodynamic model parameters. The model parameters can be used to calculate phase diagrams and Gibbs energies of all phases as functions of temperature and composition. This database can be incorporated with the present thermodynamic database in FactSage software to perform complex chemical reactions and phase diagram calculations for RE magnet recycling process.

Characterization and Computational Modeling of Minor Phases in Alloy LSHR

NASA Technical Reports Server (NTRS)

Jou, Herng-Jeng; Olson, Gregory; Gabb, Timothy; Garg, Anita; Miller, Derek

2012-01-01

The minor phases of powder metallurgy disk superalloy LSHR were studied. Samples were consistently heat treated at three different temperatures for long times to approach equilibrium. Additional heat treatments were also performed for shorter times, to assess minor phase kinetics in non-equilibrium conditions. Minor phases including MC carbides, M23C6 carbides, M3B2 borides, and sigma were identified. Their average sizes and total area fractions were determined. CALPHAD thermodynamics databases and PrecipiCalc(TradeMark), a computational precipitation modeling tool, were employed with Ni-base thermodynamics and diffusion databases to model and simulate the phase microstructural evolution observed in the experiments with an objective to identify the model limitations and the directions of model enhancement.

Evolution of the protolunar disk: Dynamics, cooling timescale and implantation of volatiles onto the Earth

NASA Astrophysics Data System (ADS)

Charnoz, Sébastien; Michaut, Chloé

2015-11-01

It is thought that the Moon accreted from the protolunar disk that was assembled after the last giant impact on Earth. Due to its high temperature, the protolunar disk may act as a thermochemical reactor in which the material is processed before being incorporated into the Moon. Outstanding issues like devolatilisation and istotopic evolution are tied to the disk evolution, however its lifetime, dynamics and thermodynamics are unknown. Here, we numerically explore the long term viscous evolution of the protolunar disk using a one dimensional model where the different phases (vapor and condensed) are vertically stratified. Viscous heating, radiative cooling, phase transitions and gravitational instability are accounted for whereas Moon's accretion is not considered for the moment. The viscosity of the gas, liquid and solid phases dictates the disk evolution. We find that (1) the vapor condenses into liquid in ∼10 years, (2) a large fraction of the disk mass flows inward forming a hot and compact liquid disk between 1 and 1.7 Earth's radii, a region where the liquid is gravitationally stable and can accumulate, (3) the disk finally solidifies in 103 to 105 years. Viscous heating is never balanced by radiative cooling. If the vapor phase is abnormally viscous, due to magneto-rotational instability for instance, most of the disk volatile components are transported to Earth leaving a disk enriched in refractory elements. This opens a way to form a volatile-depleted Moon and would suggest that the missing Moon's volatiles are buried today into the Earth. The disk cooling timescale may be long enough to allow for planet/disk isotopic equilibration. However large uncertainties on the disk physics remain because of the complexity of its multi-phased structure.

Multiphase Dynamics of Magma Oceans

NASA Astrophysics Data System (ADS)

Boukaré, Charles-Edouard; Ricard, Yanick; Parmentier, Edgar M.

2017-04-01

Since the earliest study of the Apollo lunar samples, the magma ocean hypothesis has received increasing consideration for explaining the early evolution of terrestrial planets. Giant impacts seem to be able to melt significantly large planets at the end of their accretion. The evolution of the resulting magma ocean would set the initial conditions (thermal and compositionnal structure) for subsequent long-term solid-state planet dynamics. However, magma ocean dynamics remains poorly understood. The major challenge relies on understanding interactions between the physical properties of materials (e.g., viscosity (at liquid or solid state), buoyancy) and the complex dynamics of an extremely vigorously convecting system. Such complexities might be neglected in cases where liquidus/adiabat interactions and density stratification leads to stable situations. However, interesting possibilities arise when exploring magma ocean dynamics in other regime. In the case of the Earth, recent studies have shown that the liquidus might intersect the adiabat at mid-mantle depth and/or that solids might be buoyant at deep mantle conditions. These results require the consideration of more sophisticated scenarios. For instance, how does bottom-up crystallization look with buoyant crystals? To understand this complex dynamics, we develop a multiphase phase numerical code that can handle simultaneously phase change, the convection in each phase and in the slurry, as well as the compaction or decompaction of the two phases. Although our code can only run in a limited parameter range (Rayleigh number, viscosity contrast between phases, Prandlt number), it provides a rich dynamics that illustrates what could have happened. For a given liquidus/adiabat configuration and density contrast between melt and solid, we explore magma ocean scenarios by varying the relative timescales of three first order processes: solid-liquid separation, thermo-chemical convective motions and magma ocean cooling.

Propagation of Reactions in Thermally-damaged PBX-9501

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tringe, J W; Glascoe, E A; Kercher, J R

A thermally-initiated explosion in PBX-9501 (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) is observed in situ by flash x-ray imaging, and modeled with the LLNL multi-physics arbitrary-Lagrangian-Eulerian code ALE3D. The containment vessel deformation provides a useful estimate of the reaction pressure at the time of the explosion, which we calculate to be in the range 0.8-1.4 GPa. Closely-coupled ALE3D simulations of these experiments, utilizing the multi-phase convective burn model, provide detailed predictions of the reacted mass fraction and deflagration front acceleration. During the preinitiation heating phase of these experiments, the solid HMX portion of the PBX-9501 undergoes a {beta}-phase to {delta}-phase transition which damages the explosivemore » and induces porosity. The multi-phase convective burn model results demonstrate that damaged particle size and pressure are critical for predicting reaction speed and violence. In the model, energetic parameters are taken from LLNL's thermochemical-kinetics code Cheetah and burn rate parameters from Son et al. (2000). Model predictions of an accelerating deflagration front are in qualitative agreement with the experimental images assuming a mode particle diameter in the range 300-400 {micro}m. There is uncertainty in the initial porosity caused by thermal damage of PBX-9501 and, thus, the effective surface area for burning. To better understand these structures, we employ x-ray computed tomography (XRCT) to examine the microstructure of PBX-9501 before and after thermal damage. Although lack of contrast between grains and binder prevents the determination of full grain size distribution in this material, there are many domains visible in thermally damaged PBX-9501 with diameters in the 300-400 {micro}m range.« less

Bayesian Atmospheric Radiative Transfer (BART): Model, Statistics Driver, and Application to HD 209458b

NASA Astrophysics Data System (ADS)

Cubillos, Patricio; Harrington, Joseph; Blecic, Jasmina; Stemm, Madison M.; Lust, Nate B.; Foster, Andrew S.; Rojo, Patricio M.; Loredo, Thomas J.

2014-11-01

Multi-wavelength secondary-eclipse and transit depths probe the thermo-chemical properties of exoplanets. In recent years, several research groups have developed retrieval codes to analyze the existing data and study the prospects of future facilities. However, the scientific community has limited access to these packages. Here we premiere the open-source Bayesian Atmospheric Radiative Transfer (BART) code. We discuss the key aspects of the radiative-transfer algorithm and the statistical package. The radiation code includes line databases for all HITRAN molecules, high-temperature H2O, TiO, and VO, and includes a preprocessor for adding additional line databases without recompiling the radiation code. Collision-induced absorption lines are available for H2-H2 and H2-He. The parameterized thermal and molecular abundance profiles can be modified arbitrarily without recompilation. The generated spectra are integrated over arbitrary bandpasses for comparison to data. BART's statistical package, Multi-core Markov-chain Monte Carlo (MC3), is a general-purpose MCMC module. MC3 implements the Differental-evolution Markov-chain Monte Carlo algorithm (ter Braak 2006, 2009). MC3 converges 20-400 times faster than the usual Metropolis-Hastings MCMC algorithm, and in addition uses the Message Passing Interface (MPI) to parallelize the MCMC chains. We apply the BART retrieval code to the HD 209458b data set to estimate the planet's temperature profile and molecular abundances. This work was supported by NASA Planetary Atmospheres grant NNX12AI69G and NASA Astrophysics Data Analysis Program grant NNX13AF38G. JB holds a NASA Earth and Space Science Fellowship.

From atomic structure to excess entropy: a neutron diffraction and density functional theory study of CaO-Al2O3-SiO2 melts

NASA Astrophysics Data System (ADS)

Liu, Maoyuan; Jacob, Aurélie; Schmetterer, Clemens; Masset, Patrick J.; Hennet, Louis; Fischer, Henry E.; Kozaily, Jad; Jahn, Sandro; Gray-Weale, Angus

2016-04-01

Calcium aluminosilicate \\text{CaO}-\\text{A}{{\\text{l}}2}{{\\text{O}}3}-\\text{Si}{{\\text{O}}2} (CAS) melts with compositions {{≤ft(\\text{CaO}-\\text{Si}{{\\text{O}}2}\\right)}x}{{≤ft(\\text{A}{{\\text{l}}2}{{\\text{O}}3}\\right)}1-x} for x  <  0.5 and {{≤ft(\\text{A}{{\\text{l}}2}{{\\text{O}}3}\\right)}x}{{≤ft(\\text{Si}{{\\text{O}}2}\\right)}1-x} for x≥slant 0.5 are studied using neutron diffraction with aerodynamic levitation and density functional theory molecular dynamics modelling. Simulated structure factors are found to be in good agreement with experimental structure factors. Local atomic structures from simulations reveal the role of calcium cations as a network modifier, and aluminium cations as a non-tetrahedral network former. Distributions of tetrahedral order show that an increasing concentration of the network former Al increases entropy, while an increasing concentration of the network modifier Ca decreases entropy. This trend is opposite to the conventional understanding that increasing amounts of network former should increase order in the network liquid, and so decrease entropy. The two-body correlation entropy S 2 is found to not correlate with the excess entropy values obtained from thermochemical databases, while entropies including higher-order correlations such as tetrahedral order, O-M-O or M-O-M bond angles and Q N environments show a clear linear correlation between computed entropy and database excess entropy. The possible relationship between atomic structures and excess entropy is discussed.

Thermodynamic assessments and inter-relationships between systems involving Al, Am, Ga, Pu, and U

NASA Astrophysics Data System (ADS)

Perron, A.; Turchi, P. E. A.; Landa, A.; Oudot, B.; Ravat, B.; Delaunay, F.

2016-12-01

A newly developed self-consistent CALPHAD thermodynamic database involving Al, Am, Ga, Pu, and U is presented. A first optimization of the slightly characterized Am-Al and completely unknown Am-Ga phase diagrams is proposed. To this end, phase diagram features as crystal structures, stoichiometric compounds, solubility limits, and melting temperatures have been studied along the U-Al → Pu-Al → Am-Al, and U-Ga → Pu-Ga → Am-Ga series, and the thermodynamic assessments involving Al and Ga alloying are compared. In addition, two distinct optimizations of the Pu-Al phase diagram are proposed to account for the low temperature and Pu-rich region controversy. The previously assessed thermodynamics of the other binary systems (Am-Pu, Am-U, Pu-U, and Al-Ga) is also included in the database and is briefly described in the present work. Finally, predictions on phase stability of ternary and quaternary systems of interest are reported to check the consistency of the database.

Thermodynamic assessments and inter-relationships between systems involving Al, Am, Ga, Pu, and U

DOE PAGES

Perron, A.; Turchi, P. E. A.; Landa, A.; ...

2016-12-01

We present a newly developed self-consistent CALPHAD thermodynamic database involving Al, Am, Ga, Pu, and U. A first optimization of the slightly characterized Am-Al and completely unknown Am-Ga phase diagrams is proposed. To this end, phase diagram features as crystal structures, stoichiometric compounds, solubility limits, and melting temperatures have been studied along the U-Al → Pu-Al → Am-Al, and U-Ga → Pu-Ga → Am-Ga series, and the thermodynamic assessments involving Al and Ga alloying are compared. In addition, two distinct optimizations of the Pu-Al phase diagram are proposed to account for the low temperature and Pu-rich region controversy. We includedmore » the previously assessed thermodynamics of the other binary systems (Am-Pu, Am-U, Pu-U, and Al-Ga) in the database and is briefly described in the present work. In conclusion, predictions on phase stability of ternary and quaternary systems of interest are reported to check the consistency of the database.« less

Contingency Contractor Optimization Phase 3 Sustainment Database Design Document - Contingency Contractor Optimization Tool - Prototype

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frazier, Christopher Rawls; Durfee, Justin David; Bandlow, Alisa

The Contingency Contractor Optimization Tool – Prototype (CCOT-P) database is used to store input and output data for the linear program model described in [1]. The database allows queries to retrieve this data and updating and inserting new input data.

Comparison of published and unpublished phase I clinical cancer trials: an analysis of the CliniclTrials.gov database.

PubMed

Shepshelovich, D; Goldvaser, H; Wang, L; Abdul Razak, A R

2017-12-13

Introduction The role of phase I cancer trials is constantly evolving and they are increasingly being used in 'go/no' decisions in drug development. As a result, there is a growing need to ensure trials are published when completed. There are limited data on the publication rate and the factors associated with publication in phase I trials. Methods The ClinicalTrials.gov database was searched for completed adult phase I cancer trials with reported results. PubMed was searched for matching publications published prior to April 1, 2017. Logistic regression was used to identify factors associated with unpublished trials. Linear regression was used to explore factors associated with time lag from study database lock to publication for published trials. Results The study cohort included 319 trials. 95 (30%) trials had no matching publication. Thirty (9%) trials were not published in abstract form as well. On multivariable analysis, the most significant factor associated with unpublished trials was industry funding (odds ratio 3.3, 95% confidence interval 1.7-6.6, p=0.019). For published trials, time lag between database lock and publication was longer by 10.9 months (standard error 3.6, p<0.001) for industry funded trials compared with medical center funded trials. Conclusions Timely publishing of early cancer clinical trials results remains unsatisfactory. Industry funded phase I cancer trials were more likely to remain unpublished, and were associated with a longer time lag from database lock to publication. Policies that promote transparency and data sharing in clinical trial research might improve accountability among industry and investigators and improve timely results publication.

Investigation of Thermochemistry Associated with the Carbon–Carbon Coupling Reactions of Furan and Furfural Using ab Initio Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Cong; Assary, Rajeev S.; Curtiss, Larry A.

2014-06-26

Upgrading of furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan, can be coupled with various C1 to C4 lower molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase tomore » produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (~25 kcal/mol) are lower than the cellulose activation or decomposition reactions (~50 kcal/mol). Cycloaddition of C5-C8 cyclo-ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ~20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.« less

Molecular energetics of cytosine revisited: a joint computational and experimental study.

PubMed

Gomes, José R B; Ribeiro da Silva, Maria D M C; Freitas, Vera L S; Ribeiro da Silva, Manuel A V

2007-08-02

A static bomb calorimeter has been used to measure the standard molar energy of combustion, in oxygen, at T = 298.15 K, of a commercial sample of cytosine. From this energy, the standard (p degrees = 0.1 MPa) molar enthalpy of formation in the crystalline state was derived as -(221.9 +/- 1.7) kJ.mol(-1). This value confirms one experimental value already published in the literature but differs from another literature value by 13.5 kJ.mol(-1). Using the present standard molar enthalpy of formation in the condensed phase and the enthalpy of sublimation due to Burkinshaw and Mortimer [J. Chem. Soc., Dalton Trans. 1984, 75], (155.0 +/- 3.0) kJ.mol(-1), results in a value for the gas-phase standard molar enthalpy of formation for cytosine of -66.9 kJ.mol(-1). A similar value, -65.1 kJ.mol(-1), has been estimated after G3MP2B3 calculations combined with the reaction of atomization on three different tautomers of cytosine. In agreement with experimental evidence, the hydroxy-amino tautomer is the most stable form of cytosine in the gas phase. The enthalpies of formation of the other two tautomers were also estimated as -60.7 kJ.mol(-1) and -57.2 kJ.mol(-1) for the oxo-amino and oxo-imino tautomers, respectively. The same composite approach was also used to compute other thermochemical data, which is difficult to be measured experimentally, such as C-H, N-H, and O-H bond dissociation enthalpies, gas-phase acidities, and ionization enthalpies.

Thermochemical emission and transformation of chlorinated paraffins in inert and oxidizing atmospheres.

PubMed

Xin, Shanzhi; Gao, Wei; Wang, Yawei; Jiang, Guibin

2017-10-01

Chlorinated paraffins (CPs) generally function as flame retardants and plasticizers in various materials. They are most likely to be processed by thermal processes during the entire life cycle. However, data on the formation and emission of CPs during thermal processes are still not fully understood. In this study, we simulated industrial thermal processes to investigate the emission of medium-chain chlorinated paraffins (MCCPs) and short-chain chlorinated paraffins (SCCPs) using commercial CP52 as the feedstock. We found that CP52 decomposed very easily at 210-320 °C. The decomposition of CPs generated large quantities of MCCPs and SCCPs. These remained in the residue at low temperature (∼200 °C) and were gradually released into the gas phase at higher temperatures. MCCPs and SCCPs were not detected in either the residue or the gas phase when the temperature exceeded 400 °C. However, considerable concentrations of aromatic and chlorinated aromatic hydrocarbons (Cl-PAHs) were identified in the gas phase, and they were formed as the amount of SCCPs and MCCPs decreased. Cl-PAHs were dominated by low-chlorinated chlorobenzenes, polychlorinated biphenyls, and polychlorinated naphthalenes. Oxygen promoted the release and decomposition of SCCPs in the gas phase. The results of the present study revealed the release of MCCPs and SCCPs and their synergistic emission with Cl-PAHs when CPs were subjected to heat. This work may also provide data for developing multiple techniques to control the emission of CPs and Cl-PAHs. Copyright © 2017 Elsevier Ltd. All rights reserved.

On the Fracture Toughness and Crack Growth Resistance of Bio-Inspired Thermal Spray Hybrid Composites

NASA Astrophysics Data System (ADS)

Resnick, Michael Murray

Surface exploration of the Moon and Asteroids can provide important information to scientists regarding the origins of the solar-system and life . Small robots and sensor modules can enable low-cost surface exploration. In the near future, they are the main machines providing these answers. Advanced in electronics, sensors and actuators enable ever smaller platforms, with compromising functionality. However similar advances haven't taken place for power supplies and thermal control system. The lunar south pole has temperatures in the range of -100 to -150 °C. Similarly, asteroid surfaces can encounter temperatures of -150 °C. Most electronics and batteries do not work below -40 °C. An effective thermal control system is critical towards making small robots and sensors module for extreme environments feasible. In this work, the feasibility of using thermochemical storage materials as a possible thermal control solution is analyzed for small robots and sensor modules for lunar and asteroid surface environments. The presented technology will focus on using resources that is readily generated as waste product aboard a spacecraft or is available off-world through In-Situ Resource Utilization (ISRU). In this work, a sensor module for extreme environment has been designed and prototyped. Our intention is to have a network of tens or hundreds of sensor modules that can communicate and interact with each other while also gathering science data. The design contains environmental sensors like temperature sensors and IMU (containing accelerometer, gyro and magnetometer) to gather data. The sensor module would nominally contain an electrical heater and insulation. The thermal heating effect provided by this active heater is compared with the proposed technology that utilizes thermochemical storage chemicals. Our results show that a thermochemical storage-based thermal control system is feasible for use in extreme temperatures. A performance increase of 80% is predicted for the sensor modules on the asteroid Eros using thermochemical based storage system. At laboratory level, a performance increase of 8 to 9 % is observed at ambient temperatures of -32°C and -40 °C.

Solar fuels production as a sustainable alternative for substituting fossil fuels: COSOLπ project

NASA Astrophysics Data System (ADS)

Hernando Romero-Paredes, R.; Alvarado-Gil, Juan José; Arancibia-Bulnes, Camilo Alberto; Ramos-Sánchez, Víctor Hugo; Villafán-Vidales, Heidi Isabel; Espinosa-Paredes, Gilberto; Abanades, Stéphane

2017-06-01

This article presents, in summary form, the characteristics of COSOLπ development project and some of the results obtained to date. The benefits of the work of this project will include the generation of a not polluting transportable energy feedstock from a free, abundant and available primary energy source, in an efficient method with no greenhouse gas emission. This will help to ensure energy surety to a future transportation/energy infrastructure, without any fuel import. Further technological development of thermochemical production of clean fuels, together with solar reactors and also with the possibility of determining the optical and thermal properties of the materials involved a milestone in the search for new processes for industrialization. With the above in mind, important national academic institutions: UAM, UNAM, CINVESTAV, UACH, UNISON among others, have been promoting research in solar energy technologies. The Goals and objectives are to conduct research and technological development driving high-temperature thermochemical processes using concentrated solar radiation as thermal energy source for the future sustainable development of industrial processes. It focuses on the production of clean fuels such as H2, syngas, biofuels, without excluding the re-value of materials used in the industry. This project conducts theoretical and experimental studies for the identification, characterization, and optimization of the most promising thermochemical cycles, and for the thorough investigation of the reactive chemical systems. It applies material science and nano-engineering to improve chemicals properties and stability upon cycling. The characterization of materials will serve to measure the chemical composition and purity (MOX fraction-1) of each of the samples. The characterizations also focus on the solid particle morphology (shape, size, state of aggregation, homogeneity, specific surface) images obtained from SEM / TEM and BET measurements. Likewise will the thermal and optical characterization of the influence that these parameters represent in the solar reactor. The experimental and theoretical results obtained for each redox system will be compared and analyzed to determine the cycle with the highest potential. Advances on simulation, design, construction and experimentation on solar reactors to conduct thermochemical splitting water reactions are presented.

Determination of Geochemical Bio-Signatures in Mars-Like Basaltic Environments

PubMed Central

Olsson-Francis, Karen; Pearson, Victoria K.; Steer, Elisabeth D.; Schwenzer, Susanne P.

2017-01-01

Bio-signatures play a central role in determining whether life existed on early Mars. Using a terrestrial basalt as a compositional analog for the martian surface, we applied a combination of experimental microbiology and thermochemical modeling techniques to identify potential geochemical bio-signatures for life on early Mars. Laboratory experiments were used to determine the short-term effects of biota on the dissolution of terrestrial basalt, and the formation of secondary alteration minerals. The chemoorganoheterotrophic bacterium, Burkholderia sp. strain B_33, was grown in a minimal growth medium with and without terrestrial basalt as the sole nutrient source. No growth was detected in the absence of the basalt. In the presence of basalt, during exponential growth, the pH decreased rapidly from pH 7.0 to 3.6 and then gradually increased to a steady-state of equilibrium of between 6.8 and 7.1. Microbial growth coincided with an increase in key elements in the growth medium (Si, K, Ca, Mg, and Fe). Experimental results were compared with theoretical thermochemical modeling to predict growth of secondary alteration minerals, which can be used as bio-signatures, over a geological timescale. We thermochemically modeled the dissolution of the basalt (in the absence of biota) in very dilute brine at 25°C, 1 bar; the pH was buffered by the mineral dissolution and precipitation reactions. Preliminary results suggested that at the water to rock ratio of 1 × 107, zeolite, hematite, chlorite, kaolinite, and apatite formed abiotically. The biotic weathering processes were modeled by varying the pH conditions within the model to adjust for biologic influence. The results suggested that, for a basaltic system, the microbially-mediated dissolution of basalt would result in “simpler” secondary alteration, consisting of Fe-hydroxide and kaolinite, under conditions where the abiotic system would also form chlorite. The results from this study demonstrate that, by using laboratory-based experiments and thermochemical modeling, it is possible to identify secondary alteration minerals that could potentially be used to distinguish between abiotic and biotic weathering processes on early Mars. This work will contribute to the interpretation of data from past, present, and future life detection missions to Mars. PMID:28943863

Determination of Geochemical Bio-Signatures in Mars-Like Basaltic Environments.

PubMed

Olsson-Francis, Karen; Pearson, Victoria K; Steer, Elisabeth D; Schwenzer, Susanne P

2017-01-01

Bio-signatures play a central role in determining whether life existed on early Mars. Using a terrestrial basalt as a compositional analog for the martian surface, we applied a combination of experimental microbiology and thermochemical modeling techniques to identify potential geochemical bio-signatures for life on early Mars. Laboratory experiments were used to determine the short-term effects of biota on the dissolution of terrestrial basalt, and the formation of secondary alteration minerals. The chemoorganoheterotrophic bacterium, Burkholderia sp. strain B_33, was grown in a minimal growth medium with and without terrestrial basalt as the sole nutrient source. No growth was detected in the absence of the basalt. In the presence of basalt, during exponential growth, the pH decreased rapidly from pH 7.0 to 3.6 and then gradually increased to a steady-state of equilibrium of between 6.8 and 7.1. Microbial growth coincided with an increase in key elements in the growth medium (Si, K, Ca, Mg, and Fe). Experimental results were compared with theoretical thermochemical modeling to predict growth of secondary alteration minerals, which can be used as bio-signatures, over a geological timescale. We thermochemically modeled the dissolution of the basalt (in the absence of biota) in very dilute brine at 25°C, 1 bar; the pH was buffered by the mineral dissolution and precipitation reactions. Preliminary results suggested that at the water to rock ratio of 1 × 10 7 , zeolite, hematite, chlorite, kaolinite, and apatite formed abiotically. The biotic weathering processes were modeled by varying the pH conditions within the model to adjust for biologic influence. The results suggested that, for a basaltic system, the microbially-mediated dissolution of basalt would result in "simpler" secondary alteration, consisting of Fe-hydroxide and kaolinite, under conditions where the abiotic system would also form chlorite. The results from this study demonstrate that, by using laboratory-based experiments and thermochemical modeling, it is possible to identify secondary alteration minerals that could potentially be used to distinguish between abiotic and biotic weathering processes on early Mars. This work will contribute to the interpretation of data from past, present, and future life detection missions to Mars.

ARTI Refrigerant Database

DOE Office of Scientific and Technical Information (OSTI.GOV)

Calm, J.M.

The Refrigerant Database consolidates and facilitates access to information to assist industry in developing equipment using alternative refrigerants. The underlying purpose is to accelerate phase out of chemical compounds of environmental concern.

Bayesian Calibration of Thermodynamic Databases and the Role of Kinetics

NASA Astrophysics Data System (ADS)

Wolf, A. S.; Ghiorso, M. S.

2017-12-01

Self-consistent thermodynamic databases of geologically relevant materials (like Berman, 1988; Holland and Powell, 1998, Stixrude & Lithgow-Bertelloni 2011) are crucial for simulating geological processes as well as interpreting rock samples from the field. These databases form the backbone of our understanding of how fluids and rocks interact at extreme planetary conditions. Considerable work is involved in their construction from experimental phase reaction data, as they must self-consistently describe the free energy surfaces (including relative offsets) of potentially hundreds of interacting phases. Standard database calibration methods typically utilize either linear programming or least squares regression. While both produce a viable model, they suffer from strong limitations on the training data (which must be filtered by hand), along with general ignorance of many of the sources of experimental uncertainty. We develop a new method for calibrating high P-T thermodynamic databases for use in geologic applications. The model is designed to handle pure solid endmember and free fluid phases and can be extended to include mixed solid solutions and melt phases. This new calibration effort utilizes Bayesian techniques to obtain optimal parameter values together with a full family of statistically acceptable models, summarized by the posterior. Unlike previous efforts, the Bayesian Logistic Uncertain Reaction (BLUR) model directly accounts for both measurement uncertainties and disequilibrium effects, by employing a kinetic reaction model whose parameters are empirically determined from the experiments themselves. Thus, along with the equilibrium free energy surfaces, we also provide rough estimates of the activation energies, entropies, and volumes for each reaction. As a first application, we demonstrate this new method on the three-phase aluminosilicate system, illustrating how it can produce superior estimates of the phase boundaries by incorporating constraints from all available data, while automatically handling variable data quality due to a combination of measurement errors and kinetic effects.

Practical Quantum Private Database Queries Based on Passive Round-Robin Differential Phase-shift Quantum Key Distribution

PubMed Central

Li, Jian; Yang, Yu-Guang; Chen, Xiu-Bo; Zhou, Yi-Hua; Shi, Wei-Min

2016-01-01

A novel quantum private database query protocol is proposed, based on passive round-robin differential phase-shift quantum key distribution. Compared with previous quantum private database query protocols, the present protocol has the following unique merits: (i) the user Alice can obtain one and only one key bit so that both the efficiency and security of the present protocol can be ensured, and (ii) it does not require to change the length difference of the two arms in a Mach-Zehnder interferometer and just chooses two pulses passively to interfere with so that it is much simpler and more practical. The present protocol is also proved to be secure in terms of the user security and database security. PMID:27539654

Thermodynamic database for the Co-Pr system.

PubMed

Zhou, S H; Kramer, M J; Meng, F Q; McCallum, R W; Ott, R T

2016-03-01

In this article, we describe data on (1) compositions for both as-cast and heat treated specimens were summarized in Table 1; (2) the determined enthalpy of mixing of liquid phase is listed in Table 2; (3) thermodynamic database of the Co-Pr system in TDB format for the research articled entitle Chemical partitioning for the Co-Pr system: First-principles, experiments and energetic calculations to investigate the hard magnetic phase W.

Thermodynamic database for the Co-Pr system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, S. H.; Kramer, M. J.; Meng, F. Q.

2016-01-21

In this article, we describe data on (1) compositions for both as-cast and heat treated specimens were summarized in Table 1; (2) the determined enthalpy of mixing of liquid phase is listed in Table 2; (3) thermodynamic database of the Co-Pr system in TDB format for the research articled entitle Chemical partitioning for the Co-Pr system: First-principles, experiments and energetic calculations to investigate the hard magnetic phase W.

Database Management in Design Optimization.

DTIC Science & Technology

1983-10-30

processing program(s) engaged in the task of preparing input data for the (finite-element) analysis and optimization phases primary storage the main...and extraction of data from the database for further processing . It can be divided into two phases: a) The process of selection and identification of ...user wishes to stop the reading or the writing process . The meaning of END depends on the method specified for retrieving data: a) Row-wise - then

Thermodynamic database for the Co-Pr system

DOE PAGES

Zhou, S. H.; Kramer, M. J.; Meng, F. Q.; ...

2016-03-01

In this article, we describe data on (1) compositions for both as-cast and heat treated specimens were summarized in Table 1; (2) the determined enthalpy of mixing of liquid phase is listed in Table 2; (3) thermodynamic database of the Co-Pr system in TDB format for the research articled entitled ''Chemical partitioning for the Co-Pr system: First-principles, experiments and energetic calculations to investigate the hard magnetic phase W.''

Thermo-chemical Ice Penetrator for Icy Moons

NASA Astrophysics Data System (ADS)

Arenberg, J. W.; Lee, G.; Harpole, G.; Zamel, J.; Sen, B.; Ross, F.; Retherford, K. D.

2016-12-01

The ability to place sensors or to take samples below the ice surface enables a wide variety of potential scientific investigations. Penetrating an ice cap can be accomplished via a mechanical drill, laser drill, kinetic impactor, or heated penetrator. This poster reports on the development of technology for the latter most option, namely a self-heated probe driven by an exothermic chemical reaction: a Thermo-chemical ice penetrator (TChIP). Our penetrator design employs a eutectic mix of alkali metals that produce an exothermic reaction upon contact with an icy surface. This reaction increases once the ice starts melting, so no external power is required. This technology is inspired by a classified Cold-War era program developed at Northrop Grumman for the US Navy. Terrestrial demonstration of this technology took place in the Arctic; however, this device cannot be considered high TRL for application at the icy moons of the solar system due to the environmental differences between Earth's Arctic and the icy moons. These differences demand a TChIP design specific to these cold, low mass, airless worlds. It is expected that this model of TChIP performance will be complex, incorporating all of the forces on the penetrator, gravity, the thermo-chemistry at the interface between penetrator and ice, and multi-phase heat and mass transport, and hydrodynamics. Our initial efforts are aimed at the development of a validated set of tools and simulations to predict the performance of the penetrator for both the environment found on these icy moons and for a terrestrial environment. The purpose of the inclusion of the terrestrial environment is to aid in model validation. Once developed and validated, our models will allow us to design penetrators for a specific scientific application on a specific body. This poster discusses the range of scientific investigations that are enabled by TChIP. We also introduce the development plan to advance TChIP to the point where it can be considered for infusion into a program.

Technology for a Thermo-chemical Ice Penetrator for Icy Moons

NASA Astrophysics Data System (ADS)

Arenberg, Jonathan; Harpole, George; Zamel, James; Sen, Bashwar; Lee, Greg; Ross, Floyd; Retherford, Kurt D.

2016-10-01

The ability to place sensors or to take samples below the ice surface enables a wide variety of potential scientific investigations. Penetrating an ice cap can be accomplished via a mechanical drill, laser drill, kinetic impactor, or heated penetrator. This poster reports on the development of technology for the latter most option, namely a self-heated probe driven by an exothermic chemical reaction: a Thermo-chemical ice penetrator (TChIP). Our penetrator design employs a eutectic mix of alkali metals that produce an exothermic reaction upon contact with an icy surface. This reaction increases once the ice starts melting, so no external power is required. This technology is inspired by a classified Cold-War era program developed at Northrop Grumman for the US Navy. Terrestrial demonstration of this technology took place in the Arctic; however, this device cannot be considered high TRL for application at the icy moons of the solar system due to the environmental differences between Earth's Arctic and the icy moons. These differences demand a TChIP design specific to these cold, low mass, airless worlds. It is expected that this model of TChIP performance will be complex, incorporating all of the forces on the penetrator, gravity, the thermo-chemistry at the interface between penetrator and ice, and multi-phase heat and mass transport, and hydrodynamics. Our initial efforts are aimed at the development of a validated set of tools and simulations to predict the performance of the penetrator for both the environment found on these icy moons and for a terrestrial environment. The purpose of the inclusion of the terrestrial environment is to aid in model validation. Once developed and validated, our models will allow us to design penetrators for a specific scientific application on a specific body. This poster discusses the range of scientific investigations that are enabled by TChIP. We also introduce the development plan to advance TChIP to the point where it can be considered for infusion into a program.

Modeling the gas-phase thermochemistry of organosulfur compounds.

PubMed

Vandeputte, Aäron G; Sabbe, Maarten K; Reyniers, Marie-Françoise; Marin, Guy B

2011-06-27

Key to understanding the involvement of organosulfur compounds in a variety of radical chemistries, such as atmospheric chemistry, polymerization, pyrolysis, and so forth, is knowledge of their thermochemical properties. For organosulfur compounds and radicals, thermochemical data are, however, much less well documented than for hydrocarbons. The traditional recourse to the Benson group additivity method offers no solace since only a very limited number of group additivity values (GAVs) is available. In this work, CBS-QB3 calculations augmented with 1D hindered rotor corrections for 122 organosulfur compounds and 45 organosulfur radicals were used to derive 93 Benson group additivity values, 18 ring-strain corrections, 2 non-nearest-neighbor interactions, and 3 resonance corrections for standard enthalpies of formation, standard molar entropies, and heat capacities for organosulfur compounds and organosulfur radicals. The reported GAVs are consistent with previously reported GAVs for hydrocarbons and hydrocarbon radicals and include 77 contributions, among which 26 radical contributions, which, to the best of our knowledge, have not been reported before. The GAVs allow one to estimate the standard enthalpies of formation at 298 K, the standard entropies at 298 K, and standard heat capacities in the temperature range 300-1500 K for a large set of organosulfur compounds, that is, thiols, thioketons, polysulfides, alkylsulfides, thials, dithioates, and cyclic sulfur compounds. For a validation set of 26 organosulfur compounds, the mean absolute deviation between experimental and group additively modeled enthalpies of formation amounts to 1.9  kJ  mol(-1). For an additional set of 14 organosulfur compounds, it was shown that the mean absolute deviations between calculated and group additively modeled standard entropies and heat capacities are restricted to 4 and 2 J  mol(-1)  K(-1), respectively. As an alternative to Benson GAVs, 26 new hydrogen-bond increments are reported, which can also be useful for the prediction of radical thermochemistry. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Threshold collision-induced dissociation and theoretical study of protonated azobenzene

NASA Astrophysics Data System (ADS)

Rezaee, Mohammadreza; McNary, Christopher P.; Armentrout, P. B.

2017-10-01

Protonated azobenzene (AB), H+(C6H5N2C6H5), has been studied using threshold collision-induced dissociation in a guided ion beam tandem mass spectrometer. Product channels observed are C6H5N2+ + C6H6 and C6H5+ + N2 + C6H6. The experimental kinetic energy-dependent cross sections were analyzed using a statistical model that accounts for internal and kinetic energy distributions of the reactants, multiple collisions, and kinetic shifts. From this analysis, the activation energy barrier height of 2.02 ± 0.11 eV for benzene loss is measured. To identify the transition states (TSs) and intermediates (IMs) for these dissociations, relaxed potential energy surface (PES) scans were performed at the B3LYP/aug-cc-pVTZ level of theory. The PES indicates that there is a substantial activation energy along the dissociation reaction coordinate that is the rate-limiting step for benzene loss and at some levels of theory, for subsequent N2 loss as well. Relative energies of the reactant, TSs, IMs, and products were calculated at B3LYP, wB97XD, M06, PBEPBE, and MP2(full) levels of theory using both 6-311++G(2d,2p) and aug-cc-pVTZ basis sets. Comparison of the experimental results with theoretical values from various computational methods indicates how well these theoretical methods can predict thermochemical properties. In addition to these density functional theory and MP2 methods, several high accuracy multi-level calculations such as CBS-QB3, G3, G3MP2, G3B3MP2, G4, and G4MP2 were performed to determine the thermochemical properties of AB including the proton affinity and gas-phase basicity, and to compare the performance of different theoretical methods.

Evolution and structure of Mercury's interior from MESSENGER observations

NASA Astrophysics Data System (ADS)

Tosi, Nicola

2015-04-01

During the past four years, the MESSENGER mission (MErcury Surface, Space Environment, GEochemistry and Ranging) has delivered a wealth of information that has been dramatically advancing the understanding of the geological, chemical, and physical state of Mercury. Taking into account the latest constraints on the interior structure, surface composition, volcanic and tectonic history, we employed numerical models to simulate the thermo-chemical evolution of the planet's interior [1]. Typical evolution scenarios that allow the observational constraints to be satisfied consist of an initial phase of mantle heating accompanied by planetary expansion and the production of a substantial amount of partial melt. The evolution subsequent to 2 Ga is characterised by secular cooling that proceeds approximately at a constant rate and implies that contraction should be still ongoing. Most of the models also predict mantle convection to cease after 3-4 Ga, indicating that Mercury may be no longer dynamically active. In addition, the topography, measured by laser altimetry and the gravity field, obtained from radio-tracking, represent fundamental observations that can be interpreted in terms of the chemical and mechanical structure of the interior. The observed geoid-to-topography ratios at intermediate wavelengths are well explained by the isostatic compensation of the topography associated with lateral variations of the crustal thickness, whose mean value can be estimated to be ~35 km, broadly confirming the predictions of the evolution simulations [2]. Finally, we will show that the degree-2 and 4 of the topography and geoid spectra can be explained in terms of the long-wavelength deformation of the lithosphere resulting from deep thermal anomalies caused by the large latitudinal and longitudinal variations in temperature experienced by Mercury's surface. [1] Tosi N., M. Grott, A.-C. Plesa and D. Breuer (2013). Thermo-chemical evolution of Mercury's interior. Journal of Geophysical Research - Planets, 118, 2474-2487. [2] Padovan S., M. Wieczorek, J.-L. Margot, N. Tosi, and S. Solomon (2015). Thickness of the crust of Mercury from geoid-to-topography ratios. Geophysical Research Letters. In press.

Impact-induced melting and heating of planetary interiors - implications for the thermo-chemical evolution of planets and crystallization of magma oceans

NASA Astrophysics Data System (ADS)

Wuennemann, K.; Manske, L.; Zhu, M.; Nakajima, M.; Breuer, D.; Schwinger, S.; Plesa, A. C.

2017-12-01

Large collisions and giant impact events play an important role in the thermo-chemical evolution of planets during their early and late accretion phases. Besides material that is delivered by differentiated and primitive projectiles a significant amount of the kinetic impact energy is transferred to the planets interior resulting in heating and widespread melting of matter. As a consequence, giant impacts are thought to form global magma oceans. The amount and distribution of impact-induced heating and melting has been previously estimated by scaling laws derived from small-scale impact simulations and experiments, simple theoretical considerations, and observations at terrestrial craters. We carried out a suite of numerical models using the iSALE shock physics code and an SPH code combined with the ANEOS package to investigate the melt production in giant impacts and planetary collision events as a function of impactor size and velocity, and the target temperature. Our results are consistent with previously derived scaling laws only for smaller impactors (<10 km in diameter), but significantly deviate for larger impactors: (1) for hot planets, where the temperature below the lithosphere lies close to the solidus temperature, the melt production is significantly increased for impactors comparable in the size to the depth of the lithosphere. The resulting crater structures would drown in their own melt and only large igneous provinces (local magma oceans) would remain visible at the surface;(2) even bigger impacts (planetary collisions) generate global magma oceans; (3) impacts into a completely solidified (cold) target result in more localized heating in comparison to impacts into a magma ocean, where the impact-induced heating is distributed over a larger volume. In addition, we investigate the influence of impacts on a cooling and crystallization of magma oceans and use the lunar magma ocean as an example.

Space shuttle phase B wind tunnel model and test information. Volume 3: Launch configuration

NASA Technical Reports Server (NTRS)

Glynn, J. L.; Poucher, D. E.

1988-01-01

Archived wind tunnel test data are available for flyback booster or other alternate recoverable configuration as well as reusable orbiters studied during initial development (Phase B) of the Space Shuttle, including contractor data for an extensive variety of configurations with an array of wing and body planforms. The test data have been compiled into a database and are available for application to current winged flyback or recoverable booster aerodynamic studies. The Space Shuttle Phase B Wind Tunnel Database is structured by vehicle component and configuration. Basic components include booster, orbiter, and launch vehicle. Booster configuration types include straight and delta wings, canard, cylindrical, retroglide and twin body. Orbiter configurations include straight and delta wings, lifting body, drop tanks and double delta wings. Launch configurations include booster and orbiter components in various stacked and tandem combinations. The digital database consists of 220 files containing basic tunnel data. Database structure is documented in a series of reports which include configuration sketches for the various planforms tested. This is Volume 3 -- launch configurations.

Matthew Oliver | NREL

Science.gov Websites

Process Development Unit. NREL's Thermal and Catalytic Process Development Unit can process 1/2 ton per biomass to fuels and chemicals Affiliated Research Programs Thermochemical Process Integration, Scale-Up

Process for thermochemically producing hydrogen

DOEpatents

Bamberger, Carlos E.; Richardson, Donald M.

1976-01-01

Hydrogen is produced by the reaction of water with chromium sesquioxide and strontium oxide. The hydrogen producing reaction is combined with other reactions to produce a closed chemical cycle for the thermal decomposition of water.

Kinetic calculations of explosives with slow-burning constituents

NASA Astrophysics Data System (ADS)

Howard, W. Michael; Souers, P. Clark; Fried, Laurence E.

1998-07-01

The equilibrium thermochemical code CHEETAH V1.40 has been modified to detonate part of the explosive and binder. An Einstein thermal description of the unreacted constituents is used, and the Einstein temperature may be increased to reduce heat absorption. We study the effect of the reactivity and thermal transport on the detonation velocity. Hydroxy-terminated-polybutadiene binders have low energy and density and would degrade the detonation velocity if they burned. Runs with unburned binder are closer to the measured values. Aluminum and ammonium perchlorate are also largely unburned within the sonic reaction zone that determines the detonation velocity. All three materials appear not to fully absorb heat as well. The normal assumption of total reaction in a thermochemical code is clearly not true for these special cases, where the detonation velocities have widely different values for different combinations of processes.

Research and evaluation of biomass resources/conversion/utilization systems. Biomass allocation model. Volume 1: Test and appendices A & B

NASA Astrophysics Data System (ADS)

Stringer, R. P.; Ahn, Y. K.; Chen, H. T.; Helm, R. W.; Nelson, E. T.; Shields, K. J.

1981-08-01

A biomass allocation model was developed to show the most profitable combination of biomass feedstocks, thermochemical conversion processes, and fuel products to serve the seasonal conditions in a regional market. This optimization model provides a tool for quickly calculating which of a large number of potential biomass missions is the most profitable mission. Other components of the system serve as a convenient storage and retrieval mechanism for biomass marketing and thermochemical conversion processing data. The system can be accessed through the use of a computer terminal, or it could be adapted to a microprocessor. A User's Manual for the system is included. Biomass derived fuels included in the data base are the following: medium Btu gas, low Btu gas, substitute natural gas, ammonia, methanol, electricity, gasoline, and fuel oil.

The influence of Ag content and annealing time on structural and optical properties of SGS antimony-germanate glass doped with Er3+ ions

NASA Astrophysics Data System (ADS)

Zmojda, J.; Kochanowicz, M.; Miluski, P.; Baranowska, A.; Basa, A.; Jadach, R.; Sitarz, M.; Dorosz, D.

2018-05-01

A series of erbium doped SGS antimony-germanate glass embedding silver (Ag0) nanoparticles have been synthesized by a one-step melt-quench thermochemical reduction technique. The effect of NPs concentration and annealing time on the structural and photoluminescent (PL) properties were investigated. The Raman spectra as a function of temperature measured in-situ allow to determine the structural changes in vicinity of Ag+ ions and confirmed thermochemical reduction of Ag+ ions by Sb3+ ions. The surface plasmon resonance absorption band was evidenced near 450 nm. The impact of local field effect generated by Ag0 nanoparticles (NPs) and energy transfer from surface of silver NPs to trivalent erbium ions on near-infrared and up-conversion luminescence was described in terms of enhancement and quench phenomena.

Thermo-chemical pretreatment and enzymatic hydrolysis for enhancing saccharification of catalpa sawdust.

PubMed

Jin, Shuguang; Zhang, Guangming; Zhang, Panyue; Li, Fan; Fan, Shiyang; Li, Juan

2016-04-01

To improve the reducing sugar production from catalpa sawdust, thermo-chemical pretreatments were examined and the chemicals used including NaOH, Ca(OH)2, H2SO4, and HCl. The hemicellulose solubilization and cellulose crystallinity index (CrI) were significantly increased after thermo-alkaline pretreatments, and the thermo-Ca(OH)2 pretreatment showed the best improvement for reducing sugar production comparing to other three pretreatments. The conditions of thermo-Ca(OH)2 pretreatment and enzymatic hydrolysis were systematically optimized. Under the optimal conditions, the reducing sugar yield increased by 1185.7% comparing to the control. This study indicates that the thermo-Ca(OH)2 pretreatment is ideal for the saccharification of catalpa sawdust and that catalpa sawdust is a promising raw material for biofuel. Copyright © 2016 Elsevier Ltd. All rights reserved.

Combining mineral physics with seismic observations: What can we deduce about the thermochemical structure of the Earth's deep interior?

NASA Astrophysics Data System (ADS)

Cobden, L. J.

2017-12-01

Mineral physics provides the essential link between seismic observations of the Earth's interior, and laboratory (or computer-simulated) measurements of rock properties. In this presentation I will outline the procedure for quantitative conversion from thermochemical structure to seismic structure (and vice versa) using the latest datasets from seismology and mineralogy. I will show examples of how this method can allow us to infer major chemical and dynamic properties of the deep mantle. I will also indicate where uncertainties and limitations in the data require us to exercise caution, in order not to "over-interpret" seismic observations. Understanding and modelling these uncertainties serves as a useful guide for mineralogists to ascertain which mineral parameters are most useful in seismic interpretation, and enables seismologists to optimise their data assembly and inversions for quantitative interpretations.

Continuous thermochemical conversion process to produce oil from swine manure

USGS Publications Warehouse

Ocfemia, K.; Zhang, Y.; Funk, T.; Christianson, L.; Chen, S.

2004-01-01

Thermochemical conversion (TCC) of livestock manure is a novel technology that has shown very promising results in treating waste and producing oil. A batch TCC system that was previously developed successfully converted 70% of swine manure volatile solids to oil and reduced manure chemical oxygen demand by ??? 75%. The necessary retention time to achieve an oil product was largely dependent on the operating temperature. The highest oil production efficiency was 80% of the volatile solids (or 70 wt % of the total solids). The average carbon and hydrogen contents were ??? 72 and 9%, respectively. The heating values for 80% of the oil products ranged from 32,000 to 36,700 kJ/kg. This is an abstract of a paper presented at the AWMA 97th Annual Conference and Exhibition (Indianapolis, IN 6/22-25/2004).

Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

PubMed

Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

2015-01-07

Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

Thermochemical characterization of some thermally stable thermoplastic and thermoset polymers

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Gilwee, W. J., Jr.; Parker, J. A.

1979-01-01

The thermochemical and flammability properties of some thermally stable polymers considered for use in aircraft interiors are described. The properties studied include: (1) thermomechanical properties such as glass transition and melt temperature; (2) dynamic thermogravimetric analysis in anaerobic environment; (3) flammability properties such as oxygen index, flame spread, and smoke evolution; and (4) selected physical properties. The thermoplastic polymers evaluated include polyphenylene sulfide, polyaryl sulfone, 9,9-bis(4-hydroxyphenyl)-fluorene polycarbonate-poly(dimethylsiloxane) and polyether sulfone. The thermoset polymers evaluated include epoxy, bismaleimide, a modified phenolic, and polyaromatic melamine resin. These resins were primarily used in the fabrication of glass-reinforced prepregs for the construction of experimental panels. Test results and relative rankings of some of the flammability parameters are presented, and the relationship of the molecular structure, char yield, and flammability properties of these polymers are discussed.

Innovative pretreatment strategies for biogas production.

PubMed

Patinvoh, Regina J; Osadolor, Osagie A; Chandolias, Konstantinos; Sárvári Horváth, Ilona; Taherzadeh, Mohammad J

2017-01-01

Biogas or biomethane is traditionally produced via anaerobic digestion, or recently by thermochemical or a combination of thermochemical and biological processes via syngas (CO and H 2 ) fermentation. However, many of the feedstocks have recalcitrant structure and are difficult to digest (e.g., lignocelluloses or keratins), or they have toxic compounds (such as fruit flavors or high ammonia content), or not digestible at all (e.g., plastics). To overcome these challenges, innovative strategies for enhanced and economically favorable biogas production were proposed in this review. The strategies considered are commonly known physical pretreatment, rapid decompression, autohydrolysis, acid- or alkali pretreatments, solvents (e.g. for lignin or cellulose) pretreatments or leaching, supercritical, oxidative or biological pretreatments, as well as combined gasification and fermentation, integrated biogas production and pretreatment, innovative biogas digester design, co-digestion, and bio-augmentation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Additive erosion reduction influences in the turbulent boundary layer

NASA Astrophysics Data System (ADS)

Buckingham, A. C.

1981-05-01

Results of a sequence of flow, heat and mass transfer calculations are presented which theoretically characterize the erosive environment at the wall surface of refractory metal coated and uncoated gun barrels. The theoretical results include analysis of the wall surface temperature, heat flux, and shear stress time histories on thin (10 mil.) Cr, Mo, Nb, and Ta plated steel barrel walls as uncoated steel walls. The calculations combine effects of a number of separate processes which were previously (and purposely) studied individually. These include solid particle additive concentrations, gas wall thermochemical influences, and transient turbulent wall boundary layer flow with multicomponent molecular diffusion and reactions from interaction of propellant combustion and the eroding surface. The boundary layer model includes particulate additive concentrations as well as propellant combustion products, considered for the present to be in the local thermochemical equilibrium.

Some current problems in oxidation kinetics

NASA Technical Reports Server (NTRS)

Benson, S. W.

1972-01-01

Experimental data in low temperature and high temperature oxidations are examined from the point of view of reported quantitative inconsistencies. Activation energies for tBuO2 metathesis reactions with alkanes appear to be 7 kcal/mole higher than for comparable reactions of HO2. Related isomerization reactions are examined in the light of these differences without reaching any simple conclusions. The Russell mechanism for a 6-membered, cyclic, transition state for termination of primary and secondary alkyl peroxy radicals is shown to be either inconsistent with thermochemical data, or else unique to solution reactions. Addition reactions of O3 with olefins and acetylenes are shown thermochemically to have the possibility of following concerted and biradical pathways, respectively. Recent data showing strong inhibition by PbO coated surfaces of both oxidation and pyrolysis of i-C4H10 are examined in terms of mechanism.

Ethanol extraction of phytosterols from corn fiber

DOEpatents

Abbas, Charles; Beery, Kyle E.; Binder, Thomas P.; Rammelsberg, Anne M.

2010-11-16

The present invention provides a process for extracting sterols from a high solids, thermochemically hydrolyzed corn fiber using ethanol as the extractant. The process includes obtaining a corn fiber slurry having a moisture content from about 20 weight percent to about 50 weight percent solids (high solids content), thermochemically processing the corn fiber slurry having high solids content of 20 to 50% to produce a hydrolyzed corn fiber slurry, dewatering the hydrolyzed corn fiber slurry to achieve a residual corn fiber having a moisture content from about 30 to 80 weight percent solids, washing the residual corn fiber, dewatering the washed, hydrolyzed corn fiber slurry to achieve a residual corn fiber having a moisture content from about 30 to 80 weight percent solids, and extracting the residual corn fiber with ethanol and separating at least one sterol.

Nuclear driven water decomposition plant for hydrogen production

NASA Technical Reports Server (NTRS)

Parker, G. H.; Brecher, L. E.; Farbman, G. H.

1976-01-01

The conceptual design of a hydrogen production plant using a very-high-temperature nuclear reactor (VHTR) to energize a hybrid electrolytic-thermochemical system for water decomposition has been prepared. A graphite-moderated helium-cooled VHTR is used to produce 1850 F gas for electric power generation and 1600 F process heat for the water-decomposition process which uses sulfur compounds and promises performance superior to normal water electrolysis or other published thermochemical processes. The combined cycle operates at an overall thermal efficiency in excess of 45%, and the overall economics of hydrogen production by this plant have been evaluated predicated on a consistent set of economic ground rules. The conceptual design and evaluation efforts have indicated that development of this type of nuclear-driven water-decomposition plant will permit large-scale economic generation of hydrogen in the 1990s.

Effects of Dopant Metal Variation and Material Synthesis Method on the Material Properties of Mixed Metal Ferrites in Yttria Stabilized Zirconia for Solar Thermochemical Fuel Production

DOE PAGES

Leonard, Jeffrey; Reyes, Nichole; Allen, Kyle M.; ...

2015-01-01

Mixed metal ferrites have shown much promise in two-step solar-thermochemical fuel production. Previous work has typically focused on evaluating a particular metal ferrite produced by a particular synthesis process, which makes comparisons between studies performed by independent researchers difficult. A comparative study was undertaken to explore the effects different synthesis methods have on the performance of a particular material during redox cycling using thermogravimetry. This study revealed that materials made via wet chemistry methods and extended periods of high temperature calcination yield better redox performance. Differences in redox performance between materials made via wet chemistry methods were minimal and thesemore » demonstrated much better performance than those synthesized via the solid state method. Subsequently, various metal ferrite samples (NiFe 2 O 4 , MgFe 2 O 4 , CoFe 2 O 4 , and MnFe 2 O 4 ) in yttria stabilized zirconia (8YSZ) were synthesized via coprecipitation and tested to determine the most promising metal ferrite combination. It was determined that 10 wt.% CoFe 2 O 4 in 8YSZ produced the highest and most consistent yields of O 2 and CO. By testing the effects of synthesis methods and dopants in a consistent fashion, those aspects of ferrite preparation which are most significant can be revealed. More importantly, these insights can guide future efforts in developing the next generation of thermochemical fuel production materials.« less

Pretreatment of Cottage Cheese to Enhance Biogas Production

PubMed Central

Salgaonkar, Bhakti; Mutnuri, Srikanth

2014-01-01

This study evaluated the possibility of pretreating selected solid fraction of an anaerobic digester treating food waste to lower the hydraulic retention time and increase the methane production. The study investigated the effect of different pretreatments (thermal, chemical, thermochemical and enzymatic) for enhanced methane production from cottage cheese. The most effective pretreatments were thermal and enzymatic. Highest solubilisation of COD was observed in thermal pretreatment, followed by thermochemical. In single enzyme systems, lipase at low concentration gave significantly higher methane yield than for the experiments without enzyme additions. The highest lipase dosages decreased methane yield from cottage cheese. However, in case of protease enzyme an increase in concentration of the enzyme showed higher methane yield. In the case of mixed enzyme systems, pretreatment at 1 : 2 ratio of lipase : protease showed higher methane production in comparison with 1 : 1 and 2 : 1 ratios. Methane production potentials for different pretreatments were as follows: thermal 357 mL/g VS, chemical 293 mL/g VS, and thermochemical 441 mL/g VS. The average methane yield from single enzyme systems was 335 mL/g VS for lipase and 328 mL/g VS for protease. Methane potentials for mixed enzyme ratios were 330, 360, and 339 mL/g VS for 1 : 1, 1 : 2, and 2 : 1 lipase : protease, respectively. PMID:24995288

Classification of ECG beats using deep belief network and active learning.

PubMed

G, Sayantan; T, Kien P; V, Kadambari K

2018-04-12

A new semi-supervised approach based on deep learning and active learning for classification of electrocardiogram signals (ECG) is proposed. The objective of the proposed work is to model a scientific method for classification of cardiac irregularities using electrocardiogram beats. The model follows the Association for the Advancement of medical instrumentation (AAMI) standards and consists of three phases. In phase I, feature representation of ECG is learnt using Gaussian-Bernoulli deep belief network followed by a linear support vector machine (SVM) training in the consecutive phase. It yields three deep models which are based on AAMI-defined classes, namely N, V, S, and F. In the last phase, a query generator is introduced to interact with the expert to label few beats to improve accuracy and sensitivity. The proposed approach depicts significant improvement in accuracy with minimal queries posed to the expert and fast online training as tested on the MIT-BIH Arrhythmia Database and the MIT-BIH Supra-ventricular Arrhythmia Database (SVDB). With 100 queries labeled by the expert in phase III, the method achieves an accuracy of 99.5% in "S" versus all classifications (SVEB) and 99.4% accuracy in "V " versus all classifications (VEB) on MIT-BIH Arrhythmia Database. In a similar manner, it is attributed that an accuracy of 97.5% for SVEB and 98.6% for VEB on SVDB database is achieved respectively. Graphical Abstract Reply- Deep belief network augmented by active learning for efficient prediction of arrhythmia.

High-temperature experimental and thermodynamic modelling research on the pyrometallurgical processing of copper

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Shishin, Denis; Decterov, Sergei A.; Hayes, Peter C.; Jak, Evgueni

2017-01-01

Uncertainty in the metal price and competition between producers mean that the daily operation of a smelter needs to target high recovery of valuable elements at low operating cost. Options for the improvement of the plant operation can be examined and decision making can be informed based on accurate information from laboratory experimentation coupled with predictions using advanced thermodynamic models. Integrated high-temperature experimental and thermodynamic modelling research on phase equilibria and thermodynamics of copper-containing systems have been undertaken at the Pyrometallurgy Innovation Centre (PYROSEARCH). The experimental phase equilibria studies involve high-temperature equilibration, rapid quenching and direct measurement of phase compositions using electron probe X-ray microanalysis (EPMA). The thermodynamic modelling deals with the development of accurate thermodynamic database built through critical evaluation of experimental data, selection of solution models, and optimization of models parameters. The database covers the Al-Ca-Cu-Fe-Mg-O-S-Si chemical system. The gas, slag, matte, liquid and solid metal phases, spinel solid solution as well as numerous solid oxide and sulphide phases are included. The database works within the FactSage software environment. Examples of phase equilibria data and thermodynamic models of selected systems, as well as possible implementation of the research outcomes to selected copper making processes are presented.

Thermochemical investigations in the system Cd–Gd

PubMed Central

Reichmann, Thomas L.; Ganesan, Rajesh; Ipser, Herbert

2014-01-01

Vapour pressure measurements were performed in terms of a non-isothermal isopiestic method to determine vapour pressures of Cd in the system Cd–Gd between 693 and 1045 K. From these results thermodynamic activities of Cd were derived as a function of temperature for the composition range 52–86 at.% Cd. By employing an adapted Gibbs–Helmholtz equation, partial molar enthalpies of mixing of Cd were obtained for the corresponding composition range, which were used to convert the activity values of Cd to a common average sample temperature of 773 K. The relatively large variation of the activity across the homogeneity ranges of the phases Cd2Gd and Cd45Gd11 indicates that they probably belong to the most stable intermetallic compounds in this system. An activity value of Gd for the two phase field Cd6Gd+L was available from literature and served as an integration constant for a Gibbs–Duhem integration. Integral Gibbs energies are presented between 51 and 100 at.% Cd at 773 K, referred to Cd(l) and α-Gd(s) as standard states. Gibbs energies of formation for the exact stoichiometric compositions of the phases Cd58Gd13, Cd45Gd11, Cd3Gd and Cd2Gd were obtained at 773 K as about −19.9, −21.1, −24.8, and −30.0 kJ g atom−1, respectively. PMID:25328283

Dehydration kinetics of talc and 10 Å phase: Consequences for subduction zone seismicity

NASA Astrophysics Data System (ADS)

Chollet, Mélanie; Daniel, Isabelle; Koga, Kenneth T.; Petitgirard, Sylvain; Morard, Guillaume

2009-06-01

The process of dehydration embrittlement is usually proposed as an explanation for the presence of intermediate-depth earthquakes in subduction zones. It assumes that the release of water by hydrous mineral breakdown is fast enough to provoke brittle failure. We performed high-pressure, high-temperature, dehydration experiments of talc and 10 Å phase coupled with in situ measurement of reaction kinetics using synchrotron X-ray diffraction. Newly developed, X-ray transparent, pressure-sealed, titanium capsule ensured a closed thermochemical environment. From isothermal kinetics data fitted to the Avrami's equation and from the texture of reaction products, we conclude that dehydration rates of these minerals are limited by diffusion. Predicted minimum rates of fluid release range from 10 - 4 to 9 × 10 - 6 m 3fluid m - 3 rock s - 1 , and are fast enough to provoke hydraulic rupture since Maxwell relaxation rate of rocks relevant of subduction zones are slower than the rate of fluid release. These rates are comparable between talc, 10 Å phase and antigorite also [Perrillat, J.-P., Daniel, I., Koga, K.T., Reynard, B., Cardon, H., Crichton, W.A., 2005. Kinetics of antigorite dehydration: a real-time X-ray diffraction study. Earth Planet. Sci. Lett. 236, 899-913]. Consequently, we suggest that the dehydration of hydrous minerals may eventually be fast enough to trigger the intermediate-depth earthquakes, and that the deepest among intermediate-depth earthquakes may actually locate the limits for dehydration of hydrous minerals in the downgoing lithosphere.

Alteration minerals in impact-generated hydrothermal systems - Exploring host rock variability

NASA Astrophysics Data System (ADS)

Schwenzer, Susanne P.; Kring, David A.

2013-09-01

Impact-generated hydrothermal systems have been previously linked to the alteration of Mars’ crust and the production of secondary mineral assemblages seen from orbit. The sensitivity of the resultant assemblages has not yet been evaluated as a function of precursor primary rock compositions. In this work, we use thermochemical modeling to explore the variety of minerals that could be produced by altering several known lithologies based on martian meteorite compositions. For a basaltic host rock lithology (Dhofar 378, Humphrey) the main alteration phases are feldspar, zeolite, pyroxene, chlorite, clay (nontronite, kaolinite), and hematite; for a lherzolithic host rock lithology (LEW 88516) the main alteration phases are amphibole, serpentine, chlorite, clay (nontronite, kaolinite), and hematite; and for an ultramafic host rock lithology (Chassigny) the main minerals are secondary olivine, serpentine, magnetite, quartz, and hematite. These assemblages and proportions of phases in each of those cases depend on W/R and temperature. Integrating geologic, hydrologic and alteration mineral evidence, we have developed a model to illustrate the distribution of alteration assemblages that occur in different levels of an impact structure. At the surface, hot, hydrous alteration affects the ejecta and melt sheet producing clay and chlorite. Deeper in the subsurface and depending on the permeability of the rock, a variety of minerals - smectite, chlorite, serpentine, amphiboles and hematite - are produced in a circulating hydrothermal system. These modeled mineral distributions should assist with interpretation of orbital observations and help guide surface exploration by rovers and sample return assets.

Conformational polymorphism and thermochemical analysis of 5,5' ''-bis[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)ethyl]-2,2':5',2' ':5' ',2' ''-quaterthiophene.

PubMed

Muguruma, Hitoshi; Hotta, Shu

2006-11-23

The titled compound exists as two polymorphic solid phases (denoted form-I and form-II). Form-I obtained by as-synthesized material is a more stable phase. Form-II is a less stable phase. Spontaneous solid-solid transformation from form-II to form-I is observed in the temperature range between room temperature and the melting point of form-I (Tm = 156.5 degrees C), and its activation energy is estimated to be 96 kJ mol-1 by Arrhenius plot. The solid-solute-solid transformation (recrystallization from solution) from form-II to form-I is also observed. In contrast, form-II is obtained only by a solid-melt-solid transformation from form-I. Therefore, the system of two polymorphs is monotropic. The solid-state NMR measurement shows that form-I has the molecular conformation of complete S-syn-anti-syn in the oligothiophene backbone, whereas form-II has that of S-all-anti. With the solution NMR data, the polymorphism could not be observed. Therefore, the polymorphs originate from the different molecular packing involving the conformational change of the molecule. This unique property is attributed to the extra bulky terminal groups of the compounds. However, despite the extra bulky terminal groups, the mentioned polymorphism is not observed in the titled compound analogue which has S-all-anti conformation (like form-II).

Origin and chemical composition of the amorphous material from the intergrain pores of self-assembled cubic ZnS:Mn nanocrystals

NASA Astrophysics Data System (ADS)

Stefan, Mariana; Vlaicu, Ioana Dorina; Nistor, Leona Cristina; Ghica, Daniela; Nistor, Sergiu Vasile

2017-12-01

We have shown in previous investigations that the low temperature collective magnetism observed in mesoporous cubic ZnS:Mn nanocrystalline powders prepared by colloidal synthesis, with nominal doping concentrations above 0.2 at.%, is due to the formation of Mn2+ clusters with distributed antiferromagnetic coupling localized in an amorphous phase found between the cubic ZnS:Mn nanocrystals. Here we investigate the composition, origin and thermal annealing behavior of this amorphous phase in such a mesoporous ZnS:Mn sample doped with 5 at.% Mn nominal concentration. Correlated analytical transmission electron microscopy, multifrequency electron paramagnetic resonance and Fourier transform infrared spectroscopy data show that the amorphous nanomaterial consists of unreacted precursor hydrated zinc and manganese acetates trapped inside the pores and on the surface of the cubic ZnS nanocrystals. The decomposition of the acetates under isochronal annealing up to 270 °C, where the mesoporous structure is still preserved, lead to changes in the nature and strength of the magnetic interactions between the aggregated Mn2+ ions. These results strongly suggest the possibility to modulate the magnetic properties of such transition metal ions doped II-VI mesoporous structures by varying the synthesis conditions and/or by post-synthesis thermochemical treatments.

A mixture-energy-consistent six-equation two-phase numerical model for fluids with interfaces, cavitation and evaporation waves

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pelanti, Marica, E-mail: marica.pelanti@ensta-paristech.fr; Shyue, Keh-Ming, E-mail: shyue@ntu.edu.tw

2014-02-15

We model liquid–gas flows with cavitation by a variant of the six-equation single-velocity two-phase model with stiff mechanical relaxation of Saurel–Petitpas–Berry (Saurel et al., 2009) [9]. In our approach we employ phasic total energy equations instead of the phasic internal energy equations of the classical six-equation system. This alternative formulation allows us to easily design a simple numerical method that ensures consistency with mixture total energy conservation at the discrete level and agreement of the relaxed pressure at equilibrium with the correct mixture equation of state. Temperature and Gibbs free energy exchange terms are included in the equations as relaxationmore » terms to model heat and mass transfer and hence liquid–vapor transition. The algorithm uses a high-resolution wave propagation method for the numerical approximation of the homogeneous hyperbolic portion of the model. In two dimensions a fully-discretized scheme based on a hybrid HLLC/Roe Riemann solver is employed. Thermo-chemical terms are handled numerically via a stiff relaxation solver that forces thermodynamic equilibrium at liquid–vapor interfaces under metastable conditions. We present numerical results of sample tests in one and two space dimensions that show the ability of the proposed model to describe cavitation mechanisms and evaporation wave dynamics.« less

On the likelihood of post-perovskite near the core-mantle boundary: A statistical interpretation of seismic observations

NASA Astrophysics Data System (ADS)

Cobden, Laura; Mosca, Ilaria; Trampert, Jeannot; Ritsema, Jeroen

2012-11-01

Recent experimental studies indicate that perovskite, the dominant lower mantle mineral, undergoes a phase change to post-perovskite at high pressures. However, it has been unclear whether this transition occurs within the Earth's mantle, due to uncertainties in both the thermochemical state of the lowermost mantle and the pressure-temperature conditions of the phase boundary. In this study we compare the relative fit to global seismic data of mantle models which do and do not contain post-perovskite, following a statistical approach. Our data comprise more than 10,000 Pdiff and Sdiff travel-times, global in coverage, from which we extract the global distributions of dln VS and dln VP near the core-mantle boundary (CMB). These distributions are sensitive to the underlying lateral variations in mineralogy and temperature even after seismic uncertainties are taken into account, and are ideally suited for investigating the likelihood of the presence of post-perovskite. A post-perovskite-bearing CMB region provides a significantly closer fit to the seismic data than a post-perovskite-free CMB region on both a global and regional scale. These results complement previous local seismic reflection studies, which have shown a consistency between seismic observations and the physical properties of post-perovskite inside the deep Earth.

Recovery Act: An Integrated Experimental and Numerical Study: Developing a Reaction Transport Model that Couples Chemical Reactions of Mineral Dissolution/Precipitation with Spatial and Temporal Flow Variations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saar, Martin O.; Seyfried, Jr., William E.; Longmire, Ellen K.

2016-06-24

A total of 12 publications and 23 abstracts were produced as a result of this study. In particular, the compilation of a thermodynamic database utilizing consistent, current thermodynamic data is a major step toward accurately modeling multi-phase fluid interactions with solids. Existing databases designed for aqueous fluids did not mesh well with existing solid phase databases. Addition of a second liquid phase (CO2) magnifies the inconsistencies between aqueous and solid thermodynamic databases. Overall, the combination of high temperature and pressure lab studies (task 1), using a purpose built apparatus, and solid characterization (task 2), using XRCT and more developed technologies,more » allowed observation of dissolution and precipitation processes under CO2 reservoir conditions. These observations were combined with results from PIV experiments on multi-phase fluids (task 3) in typical flow path geometries. The results of the tasks 1, 2, and 3 were compiled and integrated into numerical models utilizing Lattice-Boltzmann simulations (task 4) to realistically model the physical processes and were ultimately folded into TOUGH2 code for reservoir scale modeling (task 5). Compilation of the thermodynamic database assisted comparisons to PIV experiments (Task 3) and greatly improved Lattice Boltzmann (Task 4) and TOUGH2 simulations (Task 5). PIV (Task 3) and experimental apparatus (Task 1) have identified problem areas in TOUGHREACT code. Additional lab experiments and coding work has been integrated into an improved numerical modeling code.« less

Thermal Shock and Ablation Behavior of Tungsten Nozzle Produced by Plasma Spray Forming and Hot Isostatic Pressing

NASA Astrophysics Data System (ADS)

Wang, Y. M.; Xiong, X.; Zhao, Z. W.; Xie, L.; Min, X. B.; Yan, J. H.; Xia, G. M.; Zheng, F.

2015-08-01

Tungsten nozzle was produced by plasma spray forming (PSF, relative density of 86 ± 2%) followed by hot isostatic pressing (HIPing, 97 ± 2%) at 2000 °C and 180 MPa for 180 min. Scanning electron microscope, x-ray diffractometer, Archimedes method, Vickers hardness, and tensile tests have been employed to study microstructure, phase composition, density, micro-hardness, and mechanical properties of the parts. Resistance of thermal shock and ablation behavior of W nozzle were investigated by hot-firing test on solid rocket motor (SRM). Comparing with PSF nozzle, less damage was observed for HIPed sample after SRM test. Linear ablation rate of nozzle made by PSF was (0.120 ± 0.048) mm/s, while that after HIPing reduced to (0.0075 ± 0.0025) mm/s. Three types of ablation mechanisms including mechanical erosion, thermophysical erosion, and thermochemical ablation took place during hot-firing test. The order of degree of ablation was nozzle throat > convergence > dilation inside W nozzle.

Synthesis, crystal growth, structural and physicochemical studies of novel binary organic complex: 4-chloroaniline-3-hydroxy-4-methoxybenzaldehyde

NASA Astrophysics Data System (ADS)

Sharma, K. P.; Reddi, R. S. B.; Bhattacharya, S.; Rai, R. N.

2012-06-01

The solid-state reaction, which is solvent free and green synthesis, has been adopted to explore the novel compound. The phase diagram of 4-chloroaniline (CA) and 3-hydroxy-4-methoxybenzaldehyde (HMB) system shows the formation of a novel 1:1 molecular complex, and two eutectics on either sides of complex. Thermochemical studies of complex and eutectics have been carried out for various properties such as heat of fusion, entropy of fusion, Jackson's parameters, interfacial energy and excess thermodynamic functions. The formation of molecular complex was also studied by IR, NMR, elemental analysis and UV-Vis absorption spectra. The single crystal of molecular complex was grown and its XRD study confirms the formation of complex and identifies the crystal structure and atomic packing of crystal of complex. Transmission spectra of grown crystal of the complex show 70% transmittance efficiency with cut off wavelength 412 nm. The band gap and refractive index of the crystal of complex have also been studied.

Proton Affinities of Anionic Bases:  Trends Across the Periodic Table, Structural Effects, and DFT Validation.

PubMed

Swart, Marcel; Bickelhaupt, F Matthias

2006-03-01

We have carried out an extensive exploration of the gas-phase basicity of archetypal anionic bases across the periodic system using the generalized gradient approximation of density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton affinities and related thermochemical quantities:  BP86/QZ4P//BP86/TZ2P is shown to yield a mean absolute deviation of 1.6 kcal/mol for the proton affinity at 0 K with respect to high-level ab initio benchmark data. The main purpose of this work is to provide the proton affinities (and corresponding entropies) at 298 K of the anionic conjugate bases of all main-group-element hydrides of groups 14-17 and periods 2-6. We have also studied the effect of stepwise methylation of the protophilic center of the second- and third-period bases.

Computational Modeling of Meteor-Generated Ground Pressure Signatures

NASA Technical Reports Server (NTRS)

Nemec, Marian; Aftosmis, Michael J.; Brown, Peter G.

2017-01-01

We present a thorough validation of a computational approach to predict infrasonic signatures of centimeter-sized meteoroids. We assume that the energy deposition along the meteor trail is dominated by atmospheric drag and simulate the steady, inviscid flow of air in thermochemical equilibrium to compute the meteoroid's near-body pressure signature. This signature is then propagated through a stratified and windy atmosphere to the ground using a methodology adapted from aircraft sonic-boom analysis. An assessment of the numerical accuracy of the near field and the far field solver is presented. The results show that when the source of the signature is the cylindrical Mach-cone, the simulations closely match the observations. The prediction of the shock rise-time, the zero-peak amplitude of the waveform, and the duration of the positive pressure phase are consistently within 10% of the measurements. Uncertainty in the shape of the meteoroid results in a poorer prediction of the trailing part of the waveform. Overall, our results independently verify energy deposition estimates deduced from optical observations.

Oxidation/vaporization of silicide coated columbium base alloys

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Stearns, C. A.

1971-01-01

Mass spectrometric and target collection experiments were made at 1600 K to elucidate the mode of oxidative vaporization of two columbium alloys, fused-slurry-coated with a complex silicide former (Si-20Cr-Fe). At oxygen pressures up to 0.0005 torr the major vapor component detected by mass spectrometry for oxidized samples was gaseous silicon monoxide. Analysis of condensates collected at oxygen pressures of 0.1, 1.0 and 10 torr revealed that chromium-, silicon-, iron- and tungsten- containing species were the major products of vaporization. Equilibrium thermochemical diagrams were constructed for the metal-oxygen system corresponding to each constituent metal in both the coating and base alloy. The major vaporizing species are expected to be the gaseous oxides of chromium, silicon, iron and tungsten. Plots of vapor phase composition and maximum vaporization rate versus oxygen pressure were calculated for each coating constituent. The major contribution to weight loss by vaporization at oxygen pressures above 1 torr was shown to be the chromium-containing species.

BAC-MP4 predictions of thermochemistry for the gas-phase tin compounds in the Sn-H-C-Cl system.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Allendorf, Mark D.; Melius, Carl F.

2004-09-01

In this work, the BAC-MP4 method is extended for the first time to compounds in the fourth row of the periodic table, resulting in a self-consistent set of thermochemical data for 56 tin-containing molecules in the Sn-H-C-Cl system. The BAC-MP4 method combines ab initio electronic structure calculations with empirical corrections to obtain accurate heats of formation. To obtain electronic energies for tin-containing species, the standard 6-31G(d,p) basis set used in BAC-MP4 calculations is augmented with a relativistic effective core potential to describe the electronic structure of the tin atom. Both stable compounds and radical species are included in this study.more » Trends within homologous series and calculated bond dissociation energies are consistent with previous BAC-MP4 predictions for group 14 compounds and the limited data available from the literature, indicating that the method is performing well for these compounds.« less

New results in gravity dependent two-phase flow regime mapping

NASA Astrophysics Data System (ADS)

Kurwitz, Cable; Best, Frederick

2002-01-01

Accurate prediction of thermal-hydraulic parameters, such as the spatial gas/liquid orientation or flow regime, is required for implementation of two-phase systems. Although many flow regime transition models exist, accurate determination of both annular and slug regime boundaries is not well defined especially at lower flow rates. Furthermore, models typically indicate the regime as a sharp transition where data may indicate a transition space. Texas A&M has flown in excess of 35 flights aboard the NASA KC-135 aircraft with a unique two-phase package. These flights have produced a significant database of gravity dependent two-phase data including visual observations for flow regime identification. Two-phase flow tests conducted during recent zero-g flights have added to the flow regime database and are shown in this paper with comparisons to selected transition models. .

An effective approach for iris recognition using phase-based image matching.

PubMed

Miyazawa, Kazuyuki; Ito, Koichi; Aoki, Takafumi; Kobayashi, Koji; Nakajima, Hiroshi

2008-10-01

This paper presents an efficient algorithm for iris recognition using phase-based image matching--an image matching technique using phase components in 2D Discrete Fourier Transforms (DFTs) of given images. Experimental evaluation using CASIA iris image databases (versions 1.0 and 2.0) and Iris Challenge Evaluation (ICE) 2005 database clearly demonstrates that the use of phase components of iris images makes possible to achieve highly accurate iris recognition with a simple matching algorithm. This paper also discusses major implementation issues of our algorithm. In order to reduce the size of iris data and to prevent the visibility of iris images, we introduce the idea of 2D Fourier Phase Code (FPC) for representing iris information. The 2D FPC is particularly useful for implementing compact iris recognition devices using state-of-the-art Digital Signal Processing (DSP) technology.

How to select equivalent and complimentary reversed phase liquid chromatography columns from column characterization databases.

PubMed

Borges, Endler M

2014-01-07

Three RP-LC column characterization protocols [Tanaka et al. (1989), Snyder et al. (PQRI, 2002), and NIST SRM 870 (2000)] were evaluated using both Euclidian distance and Principal Components Analysis to evaluate effectiveness at identifying equivalent columns. These databases utilize specific chromatographic properties such as hydrophobicity, hydrogen bonding, shape/steric selectivity, and ion exchange capacity of stationary phases. The chromatographic parameters of each test were shown to be uncorrelated. Despite this, the three protocols were equally successful in identifying similar and/or dissimilar stationary phases. The veracity of the results has been supported by some real life pharmaceutical separations. The use of Principal Component Analysis to identify similar/dissimilar phases appears to have some limitations in terms of loss of information. In contrast, the use of Euclidian distances is a much more convenient and reliable approach. The use of auto scaled data is favoured over the use of weighted factors as the former data transformation is less affected by the addition or removal of columns from the database. The use of these free databases and their corresponding software tools shown to be valid for identifying similar columns with equivalent chromatographic selectivity and retention as a "backup column". In addition, dissimilar columns with complimentary chromatographic selectivity can be identified for method development screening strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

Production of Hydrogen by Superadiabatic Decomposition of Hydrogen Sulfide - Final Technical Report for the Period June 1, 1999 - September 30, 2000

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rachid B. Slimane; Francis S. Lau; Javad Abbasian

2000-10-01

The objective of this program is to develop an economical process for hydrogen production, with no additional carbon dioxide emission, through the thermal decomposition of hydrogen sulfide (H{sub 2}S) in H{sub 2}S-rich waste streams to high-purity hydrogen and elemental sulfur. The novel feature of the process being developed is the superadiabatic combustion (SAC) of part of the H{sub 2}S in the waste stream to provide the thermal energy required for the decomposition reaction such that no additional energy is required. The program is divided into two phases. In Phase 1, detailed thermochemical and kinetic modeling of the SAC reactor withmore » H{sub 2}S-rich fuel gas and air/enriched air feeds is undertaken to evaluate the effects of operating conditions on exit gas products and conversion efficiency, and to identify key process parameters. Preliminary modeling results are used as a basis to conduct a thorough evaluation of SAC process design options, including reactor configuration, operating conditions, and productivity-product separation schemes, with respect to potential product yields, thermal efficiency, capital and operating costs, and reliability, ultimately leading to the preparation of a design package and cost estimate for a bench-scale reactor testing system to be assembled and tested in Phase 2 of the program. A detailed parametric testing plan was also developed for process design optimization and model verification in Phase 2. During Phase 2 of this program, IGT, UIC, and industry advisors UOP and BP Amoco will validate the SAC concept through construction of the bench-scale unit and parametric testing. The computer model developed in Phase 1 will be updated with the experimental data and used in future scale-up efforts. The process design will be refined and the cost estimate updated. Market survey and assessment will continue so that a commercial demonstration project can be identified.« less

The Wannabee Culture: Why No-One Does What They Used To.

ERIC Educational Resources Information Center

Dixon, Anne

1998-01-01

Electronic publishing has been an agent for change in not just how one publishes but in what one publishes. Describes HyperCite, a joint project with the Institution of Electrical Engineers (IEE) to create INSPEC database. Highlights include the database; the research phase (cross database searching and new interface); and what and how much was…

NHEXAS PHASE I ARIZONA STUDY--STANDARD OPERATING PROCEDURE FOR DEFINING WORKING DATABASES AND DATA ENTRY FORMS (HAND ENTRY) (UA-D-3.0)

EPA Science Inventory

The purpose of this SOP is to outline a standard approach to naming and defining variables, data types, and data entry forms. This procedure applies to all working databases created during the NHEXAS project and the "Border" study. Keywords: databases; standards.

The National...

Thermochemical nanolithography components, systems, and methods

DOEpatents

Riedo, Elisa; Marder, Seth R.; de Heer, Walt A.; Szoskiewicz, Robert J.; Kodali, Vamsi K.; Jones, Simon C.; Okada, Takashi; Wang, Debin; Curtis, Jennifer E.; Henderson, Clifford L.; Hua, Yueming

2013-06-18

Improved nanolithography components, systems, and methods are described herein. The systems and methods generally employ a resistively heated atomic force microscope tip to thermally induce a chemical change in a surface. In addition, certain polymeric compositions are also disclosed.

Kristin Smith | NREL

Science.gov Websites

Smith Photo of Kristin Smith Kristin Smith Thermochemical Process Design Engineer Kristin.Smith @nrel.gov | 303-384-7877 Orcid ID http://orcid.org/0000-0001-6397-031X Research Interests Kristin Smith is a

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, C.E.; Robinson, P.R.

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, Carlos E.; Robinson, Paul R.

1980-01-01

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Cemore » 4+/Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.« less

Active Thermochemical Tables: The Adiabatic Ionization Energy of Hydrogen Peroxide.

PubMed

Changala, P Bryan; Nguyen, T Lam; Baraban, Joshua H; Ellison, G Barney; Stanton, John F; Bross, David H; Ruscic, Branko

2017-11-22

The adiabatic ionization energy of hydrogen peroxide (HOOH) is investigated, both by means of theoretical calculations and theoretically assisted reanalysis of previous experimental data. Values obtained by three different approaches: 10.638 ± 0.012 eV (purely theoretical determination), 10.649 ± 0.005 eV (reanalysis of photoelectron spectrum), and 10.645 ± 0.010 eV (reanalysis of photoionization spectrum) are in excellent mutual agreement. Further refinement of the latter two values to account for asymmetry of the rotational profile of the photoionization origin band leads to a reduction of 0.007 ± 0.006 eV, which tends to bring them into even closer alignment with the purely theoretical value. Detailed analysis of this fundamental quantity by the Active Thermochemical Tables approach, using the present results and extant literature, gives a final estimate of 10.641 ± 0.006 eV.

Active Thermochemical Tables: The Adiabatic Ionization Energy of Hydrogen Peroxide

DOE PAGES

Changala, P. Bryan; Nguyen, T. Lam; Baraban, Joshua H.; ...

2017-09-07

The adiabatic ionization energy of hydrogen peroxide (HOOH) is investigated, both by means of theoretical calculations and theoretically-assisted reanalysis of previous experimental data. Values obtained by three different approaches: 10.638 ± 0.012 eV (purely theoretical determination), 10.649 ± 0.005 eV (reanalysis of photoelectron spectrum) and 10.645 ± 0.010 eV (reanalysis of photoionization spectrum) are in excellent mutual agreement. Further refinement of the latter two values to account for asymmetry of the rotational profile of the photoionization origin band leads to a reduction of 0.007 ± 0.006 eV, which tends to bring them into even closer alignment with the purely theoreticalmore » value. As a result, detailed analysis of this fundamental quantity by the Active Thermochemical Tables (ATcT) approach, using the present results and extant literature, gives a final estimate of 10.641 ± 0.006 eV.« less

Thermochemical factors affecting the dehalogenation of aromatics.

PubMed

Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J

2013-12-17

Halogenated aromatics are one of the largest chemical classes of environmental contaminants, and dehalogenation remains one of the most important processes by which these compounds are degraded and detoxified. The thermodynamic constraints of aromatic dehalogenation reactions are thus important for understanding the feasibility of such reactions and the redox conditions necessary for promoting them. Accordingly, the thermochemical properties of the (poly)fluoro-, (poly)chloro-, and (poly)bromobenzenes, including standard enthalpies of formation, bond dissociation enthalpies, free energies of reaction, and the redox potentials of Ar-X/Ar-H couples, were investigated using a validated density functional protocol combined with continuum solvation calculations when appropriate. The results highlight the fact that fluorinated aromatics stand distinct from their chloro- and bromo- counterparts in terms of both their relative thermodynamic stability toward dehalogenation and how different substitution patterns give rise to relevant properties, such as bond strengths and reduction potentials.

Comparative study of thermochemical processes for hydrogen production from biomass fuels.

PubMed

Biagini, Enrico; Masoni, Lorenzo; Tognotti, Leonardo

2010-08-01

Different thermochemical configurations (gasification, combustion, electrolysis and syngas separation) are studied for producing hydrogen from biomass fuels. The aim is to provide data for the production unit and the following optimization of the "hydrogen chain" (from energy source selection to hydrogen utilization) in the frame of the Italian project "Filiera Idrogeno". The project focuses on a regional scale (Tuscany, Italy), renewable energies and automotive hydrogen. Decentred and small production plants are required to solve the logistic problems of biomass supply and meet the limited hydrogen infrastructures. Different options (gasification with air, oxygen or steam/oxygen mixtures, combustion, electrolysis) and conditions (varying the ratios of biomass and gas input) are studied by developing process models with uniform hypothesis to compare the results. Results obtained in this work concern the operating parameters, process efficiencies, material and energetic needs and are fundamental to optimize the entire hydrogen chain. Copyright 2010 Elsevier Ltd. All rights reserved.

VUV Dissociative Photoionization of Quinoline in the 7-26 eV Photon Energy Range

NASA Astrophysics Data System (ADS)

Leach, Sydney; Jochims, Hans-Werner; Baumgärtel, Helmut; Champion, Norbert

2018-05-01

The dissociative photoionization of quinoline was studied by photoionization mass spectrometry and ion yield measurements over a synchrotron photon excitation energy range 7-26 eV. The ionic and neutral products were identified with the aid of thermochemical calculations that, in some cases, led to deeper understanding of photodissociation pathways and the determination of upper limits of heats of formation of ionic and neutral dissociation products. A detailed comparison between the 20 eV photon excitation and 70 eV electron impact mass spectra, coupled with estimation of thermochemical appearance energies, leads to assignment of the dissociative ionization cation and neutral products for each detected ion. Reaction schemes for formation of these products are proposed in a number of cases. Ion intensities in the photon and electron impact mass spectra were used to consider extending a rule of charge retention in simple bond cleavage to more complex cases of dissociative ionization.

Review of the Two-Step H2O/CO2-Splitting Solar Thermochemical Cycle Based on Zn/ZnO Redox Reactions

PubMed Central

Loutzenhiser, Peter G.; Meier, Anton; Steinfeld, Aldo

2010-01-01

This article provides a comprehensive overview of the work to date on the two‑step solar H2O and/or CO2 splitting thermochemical cycles with Zn/ZnO redox reactions to produce H2 and/or CO, i.e., synthesis gas—the precursor to renewable liquid hydrocarbon fuels. The two-step cycle encompasses: (1) The endothermic dissociation of ZnO to Zn and O2 using concentrated solar energy as the source for high-temperature process heat; and (2) the non-solar exothermic oxidation of Zn with H2O/CO2 to generate H2/CO, respectively; the resulting ZnO is then recycled to the first step. An outline of the underlying science and the technological advances in solar reactor engineering is provided along with life cycle and economic analyses. PMID:28883361

High-flux solar-driven thermochemical dissociation of CO2 and H2O using nonstoichiometric ceria.

PubMed

Chueh, William C; Falter, Christoph; Abbott, Mandy; Scipio, Danien; Furler, Philipp; Haile, Sossina M; Steinfeld, Aldo

2010-12-24

Because solar energy is available in large excess relative to current rates of energy consumption, effective conversion of this renewable yet intermittent resource into a transportable and dispatchable chemical fuel may ensure the goal of a sustainable energy future. However, low conversion efficiencies, particularly with CO(2) reduction, as well as utilization of precious materials have limited the practical generation of solar fuels. By using a solar cavity-receiver reactor, we combined the oxygen uptake and release capacity of cerium oxide and facile catalysis at elevated temperatures to thermochemically dissociate CO(2) and H(2)O, yielding CO and H(2), respectively. Stable and rapid generation of fuel was demonstrated over 500 cycles. Solar-to-fuel efficiencies of 0.7 to 0.8% were achieved and shown to be largely limited by the system scale and design rather than by chemistry.

Controlled Chemical Patterns with ThermoChemical NanoLithography (TCNL)

NASA Astrophysics Data System (ADS)

Carroll, Keith; Giordano, Anthony; Wang, Debin; Kodali, Vamsi; King, W. P.; Marder, S. R.; Riedo, E.; Curtis, J. E.

2012-02-01

Many research areas, both fundamental and applied, rely upon the ability to organize non-trivial assemblies of molecules on surfaces. In this work, we introduce a significant extension of ThermoChemical NanoLithography (TCNL), a high throughput chemical patterning technique that uses temperature-driven chemical reactions localized near the tip of a thermal cantilever. By combining a chemical kinetics based model with experiments, we have developed a protocol for varying the concentration of surface bound molecules. The result is an unprecedented ability to fabricate extremely complex patterns comprised of varying chemical concentrations, as demonstrated by sinusoidal patterns of amine groups with varying pitches (˜5-15 μm) and the replication of Leonardo da Vinci's Mona Lisa with dimensions of ˜30 x 40 μm^2. Programmed control of the chemical reaction rate should have widespread applications for a technique which has already been shown to nanopattern various substrates including graphene nanowires, piezoelectric crystals, and optoelectronic materials.

Regeneration of glass nanofluidic chips through a multiple-step sequential thermochemical decomposition process at high temperatures.

PubMed

Xu, Yan; Wu, Qian; Shimatani, Yuji; Yamaguchi, Koji

2015-10-07

Due to the lack of regeneration methods, the reusability of nanofluidic chips is a significant technical challenge impeding the efficient and economic promotion of both fundamental research and practical applications on nanofluidics. Herein, a simple method for the total regeneration of glass nanofluidic chips was described. The method consists of sequential thermal treatment with six well-designed steps, which correspond to four sequential thermal and thermochemical decomposition processes, namely, dehydration, high-temperature redox chemical reaction, high-temperature gasification, and cooling. The method enabled the total regeneration of typical 'dead' glass nanofluidic chips by eliminating physically clogged nanoparticles in the nanochannels, removing chemically reacted organic matter on the glass surface and regenerating permanent functional surfaces of dissimilar materials localized in the nanochannels. The method provides a technical solution to significantly improve the reusability of glass nanofluidic chips and will be useful for the promotion and acceleration of research and applications on nanofluidics.

Assessment of relative flammability and thermochemical properties of some thermoplastic materials

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Parker, J. A.

1978-01-01

The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use and others being considered for use in aircraft interiors are described. The properties studied included (1) thermal mechanical properties such as glass transition and melt temperature, (2) changes in polymer enthalpy by differential scanning calorimetry, (3) thermogravimetric analysis in an anaerobic and oxidative environment, (4) oxygen index, (5) smoke evolution, (6) relative toxicity of the volatile products of pyrolysis, and (7) selected physical properties. The generic polymers which were evaluated included: acrylonitrile-butadiene-styrene, bisphenol A polycarbonate, bisphenol fluorenone carbonatedimethylsiloxane block polymer, phenolphthalein-bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters including molding characteristics of some of the advanced polymers are described. Test results and relative rankings of some of the flammability, smoke and toxicity properties are presented.

Baking sunflower hulls within an aluminum envelope in a common laboratory oven yields charcoal.

PubMed

Arnal, Pablo Maximiliano

2015-01-01

Charcoals have been widely used by scientist to research the removal of contaminants from water and air. One key feature of charcoal is that it keeps macropores from the parent material - though anisotropically contracted - and can even develop meso- and micropores. However, the controlled thermochemical conversion of biomass into charcoal at laboratory scale normally requires special setups which involve either vacuum or inert gas. Those setups may not be affordable in research groups or educational institutions where the research of charcoals would be highly welcome. In this work, I propose a simple and effective method to steer the thermochemical process that converts sunflower hulls (SFH) into charcoal with basic laboratory resources. The carbonization method: •Place SFH in an airtight aluminum envelope.•Thermally treat SFH within the envelope in a common laboratory oven.•Open the envelope to obtain the carbonized sunflower hulls.

Low-buoyancy thermochemical plumes resolve controversy of classical mantle plume concept

NASA Astrophysics Data System (ADS)

Dannberg, Juliane; Sobolev, Stephan V.

2015-04-01

The Earth's biggest magmatic events are believed to originate from massive melting when hot mantle plumes rising from the lowermost mantle reach the base of the lithosphere. Classical models predict large plume heads that cause kilometre-scale surface uplift, and narrow (100 km radius) plume tails that remain in the mantle after the plume head spreads below the lithosphere. However, in many cases, such uplifts and narrow plume tails are not observed. Here using numerical models, we show that the issue can be resolved if major mantle plumes contain up to 15-20% of recycled oceanic crust in a form of dense eclogite, which drastically decreases their buoyancy and makes it depth dependent. We demonstrate that, despite their low buoyancy, large enough thermochemical plumes can rise through the whole mantle causing only negligible surface uplift. Their tails are bulky (>200 km radius) and remain in the upper mantle for 100 millions of years.

An evaluation of tannery industry wastewater treatment sludge gasification by artificial neural network modeling.

PubMed

Ongen, Atakan; Ozcan, H Kurtulus; Arayıcı, Semiha

2013-12-15

This paper reports on the calorific value of synthetic gas (syngas) produced by gasification of dewatered sludge derived from treatment of tannery wastewater. Proximate and ultimate analyses of samples were performed. Thermochemical conversion alters the chemical structure of the waste. Dried air was used as a gasification agent at varying flow rates, which allowed the feedstock to be quickly converted into gas by means of different heterogeneous reactions. A lab-scale updraft fixed-bed steel reactor was used for thermochemical conversion of sludge samples. Artificial neural network (ANN) modeling techniques were used to observe variations in the syngas related to operational conditions. Modeled outputs showed that temporal changes of model predictions were in close accordance with real values. Correlation coefficients (r) showed that the ANN used in this study gave results with high sensitivity. Copyright © 2013 Elsevier B.V. All rights reserved.

Technical challenges and future direction for high-efficiency metal hydride thermal energy storage systems

NASA Astrophysics Data System (ADS)

Ward, Patrick A.; Corgnale, Claudio; Teprovich, Joseph A.; Motyka, Theodore; Hardy, Bruce; Sheppard, Drew; Buckley, Craig; Zidan, Ragaiy

2016-04-01

Recently, there has been increasing interest in thermal energy storage (TES) systems for concentrated solar power (CSP) plants, which allow for continuous operation when sunlight is unavailable. Thermochemical energy storage materials have the advantage of much higher energy densities than latent or sensible heat materials. Furthermore, thermochemical energy storage systems based on metal hydrides have been gaining great interest for having the advantage of higher energy densities, better reversibility, and high enthalpies. However, in order to achieve higher efficiencies desired of a thermal storage system by the US Department of Energy, the system is required to operate at temperatures >600 °C. Operation at temperatures >600 °C presents challenges including material selection, hydrogen embrittlement and permeation of containment vessels, appropriate selection of heat transfer fluids, and cost. Herein, the technical difficulties and proposed solutions associated with the use of metal hydrides as TES materials in CSP applications are discussed and evaluated.

Joint seismic-infrasonic processing of recordings from a repeating source of atmospheric explosions.

PubMed

Gibbons, Steven J; Ringdal, Frode; Kvaerna, Tormod

2007-11-01

A database has been established of seismic and infrasonic recordings from more than 100 well-constrained surface explosions, conducted by the Finnish military to destroy old ammunition. The recorded seismic signals are essentially identical and indicate that the variation in source location and magnitude is negligible. In contrast, the infrasonic arrivals on both seismic and infrasound sensors exhibit significant variation both with regard to the number of detected phases, phase travel times, and phase amplitudes, which would be attributable to atmospheric factors. This data set provides an excellent database for studies in sound propagation, infrasound array detection, and direction estimation.

A new phase-correlation-based iris matching for degraded images.

PubMed

Krichen, Emine; Garcia-Salicetti, Sonia; Dorizzi, Bernadette

2009-08-01

In this paper, we present a new phase-correlation-based iris matching approach in order to deal with degradations in iris images due to unconstrained acquisition procedures. Our matching system is a fusion of global and local Gabor phase-correlation schemes. The main originality of our local approach is that we do not only consider the correlation peak amplitudes but also their locations in different regions of the images. Results on several degraded databases, namely, the CASIA-BIOSECURE and Iris Challenge Evaluation 2005 databases, show the improvement of our method compared to two available reference systems, Masek and Open Source for Iris (OSRIS), in verification mode.

LEPER: Library of Experimental PhasE Relations

NASA Astrophysics Data System (ADS)

Davis, F.; Gordon, S.; Mukherjee, S.; Hirschmann, M.; Ghiorso, M.

2006-12-01

The Library of Experimental PhasE Relations (LEPER) seeks to compile published experimental determinations of magmatic phase equilibria and provide those data on the web with a searchable and downloadable interface. Compiled experimental data include the conditions and durations of experiments, the bulk compositions of experimental charges, and the identity, compositions and proportions of phases observed, and, where available, estimates of experimental and analytical uncertainties. Also included are metadata such as the type of experimental device, capsule material, and method(s) of quantitative analysis. The database may be of use to practicing experimentalists as well as the wider Earth science community. Experimentalists may find the data useful for planning new experiments and will easily be able to compare their results to the full body of previous experimentnal data. Geologists may use LEPER to compare rocks sampled in the field with experiments performed on similar bulk composition or with experiments that produced similar-composition product phases. Modelers may use LEPER to parameterize partial melting of various lithologies. One motivation for compiling LEPER is for calibration of updated and revised versions of MELTS, however, it is hoped that the availability of LEPER will facilitate formulation and calibration of additional thermodynamic or empirical models of magmatic phase relations and phase equilibria, geothermometers and more. Data entry for LEPER is occuring presently: As of August, 2006, >6200 experiments have been entered, chiefly from work published between 1997 and 2005. A prototype web interface has been written and beta release on the web is anticipated in Fall, 2006. Eventually, experimentalists will be able to submit their new experimental data to the database via the web. At present, the database contains only data pertaining to the phase equilibria of silicate melts, but extension to other experimental data involving other fluids or sub-solidus phase equilibria may be contemplated. Also, the data are at present limited to natural or near-natural systems, but in the future, extension to synthetic (i.e., CMAS, etc.) systems is also possible. Each would depend in part on whether there is community demand for such databases. A trace element adjunct to LEPER is presently in planning stages.

Development of the Connecticut product evaluation database application : Phase 1B.

DOT National Transportation Integrated Search

2010-12-01

The Federal Highway Administration (FHWA), the American Association of State Highway : Transportation Officials (AASHTO) and the Transportation Research Board (TRB), a : division of the National Research Council (NRC), maintain databases to store nat...

Effects of Solid Solution Strengthening Elements Mo, Re, Ru, and W on Transition Temperatures in Nickel-Based Superalloys with High γ'-Volume Fraction: Comparison of Experiment and CALPHAD Calculations

NASA Astrophysics Data System (ADS)

Ritter, Nils C.; Sowa, Roman; Schauer, Jan C.; Gruber, Daniel; Goehler, Thomas; Rettig, Ralf; Povoden-Karadeniz, Erwin; Koerner, Carolin; Singer, Robert F.

2018-06-01

We prepared 41 different superalloy compositions by an arc melting, casting, and heat treatment process. Alloy solid solution strengthening elements were added in graded amounts, and we measured the solidus, liquidus, and γ'-solvus temperatures of the samples by DSC. The γ'-phase fraction increased as the W, Mo, and Re contents were increased, and W showed the most pronounced effect. Ru decreased the γ'-phase fraction. Melting temperatures (i.e., solidus and liquidus) were increased by addition of Re, W, and Ru (the effect increased in that order). Addition of Mo decreased the melting temperature. W was effective as a strengthening element because it acted as a solid solution strengthener and increased the fraction of fine γ'-precipitates, thus improving precipitation strengthening. Experimentally determined values were compared with calculated values based on the CALPHAD software tools Thermo-Calc (databases: TTNI8 and TCNI6) and MatCalc (database ME-NI). The ME-NI database, which was specially adapted to the present investigation, showed good agreement. TTNI8 also showed good results. The TCNI6 database is suitable for computational design of complex nickel-based superalloys. However, a large deviation remained between the experiment results and calculations based on this database. It also erroneously predicted γ'-phase separations and failed to describe the Ru-effect on transition temperatures.

The Lung Image Database Consortium (LIDC) and Image Database Resource Initiative (IDRI): A Completed Reference Database of Lung Nodules on CT Scans

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

2011-02-15

Purpose: The development of computer-aided diagnostic (CAD) methods for lung nodule detection, classification, and quantitative assessment can be facilitated through a well-characterized repository of computed tomography (CT) scans. The Lung Image Database Consortium (LIDC) and Image Database Resource Initiative (IDRI) completed such a database, establishing a publicly available reference for the medical imaging research community. Initiated by the National Cancer Institute (NCI), further advanced by the Foundation for the National Institutes of Health (FNIH), and accompanied by the Food and Drug Administration (FDA) through active participation, this public-private partnership demonstrates the success of a consortium founded on a consensus-based process.more » Methods: Seven academic centers and eight medical imaging companies collaborated to identify, address, and resolve challenging organizational, technical, and clinical issues to provide a solid foundation for a robust database. The LIDC/IDRI Database contains 1018 cases, each of which includes images from a clinical thoracic CT scan and an associated XML file that records the results of a two-phase image annotation process performed by four experienced thoracic radiologists. In the initial blinded-read phase, each radiologist independently reviewed each CT scan and marked lesions belonging to one of three categories (''nodule{>=}3 mm,''''nodule<3 mm,'' and ''non-nodule{>=}3 mm''). In the subsequent unblinded-read phase, each radiologist independently reviewed their own marks along with the anonymized marks of the three other radiologists to render a final opinion. The goal of this process was to identify as completely as possible all lung nodules in each CT scan without requiring forced consensus. Results: The Database contains 7371 lesions marked ''nodule'' by at least one radiologist. 2669 of these lesions were marked ''nodule{>=}3 mm'' by at least one radiologist, of which 928 (34.7%) received such marks from all four radiologists. These 2669 lesions include nodule outlines and subjective nodule characteristic ratings. Conclusions: The LIDC/IDRI Database is expected to provide an essential medical imaging research resource to spur CAD development, validation, and dissemination in clinical practice.« less

Electronic Effects of 11β Substituted 17β-Estradiol Derivatives and Instrumental Effects on the Relative Gas Phase Acidity

NASA Astrophysics Data System (ADS)

Bourgoin-Voillard, Sandrine; Fournier, Françoise; Afonso, Carlos; Zins, Emilie-Laure; Jacquot, Yves; Pèpe, Claude; Leclercq, Guy; Tabet, Jean-Claude

2012-12-01

Numerous studies have highlighted the role of the proton donor characteristics of the phenol group of 17β-estradiol (E2) in its association with the estrogen receptor alpha (ERα). Since the substitutions at position C(11) have been reported to modulate this association, we hypothesized that such substitutions may modify the phenol acidity. Hence, phenol gas-phase acidity of nine C(11)-substituted E2-derivatives were evaluated using the extended Cooks' kinetic method, which is a method widely used to determine thermochemical properties by mass spectrometry. To enhance accuracy in data collection we recorded data from several instruments, including quadrupole ion trap, triple quadrupole, and hybrid QqTOF. Indeed, we report for the first time the use of the QqTOF instrument to provide a novel means to improve data accuracy by giving access to an intermediate effective temperature range. All experimental gas-phase acidity values were supported by theoretical calculations. Our results confirmed the ability of distant substituents at C(11) to modulate the phenol acidity through electrostatic interactions, electron withdrawing inductive effects, and mesomeric effects. However, no relationship was found between the phenol gas-phase acidity of investigated steroids and their binding affinity for ERα assessed in solution. Thus, our results highlight that the intrinsic properties of the hormone do not influence sufficiently the stabilization of the hormone/ERα complex. It is more likely that such stabilization would be more related to factors depending on the environment within the binding pocket such as hydrophobic, steric as well as direct intermolecular electrostatic effects between ERα residues and the substituted steroidal estrogens.

CHEETAH: A fast thermochemical code for detonation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fried, L.E.

1993-11-01

For more than 20 years, TIGER has been the benchmark thermochemical code in the energetic materials community. TIGER has been widely used because it gives good detonation parameters in a very short period of time. Despite its success, TIGER is beginning to show its age. The program`s chemical equilibrium solver frequently crashes, especially when dealing with many chemical species. It often fails to find the C-J point. Finally, there are many inconveniences for the user stemming from the programs roots in pre-modern FORTRAN. These inconveniences often lead to mistakes in preparing input files and thus erroneous results. We are producingmore » a modern version of TIGER, which combines the best features of the old program with new capabilities, better computational algorithms, and improved packaging. The new code, which will evolve out of TIGER in the next few years, will be called ``CHEETAH.`` Many of the capabilities that will be put into CHEETAH are inspired by the thermochemical code CHEQ. The new capabilities of CHEETAH are: calculate trace levels of chemical compounds for environmental analysis; kinetics capability: CHEETAH will predict chemical compositions as a function of time given individual chemical reaction rates. Initial application: carbon condensation; CHEETAH will incorporate partial reactions; CHEETAH will be based on computer-optimized JCZ3 and BKW parameters. These parameters will be fit to over 20 years of data collected at LLNL. We will run CHEETAH thousands of times to determine the best possible parameter sets; CHEETAH will fit C-J data to JWL`s,and also predict full-wall and half-wall cylinder velocities.« less