Resolving Some Paradoxes in the Thermal Decomposition Mechanism of Acetaldehyde

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

Sivaramakrishnan, Raghu; Michael, Joe V.; Harding, Lawrence B.

2015-07-16

The mechanism for the thermal decomposition of acetaldehyde has been revisited with an analysis of literature kinetics experiments using theoretical kinetics. The present modeling study was motivated by recent observations, with very sensitive diagnostics, of some unexpected products in high temperature micro-tubular reactor experiments on the thermal decomposition of CH3CHO and its deuterated analogs, CH3CDO, CD3CHO, and CD3CDO. The observations of these products prompted the authors of these studies to suggest that the enol tautomer, CH2CHOH (vinyl alcohol), is a primary intermediate in the thermal decomposition of acetaldehyde. The present modeling efforts on acetaldehyde decomposition incorporate a master equation re-analysismore » of the CH3CHO potential energy surface (PES). The lowest energy process on this PES is an isomerization of CH3CHO to CH2CHOH. However, the subsequent product channels for CH2CHOH are substantially higher in energy, and the only unimolecular process that can be thermally accessed is a re-isomerization to CH3CHO. The incorporation of these new theoretical kinetics predictions into models for selected literature experiments on CH3CHO thermal decomposition confirms our earlier experiment and theory based conclusions that the dominant decomposition process in CH3CHO at high temperatures is C-C bond fission with a minor contribution (~10-20%) from the roaming mechanism to form CH4 and CO. The present modeling efforts also incorporate a master-equation analysis of the H + CH2CHOH potential energy surface. This bimolecular reaction is the primary mechanism for removal of CH2CHOH, which can accumulate to minor amounts at high temperatures, T > 1000 K, in most lab-scale experiments that use large initial concentrations of CH3CHO. Our modeling efforts indicate that the observation of ketene, water and acetylene in the recent micro-tubular experiments are primarily due to bimolecular reactions of CH3CHO and CH2CHOH with H-atoms, and have no bearing on the unimolecular decomposition mechanism of CH3CHO. The present simulations also indicate that experiments using these micro-tubular reactors when interpreted with the aid of high-level theoretical calculations and kinetics modeling can offer insights into the chemistry of elusive intermediates in high temperature pyrolysis of organic molecules.« less

Rayleigh imaging in spectral mammography

NASA Astrophysics Data System (ADS)

Berggren, Karl; Danielsson, Mats; Fredenberg, Erik

2016-03-01

Spectral imaging is the acquisition of multiple images of an object at different energy spectra. In mammography, dual-energy imaging (spectral imaging with two energy levels) has been investigated for several applications, in particular material decomposition, which allows for quantitative analysis of breast composition and quantitative contrast-enhanced imaging. Material decomposition with dual-energy imaging is based on the assumption that there are two dominant photon interaction effects that determine linear attenuation: the photoelectric effect and Compton scattering. This assumption limits the number of basis materials, i.e. the number of materials that are possible to differentiate between, to two. However, Rayleigh scattering may account for more than 10% of the linear attenuation in the mammography energy range. In this work, we show that a modified version of a scanning multi-slit spectral photon-counting mammography system is able to acquire three images at different spectra and can be used for triple-energy imaging. We further show that triple-energy imaging in combination with the efficient scatter rejection of the system enables measurement of Rayleigh scattering, which adds an additional energy dependency to the linear attenuation and enables material decomposition with three basis materials. Three available basis materials have the potential to improve virtually all applications of spectral imaging.

Metal-ligand bond directionality in the M2-NH3 complexes (M = Cu, Ag and Au)

NASA Astrophysics Data System (ADS)

Eskandari, K.; Ebadinejad, F.

2018-05-01

The metal-ligand bonds in the M2-NH3 complexes (M = Au, Ag and Cu) are directional and the M-M-N angles tend to be linear. Natural energy decomposition analysis (NEDA) and localised molecular orbital energy decomposition analysis (LMOEDA) approaches indicate that the metal-ligand bonds in these complexes are mainly electrostatic in nature, however, the electrostatic is not the cause of the linearity of M-M-N arrangements. Instead, NEDA shows that the charge transfer and core repulsion are mainly responsible for the directionality of these bonds. In the LMOEDA point of view, the repulsion term is the main reason for the linearity of these complexes. Interacting quantum atoms (IQA) analysis shows that inter-atomic and inter-fragment interactions favour the nonlinear arrangements; however, these terms are compensated by the atomic self-energies, which stabilise the linear structure.

Mode Analyses of Gyrokinetic Simulations of Plasma Microturbulence

NASA Astrophysics Data System (ADS)

Hatch, David R.

This thesis presents analysis of the excitation and role of damped modes in gyrokinetic simulations of plasma microturbulence. In order to address this question, mode decompositions are used to analyze gyrokinetic simulation data. A mode decomposition can be constructed by projecting a nonlinearly evolved gyrokinetic distribution function onto a set of linear eigenmodes, or alternatively by constructing a proper orthogonal decomposition of the distribution function. POD decompositions are used to examine the role of damped modes in saturating ion temperature gradient driven turbulence. In order to identify the contribution of different modes to the energy sources and sinks, numerical diagnostics for a gyrokinetic energy quantity were developed for the GENE code. The use of these energy diagnostics in conjunction with POD mode decompositions demonstrates that ITG turbulence saturates largely through dissipation by damped modes at the same perpendicular spatial scales as those of the driving instabilities. This defines a picture of turbulent saturation that is very different from both traditional hydrodynamic scenarios and also many common theories for the saturation of plasma turbulence. POD mode decompositions are also used to examine the role of subdominant modes in causing magnetic stochasticity in electromagnetic gyrokinetic simulations. It is shown that the magnetic stochasticity, which appears to be ubiquitous in electromagnetic microturbulence, is caused largely by subdominant modes with tearing parity. The application of higher-order singular value decomposition (HOSVD) to the full distribution function from gyrokinetic simulations is presented. This is an effort to demonstrate the ability to characterize and extract insight from a very large, complex, and high-dimensional data-set - the 5-D (plus time) gyrokinetic distribution function.

The implications of microbial and substrate limitation for the fates of carbon in different organic soil horizon types of boreal forest ecosystems: a mechanistically based model analysis

USGS Publications Warehouse

He, Y.; Zhuang, Q.; Harden, Jennifer W.; McGuire, A. David; Fan, Z.; Liu, Y.; Wickland, Kimberly P.

2014-01-01

The large amount of soil carbon in boreal forest ecosystems has the potential to influence the climate system if released in large quantities in response to warming. Thus, there is a need to better understand and represent the environmental sensitivity of soil carbon decomposition. Most soil carbon decomposition models rely on empirical relationships omitting key biogeochemical mechanisms and their response to climate change is highly uncertain. In this study, we developed a multi-layer microbial explicit soil decomposition model framework for boreal forest ecosystems. A thorough sensitivity analysis was conducted to identify dominating biogeochemical processes and to highlight structural limitations. Our results indicate that substrate availability (limited by soil water diffusion and substrate quality) is likely to be a major constraint on soil decomposition in the fibrous horizon (40–60% of soil organic carbon (SOC) pool size variation), while energy limited microbial activity in the amorphous horizon exerts a predominant control on soil decomposition (>70% of SOC pool size variation). Elevated temperature alleviated the energy constraint of microbial activity most notably in amorphous soils, whereas moisture only exhibited a marginal effect on dissolved substrate supply and microbial activity. Our study highlights the different decomposition properties and underlying mechanisms of soil dynamics between fibrous and amorphous soil horizons. Soil decomposition models should consider explicitly representing different boreal soil horizons and soil–microbial interactions to better characterize biogeochemical processes in boreal forest ecosystems. A more comprehensive representation of critical biogeochemical mechanisms of soil moisture effects may be required to improve the performance of the soil model we analyzed in this study.

Effects of biopretreatment of corn stover with white-rot fungus on low-temperature pyrolysis products.

PubMed

Yang, Xuewei; Ma, Fuying; Yu, Hongbo; Zhang, Xiaoyu; Chen, Shulin

2011-02-01

The thermal decomposition of biopretreated corn stover during the low temperature has been studied by using the Py-GC/MS analysis and thermogravimetric analysis with the distributed activation energy model (DAEM). Results showed that biopretreatment with white-rot fungus Echinodontium taxodii 2538 can improve the low-temperature pyrolysis of biomass, by increasing the pyrolysis products of cellulose, hemicellulose (furfural and sucrose increased up to 4.68-fold and 2.94-fold respectively) and lignin (biophenyl and 3,7,11,15-tetramethyl-2-hexadecen-1-ol increased 2.45-fold and 4.22-fold, respectively). Calculated by DAEM method, it showed that biopretreatment can decrease the activation energy during the low temperature range, accelerate the reaction rate and start the thermal decomposition with lower temperature. ATR-FTIR results showed that the deconstruction of lignin and the decomposition of the main linkages between hemicellulose and lignin could contribute to the improvement of the pyrolysis at low temperature. Copyright © 2010 Elsevier Ltd. All rights reserved.

Thermal degradation of Shredded Oil Palm Empty Fruit Bunches (SOPEFB) embedded with Cobalt catalyst by Thermogravimetric Analysis (TGA)

NASA Astrophysics Data System (ADS)

Alias, R.; Hamid, N. H.; Jaapar, J.; Musa, M.; Alwi, H.; Halim, K. H. Ku

2018-03-01

Thermal behavior and decomposition kinetics of shredded oil palm empty fruit bunches (SOPEFB) were investigated in this study by using thermogravimetric analysis (TGA). The SOPEFB were analyzed under conditions of temperature 30 °C to 900 °C with nitrogen gas flow at 50 ml/min. The SOPEFB were embedded with cobalt (II) nitrate solution with concentration 5%, 10%, 15% and 20%. The TG/DTG curves shows the degradation behavior of SOPEFB following with char production for each heating rate and each concentration of cobalt catalyst. Thermal degradation occurred in three phases, water drying phase, decomposition of hemicellulose and cellulose phase, and lignin decomposition phase. The kinetic equation with relevant parameters described the activation energy required for thermal degradation at the temperature regions of 200 °C to 350 °C. Activation energy (E) for different heating rate with SOPEFB embedded with different concentration of cobalt catalyst showing that the lowest E required was at SOPEFB with 20% concentration of cobalt catalyst..

Single-wave-number representation of nonlinear energy spectrum in elastic-wave turbulence of the Föppl-von Kármán equation: energy decomposition analysis and energy budget.

PubMed

Yokoyama, Naoto; Takaoka, Masanori

2014-12-01

A single-wave-number representation of a nonlinear energy spectrum, i.e., a stretching-energy spectrum, is found in elastic-wave turbulence governed by the Föppl-von Kármán (FvK) equation. The representation enables energy decomposition analysis in the wave-number space and analytical expressions of detailed energy budgets in the nonlinear interactions. We numerically solved the FvK equation and observed the following facts. Kinetic energy and bending energy are comparable with each other at large wave numbers as the weak turbulence theory suggests. On the other hand, stretching energy is larger than the bending energy at small wave numbers, i.e., the nonlinearity is relatively strong. The strong correlation between a mode a(k) and its companion mode a(-k) is observed at the small wave numbers. The energy is input into the wave field through stretching-energy transfer at the small wave numbers, and dissipated through the quartic part of kinetic-energy transfer at the large wave numbers. Total-energy flux consistent with energy conservation is calculated directly by using the analytical expression of the total-energy transfer, and the forward energy cascade is observed clearly.

Measurement of the energy dependence of X-ray-induced decomposition of potassium chlorate.

PubMed

Pravica, Michael; Bai, Ligang; Sneed, Daniel; Park, Changyong

2013-03-21

We report the first measurements of the X-ray induced decomposition of KClO3 as a function of energy in two experiments. KClO3 was pressurized to 3.5 GPa and irradiated with monochromatic synchrotron X-rays ranging in energy from 15 to 35 keV in 5 keV increments. A systematic increase in the decomposition rate as the energy was decreased was observed, which agrees with the 1/E(3) trend for the photoelectric process, except at the lowest energy studied. A second experiment was performed to access lower energies (10 and 12 keV) using a beryllium gasket; suggesting an apparent resonance near 15 keV or 0.83 Ǻ maximizing the chemical decomposition rate. A third experiment was performed using KIO3 to ascertain the anionic dependence of the decomposition rate, which was observed to be far slower than in KClO3, suggesting that the O-O distance is the critical factor in chemical reactions. These results will be important for more efficiently initiating chemical decomposition in materials using selected X-ray wavelengths that maximize decomposition to aid useful hard X-ray-induced chemistry and contribute understanding of the mechanism of X-ray-induced decomposition of the chlorates.

Carbon dioxide emissions from the electricity sector in major countries: a decomposition analysis.

PubMed

Li, Xiangzheng; Liao, Hua; Du, Yun-Fei; Wang, Ce; Wang, Jin-Wei; Liu, Yanan

2018-03-01

The electric power sector is one of the primary sources of CO 2 emissions. Analyzing the influential factors that result in CO 2 emissions from the power sector would provide valuable information to reduce the world's CO 2 emissions. Herein, we applied the Divisia decomposition method to analyze the influential factors for CO 2 emissions from the power sector from 11 countries, which account for 67% of the world's emissions from 1990 to 2013. We decompose the influential factors for CO 2 emissions into seven areas: the emission coefficient, energy intensity, the share of electricity generation, the share of thermal power generation, electricity intensity, economic activity, and population. The decomposition analysis results show that economic activity, population, and the emission coefficient have positive roles in increasing CO 2 emissions, and their contribution rates are 119, 23.9, and 0.5%, respectively. Energy intensity, electricity intensity, the share of electricity generation, and the share of thermal power generation curb CO 2 emissions and their contribution rates are 17.2, 15.7, 7.7, and 2.8%, respectively. Through decomposition analysis for each country, economic activity and population are the major factors responsible for increasing CO 2 emissions from the power sector. However, the other factors from developed countries can offset the growth in CO 2 emissions due to economic activities.

Computer implemented empirical mode decomposition method, apparatus and article of manufacture

NASA Technical Reports Server (NTRS)

Huang, Norden E. (Inventor)

1999-01-01

A computer implemented physical signal analysis method is invented. This method includes two essential steps and the associated presentation techniques of the results. All the steps exist only in a computer: there are no analytic expressions resulting from the method. The first step is a computer implemented Empirical Mode Decomposition to extract a collection of Intrinsic Mode Functions (IMF) from nonlinear, nonstationary physical signals. The decomposition is based on the direct extraction of the energy associated with various intrinsic time scales in the physical signal. Expressed in the IMF's, they have well-behaved Hilbert Transforms from which instantaneous frequencies can be calculated. The second step is the Hilbert Transform. The final result is the Hilbert Spectrum. Thus, the invention can localize any event on the time as well as the frequency axis. The decomposition can also be viewed as an expansion of the data in terms of the IMF's. Then, these IMF's, based on and derived from the data, can serve as the basis of that expansion. The local energy and the instantaneous frequency derived from the IMF's through the Hilbert transform give a full energy-frequency-time distribution of the data which is designated as the Hilbert Spectrum.

Thermal Decomposition Behavior of Hydroxytyrosol (HT) in Nitrogen Atmosphere Based on TG-FTIR Methods.

PubMed

Tu, Jun-Ling; Yuan, Jiao-Jiao

2018-02-13

The thermal decomposition behavior of olive hydroxytyrosol (HT) was first studied using thermogravimetry (TG). Cracked chemical bond and evolved gas analysis during the thermal decomposition process of HT were also investigated using thermogravimetry coupled with infrared spectroscopy (TG-FTIR). Thermogravimetry-Differential thermogravimetry (TG-DTG) curves revealed that the thermal decomposition of HT began at 262.8 °C and ended at 409.7 °C with a main mass loss. It was demonstrated that a high heating rate (over 20 K·min -1 ) restrained the thermal decomposition of HT, resulting in an obvious thermal hysteresis. Furthermore, a thermal decomposition kinetics investigation of HT indicated that the non-isothermal decomposition mechanism was one-dimensional diffusion (D1), integral form g ( x ) = x ², and differential form f ( x ) = 1/(2 x ). The four combined approaches were employed to calculate the activation energy ( E = 128.50 kJ·mol -1 ) and Arrhenius preexponential factor (ln A = 24.39 min -1 ). In addition, a tentative mechanism of HT thermal decomposition was further developed. The results provide a theoretical reference for the potential thermal stability of HT.

Energy decomposition analysis of single bonds within Kohn-Sham density functional theory.

PubMed

Levine, Daniel S; Head-Gordon, Martin

2017-11-28

An energy decomposition analysis (EDA) for single chemical bonds is presented within the framework of Kohn-Sham density functional theory based on spin projection equations that are exact within wave function theory. Chemical bond energies can then be understood in terms of stabilization caused by spin-coupling augmented by dispersion, polarization, and charge transfer in competition with destabilizing Pauli repulsions. The EDA reveals distinguishing features of chemical bonds ranging across nonpolar, polar, ionic, and charge-shift bonds. The effect of electron correlation is assessed by comparison with Hartree-Fock results. Substituent effects are illustrated by comparing the C-C bond in ethane against that in bis(diamantane), and dispersion stabilization in the latter is quantified. Finally, three metal-metal bonds in experimentally characterized compounds are examined: a [Formula: see text]-[Formula: see text] dimer, the [Formula: see text]-[Formula: see text] bond in dizincocene, and the Mn-Mn bond in dimanganese decacarbonyl.

Influence of growth conditions on subsequent submonolayer oxide decomposition on Si(111)

NASA Astrophysics Data System (ADS)

Shklyaev, A. A.; Aono, Masakazu; Suzuki, Takanori

1996-10-01

The decomposition kinetics of oxide with a coverage between 0.1 and 0.5 ML, grown by oxidation of the Si(111)-7×7 surface at temperatures between 550 and 800 °C for oxygen pressures (Pox) between 3×10-8 and 2×10-6 Torr, is investigated with optical second-harmonic generation. Through the analysis of the pressure dependence of the initial oxide-growth rate, we separate the conditions for a slow oxide growth at Pox near Ptr(T) and for a rapid oxide growth at Pox>3Ptr(T), where Ptr(T) is the transition pressure to Si-etching regime without oxide growth. For the rapidly grown oxide, the oxide decomposition rate decreases with increasing oxide coverage, whereas the activation energy of about 3 eV does not change significantly. While in the case when the oxide is desorbed at the same temperature as are used for oxide growth, the oxide decomposition is described by an apparent activation energy of 1.5 eV. For the slowly grown oxide of 0.1 ML coverage, the oxide desorption kinetics shows a rapid decomposition stage followed by a slow stage. For the slowly grown oxide of 0.3 ML coverage, the slow stage with a large activation energy of 4.1 eV becomes dominant in the latter part of decomposition. The dependence of the desorption kinetics on the oxide-growth conditions described here could be a reason for the scattering of the kinetic parameters in the literature for O2 interaction with silicon at elevated temperatures.

Using geometric algebra to represent curvature in shell theory with applications to Starling resistors

PubMed Central

Agarwal, A.; Lasenby, J.

2017-01-01

We present a novel application of rotors in geometric algebra to represent the change of curvature tensor that is used in shell theory as part of the constitutive law. We introduce a new decomposition of the change of curvature tensor, which has explicit terms for changes of curvature due to initial curvature combined with strain, and changes in rotation over the surface. We use this decomposition to perform a scaling analysis of the relative importance of bending and stretching in flexible tubes undergoing self-excited oscillations. These oscillations have relevance to the lung, in which it is believed that they are responsible for wheezing. The new analysis is necessitated by the fact that the working fluid is air, compared to water in most previous work. We use stereographic imaging to empirically measure the relative importance of bending and stretching energy in observed self-excited oscillations. This enables us to validate our scaling analysis. We show that bending energy is dominated by stretching energy, and the scaling analysis makes clear that this will remain true for tubes in the airways of the lung. PMID:29291106

Using geometric algebra to represent curvature in shell theory with applications to Starling resistors.

PubMed

Gregory, A L; Agarwal, A; Lasenby, J

2017-11-01

We present a novel application of rotors in geometric algebra to represent the change of curvature tensor that is used in shell theory as part of the constitutive law. We introduce a new decomposition of the change of curvature tensor, which has explicit terms for changes of curvature due to initial curvature combined with strain, and changes in rotation over the surface. We use this decomposition to perform a scaling analysis of the relative importance of bending and stretching in flexible tubes undergoing self-excited oscillations. These oscillations have relevance to the lung, in which it is believed that they are responsible for wheezing. The new analysis is necessitated by the fact that the working fluid is air, compared to water in most previous work. We use stereographic imaging to empirically measure the relative importance of bending and stretching energy in observed self-excited oscillations. This enables us to validate our scaling analysis. We show that bending energy is dominated by stretching energy, and the scaling analysis makes clear that this will remain true for tubes in the airways of the lung.

Breast tissue decomposition with spectral distortion correction: A postmortem study

PubMed Central

Ding, Huanjun; Zhao, Bo; Baturin, Pavlo; Behroozi, Farnaz; Molloi, Sabee

2014-01-01

Purpose: To investigate the feasibility of an accurate measurement of water, lipid, and protein composition of breast tissue using a photon-counting spectral computed tomography (CT) with spectral distortion corrections. Methods: Thirty-eight postmortem breasts were imaged with a cadmium-zinc-telluride-based photon-counting spectral CT system at 100 kV. The energy-resolving capability of the photon-counting detector was used to separate photons into low and high energy bins with a splitting energy of 42 keV. The estimated mean glandular dose for each breast ranged from 1.8 to 2.2 mGy. Two spectral distortion correction techniques were implemented, respectively, on the raw images to correct the nonlinear detector response due to pulse pileup and charge-sharing artifacts. Dual energy decomposition was then used to characterize each breast in terms of water, lipid, and protein content. In the meantime, the breasts were chemically decomposed into their respective water, lipid, and protein components to provide a gold standard for comparison with dual energy decomposition results. Results: The accuracy of the tissue compositional measurement with spectral CT was determined by comparing to the reference standard from chemical analysis. The averaged root-mean-square error in percentage composition was reduced from 15.5% to 2.8% after spectral distortion corrections. Conclusions: The results indicate that spectral CT can be used to quantify the water, lipid, and protein content in breast tissue. The accuracy of the compositional analysis depends on the applied spectral distortion correction technique. PMID:25281953

Measurement and decomposition of energy efficiency of Northeast China-based on super efficiency DEA model and Malmquist index.

PubMed

Ma, Xiaojun; Liu, Yan; Wei, Xiaoxue; Li, Yifan; Zheng, Mengchen; Li, Yudong; Cheng, Chaochao; Wu, Yumei; Liu, Zhaonan; Yu, Yuanbo

2017-08-01

Nowadays, environment problem has become the international hot issue. Experts and scholars pay more and more attention to the energy efficiency. Unlike most studies, which analyze the changes of TFEE in inter-provincial or regional cities, TFEE is calculated with the ratio of target energy value and actual energy input based on data in cities of prefecture levels, which would be more accurate. Many researches regard TFP as TFEE to do analysis from the provincial perspective. This paper is intended to calculate more reliably by super efficiency DEA, observe the changes of TFEE, and analyze its relation with TFP, and it proves that TFP is not equal to TFEE. Additionally, the internal influences of the TFEE are obtained via the Malmquist index decomposition. The external influences of the TFFE are analyzed afterward based on the Tobit models. Analysis results demonstrate that Heilongjiang has the highest TFEE followed by Jilin, and Liaoning has the lowest TFEE. Eventually, some policy suggestions are proposed for the influences of energy efficiency and study results.

Thermogravimetric analysis and kinetic modeling of low-transition-temperature mixtures pretreated oil palm empty fruit bunch for possible maximum yield of pyrolysis oil.

PubMed

Yiin, Chung Loong; Yusup, Suzana; Quitain, Armando T; Uemura, Yoshimitsu; Sasaki, Mitsuru; Kida, Tetsuya

2018-05-01

The impacts of low-transition-temperature mixtures (LTTMs) pretreatment on thermal decomposition and kinetics of empty fruit bunch (EFB) were investigated by thermogravimetric analysis. EFB was pretreated with the LTTMs under different duration of pretreatment which enabled various degrees of alteration to their structure. The TG-DTG curves showed that LTTMs pretreatment on EFB shifted the temperature and rate of decomposition to higher values. The EFB pretreated with sucrose and choline chloride-based LTTMs had attained the highest mass loss of volatile matter (78.69% and 75.71%) after 18 h of pretreatment. For monosodium glutamate-based LTTMs, the 24 h pretreated EFB had achieved the maximum mass loss (76.1%). Based on the Coats-Redfern integral method, the LTTMs pretreatment led to an increase in activation energy of the thermal decomposition of EFB from 80.00 to 82.82-94.80 kJ/mol. The activation energy was mainly affected by the demineralization and alteration in cellulose crystallinity after LTTMs pretreatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Influence of density and environmental factors on decomposition kinetics of amorphous polylactide - Reactive molecular dynamics studies.

PubMed

Mlyniec, A; Ekiert, M; Morawska-Chochol, A; Uhl, T

2016-06-01

In this work, we investigate the influence of the surrounding environment and the initial density on the decomposition kinetics of polylactide (PLA). The decomposition of the amorphous PLA was investigated by means of reactive molecular dynamics simulations. A computational model simulates the decomposition of PLA polymer inside the bulk, due to the assumed lack of removal of reaction products from the polymer matrix. We tracked the temperature dependency of the water and carbon monoxide production to extract the activation energy of thermal decomposition of PLA. We found that an increased density results in decreased activation energy of decomposition by about 50%. Moreover, initiation of decomposition of the amorphous PLA is followed by a rapid decline in activation energy caused by reaction products which accelerates the hydrolysis of esters. The addition of water molecules decreases initial energy of activation as well as accelerates the decomposition process. Additionally, we have investigated the dependency of density on external loading. Comparison of pressures needed to obtain assumed densities shows that this relationship is bilinear and the slope changes around a density equal to 1.3g/cm(3). The conducted analyses provide an insight into the thermal decomposition process of the amorphous phase of PLA, which is particularly susceptible to decomposition in amorphous and semi-crystalline PLA polymers. Copyright © 2016 Elsevier Inc. All rights reserved.

High temperature phase decomposition in Ti{sub x}Zr{sub y}Al{sub z}N

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

Lind, Hans; Pilemalm, Robert; Rogström, Lina

2014-12-15

Through a combination of theoretical and experimental observations we study the high temperature decomposition behavior of c-(Ti{sub x}Zr{sub y}Al{sub z}N) alloys. We show that for most concentrations the high formation energy of (ZrAl)N causes a strong tendency for spinodal decomposition between ZrN and AlN while other decompositions tendencies are suppressed. In addition we observe that entropic effects due to configurational disorder favor a formation of a stable Zr-rich (TiZr)N phase with increasing temperature. Our calculations also predict that at high temperatures a Zr rich (TiZrAl)N disordered phase should become more resistant against the spinodal decomposition despite its high and positivemore » formation energy due to the specific topology of the free energy surface at the relevant concentrations. Our experimental observations confirm this prediction by showing strong tendency towards decomposition in a Zr-poor sample while a Zr-rich alloy shows a greatly reduced decomposition rate, which is mostly attributable to binodal decomposition processes. This result highlights the importance of considering the second derivative of the free energy, in addition to its absolute value in predicting decomposition trends of thermodynamically unstable alloys.« less

Lossless and Sufficient - Invariant Decomposition of Deterministic Target

NASA Astrophysics Data System (ADS)

Paladini, Riccardo; Ferro Famil, Laurent; Pottier, Eric; Martorella, Marco; Berizzi, Fabrizio

2011-03-01

The symmetric radar scattering matrix of a reciprocal target is projected on the circular polarization basis and is decomposed into four orientation invariant parameters, relative phase and relative orientation. The physical interpretation of this results is found in the wave-particle nature of radar scattering due to the circular polarization nature of elemental packets of energy. The proposed decomposition, is based on left orthogonal to left Special Unitary basis, providing the target description in term of a unitary vector. A comparison between the proposed CTD and Cameron, Kennaugh and Krogager decompositions is also pointed out. A validation by the use of both anechoic chamber data and airborne EMISAR data of DTU is used to show the effectiveness of this decomposition for the analysis of coherent targets. In the second paper we will show the application of the rotation group U(3) for the decomposition of distributed targets into nine meaningful parameters.

Thermal Decomposition of 1,5-Dinitrobiuret (DNB): Direct Dynamics Trajectory Simulations and Statistical Modeling

DTIC Science & Technology

2011-05-03

18 . NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON Dr. Tommy W. Hawkins a. REPORT Unclassified b. ABSTRACT Unclassified c. THIS PAGE...branching using Rice-Ramsperger-Kassel-Marcus (RRKM) theory, 18 and finally to the analysis of inter-conversions of primary decomposition products...theory, 18 was employed to examine the properties of the reactant, intermediate complex and transition states as a function of the total internal energy

Toward a reaction rate model of condensed-phase RDX decomposition under high temperatures

NASA Astrophysics Data System (ADS)

Schweigert, Igor

2014-03-01

Shock ignition of energetic molecular solids is driven by microstructural heterogeneities, at which even moderate stresses can result in sufficiently high temperatures to initiate material decomposition and the release of the chemical energy. Mesoscale modeling of these ``hot spots'' requires a chemical reaction rate model that describes the energy release with a sub-microsecond resolution and under a wide range of temperatures. No such model is available even for well-studied energetic materials such as RDX. In this presentation, I will describe an ongoing effort to develop a reaction rate model of condensed-phase RDX decomposition under high temperatures using first-principles molecular dynamics, transition-state theory, and reaction network analysis. This work was supported by the Naval Research Laboratory, by the Office of Naval Research, and by the DOD High Performance Computing Modernization Program Software Application Institute for Multiscale Reactive Modeling of Insensitive Munitions.

Toward a reaction rate model of condensed-phase RDX decomposition under high temperatures

NASA Astrophysics Data System (ADS)

Schweigert, Igor

2015-06-01

Shock ignition of energetic molecular solids is driven by microstructural heterogeneities, at which even moderate stresses can result in sufficiently high temperatures to initiate material decomposition and chemical energy release. Mesoscale modeling of these ``hot spots'' requires a reaction rate model that describes the energy release with a sub-microsecond resolution and under a wide range of temperatures. No such model is available even for well-studied energetic materials such as RDX. In this presentation, I will describe an ongoing effort to develop a reaction rate model of condensed-phase RDX decomposition under high temperatures using first-principles molecular dynamics, transition-state theory, and reaction network analysis. This work was supported by the Naval Research Laboratory, by the Office of Naval Research, and by the DoD High Performance Computing Modernization Program Software Application Institute for Multiscale Reactive Modeling of Insensitive Munitions.

Empirical mode decomposition apparatus, method and article of manufacture for analyzing biological signals and performing curve fitting

NASA Technical Reports Server (NTRS)

Huang, Norden E. (Inventor)

2004-01-01

A computer implemented physical signal analysis method includes four basic steps and the associated presentation techniques of the results. The first step is a computer implemented Empirical Mode Decomposition that extracts a collection of Intrinsic Mode Functions (IMF) from nonlinear, nonstationary physical signals. The decomposition is based on the direct extraction of the energy associated with various intrinsic time scales in the physical signal. Expressed in the IMF's, they have well-behaved Hilbert Transforms from which instantaneous frequencies can be calculated. The second step is the Hilbert Transform which produces a Hilbert Spectrum. Thus, the invention can localize any event on the time as well as the frequency axis. The decomposition can also be viewed as an expansion of the data in terms of the IMF's. Then, these IMF's, based on and derived from the data, can serve as the basis of that expansion. The local energy and the instantaneous frequency derived from the IMF's through the Hilbert transform give a full energy-frequency-time distribution of the data which is designated as the Hilbert Spectrum. The third step filters the physical signal by combining a subset of the IMFs. In the fourth step, a curve may be fitted to the filtered signal which may not have been possible with the original, unfiltered signal.

Empirical mode decomposition apparatus, method and article of manufacture for analyzing biological signals and performing curve fitting

NASA Technical Reports Server (NTRS)

Huang, Norden E. (Inventor)

2002-01-01

A computer implemented physical signal analysis method includes four basic steps and the associated presentation techniques of the results. The first step is a computer implemented Empirical Mode Decomposition that extracts a collection of Intrinsic Mode Functions (IMF) from nonlinear, nonstationary physical signals. The decomposition is based on the direct extraction of the energy associated with various intrinsic time scales in the physical signal. Expressed in the IMF's, they have well-behaved Hilbert Transforms from which instantaneous frequencies can be calculated. The second step is the Hilbert Transform which produces a Hilbert Spectrum. Thus, the invention can localize any event on the time as well as the frequency axis. The decomposition can also be viewed as an expansion of the data in terms of the IMF's. Then, these IMF's, based on and derived from the data, can serve as the basis of that expansion. The local energy and the instantaneous frequency derived from the IMF's through the Hilbert transform give a full energy-frequency-time distribution of the data which is designated as the Hilbert Spectrum. The third step filters the physical signal by combining a subset of the IMFs. In the fourth step, a curve may be fitted to the filtered signal which may not have been possible with the original, unfiltered signal.

Computer implemented empirical mode decomposition method apparatus, and article of manufacture utilizing curvature extrema

NASA Technical Reports Server (NTRS)

Shen, Zheng (Inventor); Huang, Norden Eh (Inventor)

2003-01-01

A computer implemented physical signal analysis method is includes two essential steps and the associated presentation techniques of the results. All the steps exist only in a computer: there are no analytic expressions resulting from the method. The first step is a computer implemented Empirical Mode Decomposition to extract a collection of Intrinsic Mode Functions (IMF) from nonlinear, nonstationary physical signals based on local extrema and curvature extrema. The decomposition is based on the direct extraction of the energy associated with various intrinsic time scales in the physical signal. Expressed in the IMF's, they have well-behaved Hilbert Transforms from which instantaneous frequencies can be calculated. The second step is the Hilbert Transform. The final result is the Hilbert Spectrum. Thus, the invention can localize any event on the time as well as the frequency axis. The decomposition can also be viewed as an expansion of the data in terms of the IMF's. Then, these IMF's, based on and derived from the data, can serve as the basis of that expansion. The local energy and the instantaneous frequency derived from the IMF's through the Hilbert transform give a full energy-frequency-time distribution of the data which is designated as the Hilbert Spectrum.

Thermal decomposition behavior of nano/micro bimodal feedstock with different solids loading

NASA Astrophysics Data System (ADS)

Oh, Joo Won; Lee, Won Sik; Park, Seong Jin

2018-01-01

Debinding is one of the most critical processes for powder injection molding. The parts in debinding process are vulnerable to defect formation, and long processing time of debinding decreases production rate of whole process. In order to determine the optimal condition for debinding process, decomposition behavior of feedstock should be understood. Since nano powder affects the decomposition behavior of feedstock, nano powder effect needs to be investigated for nano/micro bimodal feedstock. In this research, nano powder effect on decomposition behavior of nano/micro bimodal feedstock has been studied. Bimodal powders were fabricated with different ratios of nano powder, and the critical solids loading of each powder was measured by torque rheometer. Three different feedstocks were fabricated for each powder depending on solids loading condition. Thermogravimetric analysis (TGA) experiment was carried out to analyze the thermal decomposition behavior of the feedstocks, and decomposition activation energy was calculated. The result indicated nano powder showed limited effect on feedstocks in lower solids loading condition than optimal range. Whereas, it highly influenced the decomposition behavior in optimal solids loading condition by causing polymer chain scission with high viscosity.

Kinetic energy as functional of the correlation hole

NASA Astrophysics Data System (ADS)

Nalewajski, Roman F.

2003-01-01

Using the marginal decomposition of the many-body probability distribution the electronic kinetic energy is expressed as the functional of the electron density and correlation hole. The analysis covers both the molecule as a whole and its constituent subsystems. The importance of the Fisher information for locality is emphasized.

Kinetic Analysis of Isothermal Decomposition Process of Sodium Bicarbonate Using the Weibull Probability Function—Estimation of Density Distribution Functions of the Apparent Activation Energies

NASA Astrophysics Data System (ADS)

Janković, Bojan

2009-10-01

The decomposition process of sodium bicarbonate (NaHCO3) has been studied by thermogravimetry in isothermal conditions at four different operating temperatures (380 K, 400 K, 420 K, and 440 K). It was found that the experimental integral and differential conversion curves at the different operating temperatures can be successfully described by the isothermal Weibull distribution function with a unique value of the shape parameter ( β = 1.07). It was also established that the Weibull distribution parameters ( β and η) show independent behavior on the operating temperature. Using the integral and differential (Friedman) isoconversional methods, in the conversion (α) range of 0.20 ≤ α ≤ 0.80, the apparent activation energy ( E a ) value was approximately constant ( E a, int = 95.2 kJmol-1 and E a, diff = 96.6 kJmol-1, respectively). The values of E a calculated by both isoconversional methods are in good agreement with the value of E a evaluated from the Arrhenius equation (94.3 kJmol-1), which was expressed through the scale distribution parameter ( η). The Málek isothermal procedure was used for estimation of the kinetic model for the investigated decomposition process. It was found that the two-parameter Šesták-Berggren (SB) autocatalytic model best describes the NaHCO3 decomposition process with the conversion function f(α) = α0.18(1-α)1.19. It was also concluded that the calculated density distribution functions of the apparent activation energies ( ddfE a ’s) are not dependent on the operating temperature, which exhibit the highly symmetrical behavior (shape factor = 1.00). The obtained isothermal decomposition results were compared with corresponding results of the nonisothermal decomposition process of NaHCO3.

Analysis of influence mechanism of energy-related carbon emissions in Guangdong: evidence from regional China based on the input-output and structural decomposition analysis.

PubMed

Wang, Changjian; Wang, Fei; Zhang, Xinlin; Deng, Haijun

2017-11-01

It is important to analyze the influence mechanism of energy-related carbon emissions from a regional perspective to effectively achieve reductions in energy consumption and carbon emissions in China. Based on the "energy-economy-carbon emissions" hybrid input-output analysis framework, this study conducted structural decomposition analysis (SDA) on carbon emissions influencing factors in Guangdong Province. Systems-based examination of direct and indirect drivers for regional emission is presented. (1) Direct effects analysis of influencing factors indicated that the main driving factors of increasing carbon emissions were economic and population growth. Carbon emission intensity was the main contributing factor restraining carbon emissions growth. (2) Indirect effects analysis of influencing factors showed that international and interprovincial trades significantly affected the total carbon emissions. (3) Analysis of the effects of different final demands on the carbon emissions of industrial sector indicated that the increase in carbon emission arising from international and interprovincial trades is mainly concentrated in energy- and carbon-intensive industries. (4) Guangdong had to compromise a certain amount of carbon emissions during the development of its export-oriented economy because of industry transfer arising from the economic globalization, thereby pointing to the existence of the "carbon leakage" problem. At the same time, interprovincial export and import resulted in Guangdong transferring a part of its carbon emissions to other provinces, thereby leading to the occurrence of "carbon transfer."

Projection decomposition algorithm for dual-energy computed tomography via deep neural network.

PubMed

Xu, Yifu; Yan, Bin; Chen, Jian; Zeng, Lei; Li, Lei

2018-03-15

Dual-energy computed tomography (DECT) has been widely used to improve identification of substances from different spectral information. Decomposition of the mixed test samples into two materials relies on a well-calibrated material decomposition function. This work aims to establish and validate a data-driven algorithm for estimation of the decomposition function. A deep neural network (DNN) consisting of two sub-nets is proposed to solve the projection decomposition problem. The compressing sub-net, substantially a stack auto-encoder (SAE), learns a compact representation of energy spectrum. The decomposing sub-net with a two-layer structure fits the nonlinear transform between energy projection and basic material thickness. The proposed DNN not only delivers image with lower standard deviation and higher quality in both simulated and real data, and also yields the best performance in cases mixed with photon noise. Moreover, DNN costs only 0.4 s to generate a decomposition solution of 360 × 512 size scale, which is about 200 times faster than the competing algorithms. The DNN model is applicable to the decomposition tasks with different dual energies. Experimental results demonstrated the strong function fitting ability of DNN. Thus, the Deep learning paradigm provides a promising approach to solve the nonlinear problem in DECT.

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

Burnham, A K; Weese, R K; Andrzejewski, W J

Decomposition kinetics are determined for HMX (nitramine octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and CP (2-(5-cyanotetrazalato) pentaammine cobalt (III) perchlorate) separately and together. For high levels of thermal stress, the two materials decompose faster as a mixture than individually. This effect is observed both in high-temperature thermal analysis experiments and in long-term thermal aging experiments. An Arrhenius plot of the 10% level of HMX decomposition by itself from a diverse set of experiments is linear from 120 to 260 C, with an apparent activation energy of 165 kJ/mol. Similar but less extensive thermal analysis data for the mixture suggests a slightly lower activation energy formore » the mixture, and an analogous extrapolation is consistent with the amount of gas observed in the long-term detonator aging experiments, which is about 30 times greater than expected from HMX by itself for 50 months at 100 C. Even with this acceleration, however, it would take {approx}10,000 years to achieve 10% decomposition at {approx}30 C. Correspondingly, negligible decomposition is predicted by this kinetic model for a few decades aging at temperatures slightly above ambient. This prediction is consistent with additional sealed-tube aging experiments at 100-120 C, which are estimated to have an effective thermal dose greater than that from decades of exposure to temperatures slightly above ambient.« less

Thermodynamic analysis of trimethylgallium decomposition during GaN metal organic vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Sekiguchi, Kazuki; Shirakawa, Hiroki; Chokawa, Kenta; Araidai, Masaaki; Kangawa, Yoshihiro; Kakimoto, Koichi; Shiraishi, Kenji

2018-04-01

We analyzed the decomposition of Ga(CH3)3 (TMG) during the metal organic vapor phase epitaxy (MOVPE) of GaN on the basis of first-principles calculations and thermodynamic analysis. We performed activation energy calculations of TMG decomposition and determined the main reaction processes of TMG during GaN MOVPE. We found that TMG reacts with the H2 carrier gas and that (CH3)2GaH is generated after the desorption of the methyl group. Next, (CH3)2GaH decomposes into (CH3)GaH2 and this decomposes into GaH3. Finally, GaH3 becomes GaH. In the MOVPE growth of GaN, TMG decomposes into GaH by the successive desorption of its methyl groups. The results presented here concur with recent high-resolution mass spectroscopy results.

Investigation of pyrolysis kinetics of humic acids from low rank Anatolian coal by thermal analysis

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

Tonbul, Y.; Erdogan, S.

2007-07-01

Thermogravimetric analysis (TGA) of humic acid samples from low rank Anatolian (east of Turkey, Bingol) coal were investigated under atmospheric pressure. The samples were subjected for the decomposition of organic matter ambient to 800{sup o} C at four different heating rates (5, 10, 15, and 20 degrees C min{sup -1}). The humic acid samples were started at decomposition between 170 - 206{sup o}C and amount of residues varied 55-60% according to heating rate. Each of samples showed a single step mass loss. TG/DTG data of samples were analyzed to determine activation energy values by Coats and Redfern method and Arrheniusmore » method. Activation energy values are similar obtained from Coats and Redfern method and Arrhenius method and varied from 25 to 29 kJ mol{sup -1}.« less

Synthesis, crystal structure and catalytic effect on thermal decomposition of RDX and AP: An energetic coordination polymer [Pb{sub 2}(C{sub 5}H{sub 3}N{sub 5}O{sub 5}){sub 2}(NMP)·NMP]{sub n}

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

Liu, Jin-jian; Yancheng Teachers College, Yancheng 224002; Liu, Zu-Liang, E-mail: liuzl@mail.njust.edu.cn

2013-04-15

An energetic lead(II) coordination polymer based on the ligand ANPyO has been synthesized and its crystal structure has been got. The polymer was characterized by FT-IR spectroscopy, elemental analysis, DSC and TG-DTG technologies. Thermal analysis shows that there are one endothermic process and two exothermic decomposition stages in the temperature range of 50–600 °C with final residues 57.09%. The non-isothermal kinetic has also been studied on the main exothermic decomposition using the Kissinger's and Ozawa–Doyle's methods, the apparent activation energy is calculated as 195.2 KJ/mol. Furthermore, DSC measurements show that the polymer has significant catalytic effect on the thermal decompositionmore » of ammonium perchlorate. - Graphical abstract: An energetic lead(II) coordination polymer of ANPyO has been synthesized, structurally characterized and properties tested. Highlights: ► We have synthesized and characterized an energetic lead(II) coordination polymer. ► We have measured its molecular structure and thermal decomposition. ► It has significant catalytic effect on thermal decomposition of AP.« less

The solution of the optimization problem of small energy complexes using linear programming methods

NASA Astrophysics Data System (ADS)

Ivanin, O. A.; Director, L. B.

2016-11-01

Linear programming methods were used for solving the optimization problem of schemes and operation modes of distributed generation energy complexes. Applicability conditions of simplex method, applied to energy complexes, including installations of renewable energy (solar, wind), diesel-generators and energy storage, considered. The analysis of decomposition algorithms for various schemes of energy complexes was made. The results of optimization calculations for energy complexes, operated autonomously and as a part of distribution grid, are presented.

Measurement of the Energy and High-Pressure Dependence of X-ray-Induced Decomposition of Crystalline Strontium Oxalate

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

Goldberger, David; Evlyukhin, Egor; Cifligu, Petrika

We report measurements of the X-ray-induced decomposition of crystalline strontium oxalate (SrC2O4) as a function of energy and high pressure in two separate experiments. SrC2O4 at ambient conditions was irradiated with monochromatic synchrotron X-rays ranging in energy from 15 to 28 keV. A broad resonance of the decomposition yield was observed with a clear maximum when irradiating with ~20 keV X-rays and ambient pressure. Little or no decomposition was observed at 15 keV, which is below the Sr K-shell energy of 16.12 keV, suggesting that excitation of core electrons may play an important role in the destabilization of the C2O42–more » anion. A second experiment was performed to investigate the high-pressure dependence of the X-ray-induced decomposition of strontium oxalate at fixed energy. SrC2O4 was compressed in a diamond anvil cell (DAC) in the pressure range from 0 to 7.6 GPa with 1 GPa increments and irradiated in situ with 20 keV X-rays. A marked pressure dependence of the decomposition yield of SrC2O4 was observed with a decomposition yield maximum at around 1 GPa, suggesting that different crystal structures of the material play an important role in the decomposition process. This may be due in part to a phase transition observed near this pressure.« less

Measurement of the Energy and High-Pressure Dependence of X-ray-Induced Decomposition of Crystalline Strontium Oxalate.

PubMed

Goldberger, David; Evlyukhin, Egor; Cifligu, Petrika; Wang, Yonggang; Pravica, Michael

2017-09-28

We report measurements of the X-ray-induced decomposition of crystalline strontium oxalate (SrC 2 O 4 ) as a function of energy and high pressure in two separate experiments. SrC 2 O 4 at ambient conditions was irradiated with monochromatic synchrotron X-rays ranging in energy from 15 to 28 keV. A broad resonance of the decomposition yield was observed with a clear maximum when irradiating with ∼20 keV X-rays and ambient pressure. Little or no decomposition was observed at 15 keV, which is below the Sr K-shell energy of 16.12 keV, suggesting that excitation of core electrons may play an important role in the destabilization of the C 2 O 4 2- anion. A second experiment was performed to investigate the high-pressure dependence of the X-ray-induced decomposition of strontium oxalate at fixed energy. SrC 2 O 4 was compressed in a diamond anvil cell (DAC) in the pressure range from 0 to 7.6 GPa with 1 GPa increments and irradiated in situ with 20 keV X-rays. A marked pressure dependence of the decomposition yield of SrC 2 O 4 was observed with a decomposition yield maximum at around 1 GPa, suggesting that different crystal structures of the material play an important role in the decomposition process. This may be due in part to a phase transition observed near this pressure.

Thermal decomposition of ammonium hexachloroosmate.

PubMed

Asanova, T I; Kantor, I; Asanov, I P; Korenev, S V; Yusenko, K V

2016-12-07

Structural changes of (NH 4 ) 2 [OsCl 6 ] occurring during thermal decomposition in a reduction atmosphere have been studied in situ using combined energy-dispersive X-ray absorption spectroscopy (ED-XAFS) and powder X-ray diffraction (PXRD). According to PXRD, (NH 4 ) 2 [OsCl 6 ] transforms directly to metallic Os without the formation of any crystalline intermediates but through a plateau where no reactions occur. XANES and EXAFS data by means of Multivariate Curve Resolution (MCR) analysis show that thermal decomposition occurs with the formation of an amorphous intermediate {OsCl 4 } x with a possible polymeric structure. Being revealed for the first time the intermediate was subjected to determine the local atomic structure around osmium. The thermal decomposition of hexachloroosmate is much more complex and occurs within a minimum two-step process, which has never been observed before.

Carbon dioxide emissions, GDP, energy use, and population growth: a multivariate and causality analysis for Ghana, 1971-2013.

PubMed

Asumadu-Sarkodie, Samuel; Owusu, Phebe Asantewaa

2016-07-01

In this study, the relationship between carbon dioxide emissions, GDP, energy use, and population growth in Ghana was investigated from 1971 to 2013 by comparing the vector error correction model (VECM) and the autoregressive distributed lag (ARDL). Prior to testing for Granger causality based on VECM, the study tested for unit roots, Johansen's multivariate co-integration and performed a variance decomposition analysis using Cholesky's technique. Evidence from the variance decomposition shows that 21 % of future shocks in carbon dioxide emissions are due to fluctuations in energy use, 8 % of future shocks are due to fluctuations in GDP, and 6 % of future shocks are due to fluctuations in population. There was evidence of bidirectional causality running from energy use to GDP and a unidirectional causality running from carbon dioxide emissions to energy use, carbon dioxide emissions to GDP, carbon dioxide emissions to population, and population to energy use. Evidence from the long-run elasticities shows that a 1 % increase in population in Ghana will increase carbon dioxide emissions by 1.72 %. There was evidence of short-run equilibrium relationship running from energy use to carbon dioxide emissions and GDP to carbon dioxide emissions. As a policy implication, the addition of renewable energy and clean energy technologies into Ghana's energy mix can help mitigate climate change and its impact in the future.

Metal-porphyrin: a potential catalyst for direct decomposition of N(2)O by theoretical reaction mechanism investigation.

PubMed

Maitarad, Phornphimon; Namuangruk, Supawadee; Zhang, Dengsong; Shi, Liyi; Li, Hongrui; Huang, Lei; Boekfa, Bundet; Ehara, Masahiro

2014-06-17

The adsorption of nitrous oxide (N2O) on metal-porphyrins (metal: Ti, Cr, Fe, Co, Ni, Cu, or Zn) has been theoretically investigated using density functional theory with the M06L functional to explore their use as potential catalysts for the direct decomposition of N2O. Among these metal-porphyrins, Ti-porphyrin is the most active for N2O adsorption in the triplet ground state with the strongest adsorption energy (-13.32 kcal/mol). Ti-porphyrin was then assessed for the direct decomposition of N2O. For the overall reaction mechanism of three N2O molecules on Ti-porphyrin, two plausible catalytic cycles are proposed. Cycle 1 involves the consecutive decomposition of the first two N2O molecules, while cycle 2 is the decomposition of the third N2O molecule. For cycle 1, the activation energies of the first and second N2O decompositions are computed to be 3.77 and 49.99 kcal/mol, respectively. The activation energy for the third N2O decomposition in cycle 2 is 47.79 kcal/mol, which is slightly lower than that of the second activation energy of the first cycle. O2 molecules are released in cycles 1 and 2 as the products of the reaction, which requires endothermic energies of 102.96 and 3.63 kcal/mol, respectively. Therefore, the O2 desorption is mainly released in catalytic cycle 2 of a TiO3-porphyrin intermediate catalyst. In conclusion, regarding the O2 desorption step for the direct decomposition of N2O, the findings would be very useful to guide the search for potential N2O decomposition catalysts in new directions.

Kinetics of Thermal Decomposition of Ammonium Perchlorate by TG/DSC-MS-FTIR

NASA Astrophysics Data System (ADS)

Zhu, Yan-Li; Huang, Hao; Ren, Hui; Jiao, Qing-Jie

2014-01-01

The method of thermogravimetry/differential scanning calorimetry-mass spectrometry-Fourier transform infrared (TG/DSC-MS-FTIR) simultaneous analysis has been used to study thermal decomposition of ammonium perchlorate (AP). The processing of nonisothermal data at various heating rates was performed using NETZSCH Thermokinetics. The MS-FTIR spectra showed that N2O and NO2 were the main gaseous products of the thermal decomposition of AP, and there was a competition between the formation reaction of N2O and that of NO2 during the process with an iso-concentration point of N2O and NO2. The dependence of the activation energy calculated by Friedman's iso-conversional method on the degree of conversion indicated that the AP decomposition process can be divided into three stages, which are autocatalytic, low-temperature diffusion and high-temperature, stable-phase reaction. The corresponding kinetic parameters were determined by multivariate nonlinear regression and the mechanism of the AP decomposition process was proposed.

Catalytic performance of M@Ni (M = Fe, Ru, Ir) core-shell nanoparticles towards ammonia decomposition for CO x -free hydrogen production

NASA Astrophysics Data System (ADS)

Chen, Xin; Zhou, Junwei; Chen, Shuangjing; Zhang, Hui

2018-06-01

To reduce the use of precious metals and maintain the catalytic activity for NH3 decomposition reaction, it is an effective way to construct bimetallic nanoparticles with special structures. In this paper, by using density functional theory methods, we investigated NH3 decomposition reaction on three types of core-shell nanoparticles M@Ni (M = Fe, Ru, Ir) with 13 core M atoms and 42 shell Ni atoms. The size of these three particles is about 1 nm. Benefit from alloying with Ru in this nanocluster, Ru@Ni core-shell nanoparticles exhibit catalytic activity comparable to that of single metal Ru, based on the analysis of the adsorption energy and potential energy diagram of NH3 decomposition, as well as N2 desorption processes. However, as for Fe@Ni and Ir@Ni core-shell nanoparticles, their catalytic activities are still unsatisfactory compared to the active metal Ru. In addition, in order to further explain the synergistic effect of bimetallic core-shell nanoparticles, the partial density of states were also calculated. The results show that d-band electrons provided by the core metal are the main factors affecting the entire catalytic process.

Thermal properties of Bentonite Modified with 3-aminopropyltrimethoxysilane

NASA Astrophysics Data System (ADS)

Pramono, E.; Pratiwi, W.; Wahyuningrum, D.; Radiman, C. L.

2018-03-01

Chemical modifications of Bentonite (BNT) clay have been carried out by using 3-aminoprophyltrimethoxysilane (APS) in various solvent media. The degradation properties of products (BNTAPS) were characterized by thermogravimetric analysis (TGA). Samples were heated at 30 to 700°C with a heating rate 10 deg/min, and the total silane-grafted amount was determined by calculating the weight loss at 200 – 600°C. The thermogram of TGA showed that there were three main decomposition regions which are attributed to the elimination of physically adsorbed water, decomposition of silane and dehydroxylation of Bentonite. High weight loss attributed to the thermal decomposition of silane was observed between 200 to 550°C. Quantitative analysis of grafted silane results high silane loaded using a solvent with high surface energy, which indicates the type of solvent affected interaction and adsorption of APS in BNT platelets.

Thermokinetic analysis and product characterization of Medium Density Fiberboard pyrolysis.

PubMed

Aslan, Dilan Irmak; Özoğul, Buğçe; Ceylan, Selim; Geyikçi, Feza

2018-06-01

This study investigates the pyrolysis of Medium Density Fiberboard (MDF) as a potential waste management solution. Thermal behaviour of MDF was analysed via TG/DSC. The primary decomposition step occurred between 190 °C and 425 °C. Evolved gaseous products over this step were evaluated by a FTIR spectrometer coupled with TGA. Peaks for phenolic, alcohols and aldehydes were detected at the maximum decomposition temperature. Py-GC/MS analysis revealed phenols, ketones and cyclic compounds as the primary non-condensable pyrolysis products. The kinetics of pyrolysis were investigated by the widely applied Distributed Activation Energy Model, resulting in an average activation energy and pre-exponential factor of 127.40 kJ mol -1 and 8.4E+11. The results of this study suggest that pyrolyzing MDF could potentially provide renewable fuels and prevent environmental problems related with MDF disposal. Copyright © 2018 Elsevier Ltd. All rights reserved.

Use of principle velocity patterns in the analysis of structural acoustic optimization.

PubMed

Johnson, Wayne M; Cunefare, Kenneth A

2007-02-01

This work presents an application of principle velocity patterns in the analysis of the structural acoustic design optimization of an eight ply composite cylindrical shell. The approach consists of performing structural acoustic optimizations of a composite cylindrical shell subject to external harmonic monopole excitation. The ply angles are used as the design variables in the optimization. The results of the ply angle design variable formulation are interpreted using the singular value decomposition of the interior acoustic potential energy. The decomposition of the acoustic potential energy provides surface velocity patterns associated with lower levels of interior noise. These surface velocity patterns are shown to correspond to those from the structural acoustic optimization results. Thus, it is demonstrated that the capacity to design multi-ply composite cylinders for quiet interiors is determined by how well the cylinder be can designed to exhibit particular surface velocity patterns associated with lower noise levels.

Mechanistic and Kinetic Analysis of Na2SO4-Modified Laterite Decomposition by Thermogravimetry Coupled with Mass Spectrometry

PubMed Central

Yang, Song; Du, Wenguang; Shi, Pengzheng; Shangguan, Ju; Liu, Shoujun; Zhou, Changhai; Chen, Peng; Zhang, Qian; Fan, Huiling

2016-01-01

Nickel laterites cannot be effectively used in physical methods because of their poor crystallinity and fine grain size. Na2SO4 is the most efficient additive for grade enrichment and Ni recovery. However, how Na2SO4 affects the selective reduction of laterite ores has not been clearly investigated. This study investigated the decomposition of laterite with and without the addition of Na2SO4 in an argon atmosphere using thermogravimetry coupled with mass spectrometry (TG-MS). Approximately 25 mg of samples with 20 wt% Na2SO4 was pyrolyzed under a 100 ml/min Ar flow at a heating rate of 10°C/min from room temperature to 1300°C. The kinetic study was based on derivative thermogravimetric (DTG) curves. The evolution of the pyrolysis gas composition was detected by mass spectrometry, and the decomposition products were analyzed by X-ray diffraction (XRD). The decomposition behavior of laterite with the addition of Na2SO4 was similar to that of pure laterite below 800°C during the first three stages. However, in the fourth stage, the dolomite decomposed at 897°C, which is approximately 200°C lower than the decomposition of pure laterite. In the last stage, the laterite decomposed and emitted SO2 in the presence of Na2SO4 with an activation energy of 91.37 kJ/mol. The decomposition of laterite with and without the addition of Na2SO4 can be described by one first-order reaction. Moreover, the use of Na2SO4 as the modification agent can reduce the activation energy of laterite decomposition; thus, the reaction rate can be accelerated, and the reaction temperature can be markedly reduced. PMID:27333072

Energy recovery from solid waste. Volume 2: Technical report. [pyrolysis and biodegradation

NASA Technical Reports Server (NTRS)

Huang, C. J.; Dalton, C.

1975-01-01

A systems analysis of energy recovery from solid waste demonstrates the feasibility of several current processes for converting solid waste to an energy form. The social, legal, environmental, and political factors are considered in depth with recommendations made in regard to new legislation and policy. Biodegradation and thermal decomposition are the two areas of disposal that are considered with emphasis on thermal decomposition. A technical and economic evaluation of a number of available and developing energy-recovery processes is given. Based on present technical capabilities, use of prepared solid waste as a fuel supplemental to coal seems to be the most economic process by which to recover energy from solid waste. Markets are considered in detail with suggestions given for improving market conditions and for developing market stability. A decision procedure is given to aid a community in deciding on its options in dealing with solid waste, and a new pyrolysis process is suggested. An application of the methods of this study are applied to Houston, Texas.

Efficient Method for the Determination of the Activation Energy of the Iodide-Catalyzed Decomposition of Hydrogen Peroxide

ERIC Educational Resources Information Center

Sweeney, William; Lee, James; Abid, Nauman; DeMeo, Stephen

2014-01-01

An experiment is described that determines the activation energy (E[subscript a]) of the iodide-catalyzed decomposition reaction of hydrogen peroxide in a much more efficient manner than previously reported in the literature. Hydrogen peroxide, spontaneously or with a catalyst, decomposes to oxygen and water. Because the decomposition reaction is…

Efficient material decomposition method for dual-energy X-ray cargo inspection system

NASA Astrophysics Data System (ADS)

Lee, Donghyeon; Lee, Jiseoc; Min, Jonghwan; Lee, Byungcheol; Lee, Byeongno; Oh, Kyungmin; Kim, Jaehyun; Cho, Seungryong

2018-03-01

Dual-energy X-ray inspection systems are widely used today for it provides X-ray attenuation contrast of the imaged object and also its material information. Material decomposition capability allows a higher detection sensitivity of potential targets including purposely loaded impurities in agricultural product inspections and threats in security scans for example. Dual-energy X-ray transmission data can be transformed into two basis material thickness data, and its transformation accuracy heavily relies on a calibration of material decomposition process. The calibration process in general can be laborious and time consuming. Moreover, a conventional calibration method is often challenged by the nonuniform spectral characteristics of the X-ray beam in the entire field-of-view (FOV). In this work, we developed an efficient material decomposition calibration process for a linear accelerator (LINAC) based high-energy X-ray cargo inspection system. We also proposed a multi-spot calibration method to improve the decomposition performance throughout the entire FOV. Experimental validation of the proposed method has been demonstrated by use of a cargo inspection system that supports 6 MV and 9 MV dual-energy imaging.

The nexus between geopolitical uncertainty and crude oil markets: An entropy-based wavelet analysis

NASA Astrophysics Data System (ADS)

Uddin, Gazi Salah; Bekiros, Stelios; Ahmed, Ali

2018-04-01

The global financial crisis and the subsequent geopolitical turbulence in energy markets have brought increased attention to the proper statistical modeling especially of the crude oil markets. In particular, we utilize a time-frequency decomposition approach based on wavelet analysis to explore the inherent dynamics and the casual interrelationships between various types of geopolitical, economic and financial uncertainty indices and oil markets. Via the introduction of a mixed discrete-continuous multiresolution analysis, we employ the entropic criterion for the selection of the optimal decomposition level of a MODWT as well as the continuous-time coherency and phase measures for the detection of business cycle (a)synchronization. Overall, a strong heterogeneity in the revealed interrelationships is detected over time and across scales.

Evaluation of the energy transfer in the char zone during ablation. Part 2: In-depth response of ablative composites, volume 1. Ph.D. Thesis, 1975. Final Report

NASA Technical Reports Server (NTRS)

Pike, R. W.; Delvalle, E. G.

1974-01-01

The decomposition of ablative composites is described along with the transport phenomena of pyrolysis gases which result from the decomposition of these plastics as they flow through the porous char of char-forming ablators. The pyrolysis products are those formed by the thermal degradation of nylon-phenolic resin and silicone elastomer composites. Emphasis is placed on the nature and extent of chemical reactions of the pyrolysis products and the char, along with the energy absorbed by the combined pyrolysis and char zone. Chemical reactions with thermodynamically consistent kinetic data are determined in order to develop a realistic analysis for predicting the thermal performance of ablative heat shields.

Exploring Galaxy Formation and Evolution via Structural Decomposition

NASA Astrophysics Data System (ADS)

Kelvin, Lee; Driver, Simon; Robotham, Aaron; Hill, David; Cameron, Ewan

2010-06-01

The Galaxy And Mass Assembly (GAMA) structural decomposition pipeline (GAMA-SIGMA Structural Investigation of Galaxies via Model Analysis) will provide multi-component information for a sample of ~12,000 galaxies across 9 bands ranging from near-UV to near-IR. This will allow the relationship between structural properties and broadband, optical-to-near-IR, spectral energy distributions of bulge, bar, and disk components to be explored, revealing clues as to the history of baryonic mass assembly within a hierarchical clustering framework. Data is initially taken from the SDSS & UKIDSS-LAS surveys to test the robustness of our automated decomposition pipeline. This will eventually be replaced with the forthcoming higher-resolution VST & VISTA surveys data, expanding the sample to ~30,000 galaxies.

Kinetics of the cellular decomposition of supersaturated solid solutions

NASA Astrophysics Data System (ADS)

Ivanov, M. A.; Naumuk, A. Yu.

2014-09-01

A consistent description of the kinetics of the cellular decomposition of supersaturated solid solutions with the development of a spatially periodic structure of lamellar (platelike) type, which consists of alternating phases of precipitates on the basis of the impurity component and depleted initial solid solution, is given. One of the equations, which determines the relationship between the parameters that describe the process of decomposition, has been obtained from a comparison of two approaches in order to determine the rate of change in the free energy of the system. The other kinetic parameters can be described with the use of a variational method, namely, by the maximum velocity of motion of the decomposition boundary at a given temperature. It is shown that the mutual directions of growth of the lamellae of different phases are determined by the minimum value of the interphase surface energy. To determine the parameters of the decomposition, a simple thermodynamic model of states with a parabolic dependence of the free energy on the concentrations has been used. As a result, expressions that describe the decomposition rate, interlamellar distance, and the concentration of impurities in the phase that remain after the decomposition have been derived. This concentration proves to be equal to the half-sum of the initial concentration and the equilibrium concentration corresponding to the decomposition temperature.

A comparative study on pyrolysis characteristic Indonesia biomassa and low grade coal

NASA Astrophysics Data System (ADS)

Adhityatama, G. I.; Hanif, F.; Cahyono, R. B.; Hidayat, M.; Akiyama, T.

2017-05-01

A comparative study on pyrolysis of biomass and low grade coal was conducted using a thermogravimetric analyzer. Each kind of biomass and coal has a characteristic pyrolysis behavior which is explained based on its individual component characteristics. All fuels experienced a small weight loss as temperatures approached 450K because of moisture evaporation. The coal had smallest total weight loss compared to biomass due to its high content of fixed carbon, suggesting that coal would produce high amounts of char and small amounts of volatile matter (e.g., tar and gas). The biomass exhibits similar tendency regarding the decomposition process which is the hemicelluloses break down first at temperatures of 470 to 530K, cellulose follows in the temperature range 510 to 620K, and lignin is the last component to pyrolyzer at temperatures of 550 to 770K. The thermal decomposition of biomass consisted of two predominant peaks corresponding first to the decomposition of cellulose and, second, to the decomposition of lignin. Meanwhile, the coal exhibited only single peak because these fuels were predominantly composed of carbon. Based on the kinetic analysis, coal have the smaller activation energy (55.32kJ/mol) compared to biomass (range from 89.80-172.86 kJ/mol). Pyrolysis process also created more pore material in the solid product. These results were important for the optimization of energy conversion from those solid fuels. Biomass resulted lower solid product and higher tar product, thus would be suitable for liquid and gas energy production.

Cascaded systems analysis of noise and detectability in dual-energy cone-beam CT

PubMed Central

Gang, Grace J.; Zbijewski, Wojciech; Webster Stayman, J.; Siewerdsen, Jeffrey H.

2012-01-01

Purpose: Dual-energy computed tomography and dual-energy cone-beam computed tomography (DE-CBCT) are promising modalities for applications ranging from vascular to breast, renal, hepatic, and musculoskeletal imaging. Accordingly, the optimization of imaging techniques for such applications would benefit significantly from a general theoretical description of image quality that properly incorporates factors of acquisition, reconstruction, and tissue decomposition in DE tomography. This work reports a cascaded systems analysis model that includes the Poisson statistics of x rays (quantum noise), detector model (flat-panel detectors), anatomical background, image reconstruction (filtered backprojection), DE decomposition (weighted subtraction), and simple observer models to yield a task-based framework for DE technique optimization. Methods: The theoretical framework extends previous modeling of DE projection radiography and CBCT. Signal and noise transfer characteristics are propagated through physical and mathematical stages of image formation and reconstruction. Dual-energy decomposition was modeled according to weighted subtraction of low- and high-energy images to yield the 3D DE noise-power spectrum (NPS) and noise-equivalent quanta (NEQ), which, in combination with observer models and the imaging task, yields the dual-energy detectability index (d′). Model calculations were validated with NPS and NEQ measurements from an experimental imaging bench simulating the geometry of a dedicated musculoskeletal extremities scanner. Imaging techniques, including kVp pair and dose allocation, were optimized using d′ as an objective function for three example imaging tasks: (1) kidney stone discrimination; (2) iodine vs bone in a uniform, soft-tissue background; and (3) soft tissue tumor detection on power-law anatomical background. Results: Theoretical calculations of DE NPS and NEQ demonstrated good agreement with experimental measurements over a broad range of imaging conditions. Optimization results suggest a lower fraction of total dose imparted by the low-energy acquisition, a finding consistent with previous literature. The selection of optimal kVp pair reveals the combined effect of both quantum noise and contrast in the kidney stone discrimination and soft-tissue tumor detection tasks, whereas the K-edge effect of iodine was the dominant factor in determining kVp pairs in the iodine vs bone task. The soft-tissue tumor task illustrated the benefit of dual-energy imaging in eliminating anatomical background noise and improving detectability beyond that achievable by single-energy scans. Conclusions: This work established a task-based theoretical framework that is predictive of DE image quality. The model can be utilized in optimizing a broad range of parameters in image acquisition, reconstruction, and decomposition, providing a useful tool for maximizing DE-CBCT image quality and reducing dose. PMID:22894440

Metagenomic analysis of antibiotic resistance genes (ARGs) during refuse decomposition.

PubMed

Liu, Xi; Yang, Shu; Wang, Yangqing; Zhao, He-Ping; Song, Liyan

2018-04-12

Landfill is important reservoirs of residual antibiotics and antibiotic resistance genes (ARGs), but the mechanism of landfill application influence on antibiotic resistance remains unclear. Although refuse decomposition plays a crucial role in landfill stabilization, its impact on the antibiotic resistance has not been well characterized. To better understand the impact, we studied the dynamics of ARGs and the bacterial community composition during refuse decomposition in a bench-scale bioreactor after long term operation (265d) based on metagenomics analysis. The total abundances of ARGs increased from 431.0ppm in the initial aerobic phase (AP) to 643.9ppm in the later methanogenic phase (MP) during refuse decomposition, suggesting that application of landfill for municipal solid waste (MSW) treatment may elevate the level of ARGs. A shift from drug-specific (bacitracin, tetracycline and sulfonamide) resistance to multidrug resistance was observed during the refuse decomposition and was driven by a shift of potential bacteria hosts. The elevated abundance of Pseudomonas mainly contributed to the increasing abundance of multidrug ARGs (mexF and mexW). Accordingly, the percentage of ARGs encoding an efflux pump increased during refuse decomposition, suggesting that potential bacteria hosts developed this mechanism to adapt to the carbon and energy shortage when biodegradable substances were depleted. Overall, our findings indicate that the use of landfill for MSW treatment increased antibiotic resistance, and demonstrate the need for a comprehensive investigation of antibiotic resistance in landfill. Copyright © 2018. Published by Elsevier B.V.

Thermal decomposition and kinetic evaluation of decanted 2,4,6-trinitrotoluene (TNT) for reutilization as composite material

NASA Astrophysics Data System (ADS)

Ahmed, M. F.; Hussain, A.; Malik, A. Q.

2016-08-01

Use of energetic materials has long been considered for only military purposes. However, it is very recent that their practical applications in wide range of commercial fields such as mining, road building, under water blasting and rocket propulsion system have been considered. About 5mg of 2,4,6-trinitrotoluene (TNT) in serviceable (Svc) as well as unserviceable (Unsvc) form were used for their thermal decomposition and kinetic parameters investigation. Thermogravimetric/ differential thermal analysis (TG/DTA), X-ray diffraction (XRD) and Scanning electron microscope (SEM) were used to characterize two types of TNT. Arrhenius kinetic parameters like activation energy (E) and enthalpy (AH) of both TNT samples were determined using TG curves with the help of Horowitz and Metzger method. Simultaneously, thermal decomposition range was evaluated from DTA curves. Distinct diffraction peaks showing crystalline nature were obtained from XRD analysis. SEM results indicated that Unsvc TNT contained a variety of defects like cracks and porosity. Similarly, it is observed that thermal as well as kinetic behavior of both TNT samples vary to a great extent. Likewise, a prominent change in the activation energies (E) of both samples is observed. This in-depth study provides a way forward in finding solutions for the safe reutilization of decanted TNT.

Quantitative analysis of microbial biomass yield in aerobic bioreactor.

PubMed

Watanabe, Osamu; Isoda, Satoru

2013-12-01

We have studied the integrated model of reaction rate equations with thermal energy balance in aerobic bioreactor for food waste decomposition and showed that the integrated model has the capability both of monitoring microbial activity in real time and of analyzing biodegradation kinetics and thermal-hydrodynamic properties. On the other hand, concerning microbial metabolism, it was known that balancing catabolic reactions with anabolic reactions in terms of energy and electron flow provides stoichiometric metabolic reactions and enables the estimation of microbial biomass yield (stoichiometric reaction model). We have studied a method for estimating real-time microbial biomass yield in the bioreactor during food waste decomposition by combining the integrated model with the stoichiometric reaction model. As a result, it was found that the time course of microbial biomass yield in the bioreactor during decomposition can be evaluated using the operational data of the bioreactor (weight of input food waste and bed temperature) by the combined model. The combined model can be applied to manage a food waste decomposition not only for controlling system operation to keep microbial activity stable, but also for producing value-added products such as compost on optimum condition. Copyright © 2013 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Optimally growing boundary layer disturbances in a convergent nozzle preceded by a circular pipe

NASA Astrophysics Data System (ADS)

Uzun, Ali; Davis, Timothy B.; Alvi, Farrukh S.; Hussaini, M. Yousuff

2017-06-01

We report the findings from a theoretical analysis of optimally growing disturbances in an initially turbulent boundary layer. The motivation behind this study originates from the desire to generate organized structures in an initially turbulent boundary layer via excitation by disturbances that are tailored to be preferentially amplified. Such optimally growing disturbances are of interest for implementation in an active flow control strategy that is investigated for effective jet noise control. Details of the optimal perturbation theory implemented in this study are discussed. The relevant stability equations are derived using both the standard decomposition and the triple decomposition. The chosen test case geometry contains a convergent nozzle, which generates a Mach 0.9 round jet, preceded by a circular pipe. Optimally growing disturbances are introduced at various stations within the circular pipe section to facilitate disturbance energy amplification upstream of the favorable pressure gradient zone within the convergent nozzle, which has a stabilizing effect on disturbance growth. Effects of temporal frequency, disturbance input and output plane locations as well as separation distance between output and input planes are investigated. The results indicate that optimally growing disturbances appear in the form of longitudinal counter-rotating vortex pairs, whose size can be on the order of several times the input plane mean boundary layer thickness. The azimuthal wavenumber, which represents the number of counter-rotating vortex pairs, is found to generally decrease with increasing separation distance. Compared to the standard decomposition, the triple decomposition analysis generally predicts relatively lower azimuthal wavenumbers and significantly reduced energy amplification ratios for the optimal disturbances.

Proton mass decomposition

NASA Astrophysics Data System (ADS)

Yang, Yi-Bo; Chen, Ying; Draper, Terrence; Liang, Jian; Liu, Keh-Fei

2018-03-01

We report the results on the proton mass decomposition and also on the related quark and glue momentum fractions. The results are based on overlap valence fermions on four ensembles of Nf = 2 + 1 DWF configurations with three lattice spacings and volumes, and several pion masses including the physical pion mass. With 1-loop pertur-bative calculation and proper normalization of the glue operator, we find that the u, d, and s quark masses contribute 9(2)% to the proton mass. The quark energy and glue field energy contribute 31(5)% and 37(5)% respectively in the MS scheme at µ = 2 GeV. The trace anomaly gives the remaining 23(1)% contribution. The u, d, s and glue momentum fractions in the MS scheme are consistent with the global analysis at µ = 2 GeV.

Thermochemical properties of nanometer CL-20 and PETN fabricated using a mechanical milling method

NASA Astrophysics Data System (ADS)

Song, Xiaolan; Wang, Yi; An, Chongwei

2018-06-01

2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and pentaerythritol tetranitrate (PETN), with mean sizes of 73.8 nm and 267.7 nm, respectively, were fabricated on a high-energy ball-mill. Scanning electron microscope (SEM) analysis was used to image the micron-scale morphology of nano-explosives, and the particle size distribution was calculated using the statistics of individual particle sizes obtained from the SEM images. Analyses, such as X-ray diffractometer (XRD), infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS), were also used to confirm whether the crystal phase, molecular structure, and surface elements changed after a long-term milling process. The results were as expected. Thermal analysis was performed at different heating rates. Parameters, such as the activation energy (ES), activation enthalpy (ΔH≠), activation free energy (ΔG≠), activation entropy (ΔS≠), and critical temperature of thermal explosion (Tb), were calculated to determine the decomposition courses of the explosives. Moreover, the thermal decomposition mechanisms of nano CL-20 and nano PETN were investigated using thermal-infrared spectrometry online (DSC-IR) analysis, by which their gas products were also detected. The results indicated that nano CL-20 decomposed to CO2 and N2O and that nano PETN decayed to NO2, which implied a remarkable difference between the decomposition mechanisms of the two explosives. In addition, the mechanical sensitivities of CL-20 and PETN were tested, and the results revealed that nano-explosives were more insensitive than raw ones, and the possible mechanism for this was discussed. Thermal sensitivity was also investigated with a 5 s bursting point test, from which the 5 s bursting point (T5s) and the activation of the deflagration were obtained.

Kinetics of the pyrolysis of arundo, sawdust, corn stover and switch grass biomass by thermogravimetric analysis using a multi-stage model.

PubMed

Biney, Paul O; Gyamerah, Michael; Shen, Jiacheng; Menezes, Bruna

2015-03-01

A new multi-stage kinetic model has been developed for TGA pyrolysis of arundo, corn stover, sawdust and switch grass that accounts for the initial biomass weight (W0). The biomass were decomposed in a nitrogen atmosphere from 23°C to 900°C in a TGA at a single 20°C/min ramp rate in contrast with the isoconversion technique. The decomposition was divided into multiple stages based on the absolute local minimum values of conversion derivative, (dx/dT), obtained from DTG curves. This resulted in three decomposition stages for arundo, corn stover and sawdust and four stages for switch grass. A linearized multi-stage model was applied to the TGA data for each stage to determine the pre-exponential factor, activation energy, and reaction order. The activation energies ranged from 54.7 to 60.9 kJ/mol, 62.9 to 108.7 kJ/mol, and 18.4 to 257.9 kJ/mol for the first, second and the third decomposition stages respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Pi2 detection using Empirical Mode Decomposition (EMD)

NASA Astrophysics Data System (ADS)

Mieth, Johannes Z. D.; Frühauff, Dennis; Glassmeier, Karl-Heinz

2017-04-01

Empirical Mode Decomposition has been used as an alternative method to wavelet transformation to identify onset times of Pi2 pulsations in data sets of the Scandinavian Magnetometer Array (SMA). Pi2 pulsations are magnetohydrodynamic waves occurring during magnetospheric substorms. Almost always Pi2 are observed at substorm onset in mid to low latitudes on Earth's nightside. They are fed by magnetic energy release caused by dipolarization processes. Their periods lie between 40 to 150 seconds. Usually, Pi2 are detected using wavelet transformation. Here, Empirical Mode Decomposition (EMD) is presented as an alternative approach to the traditional procedure. EMD is a young signal decomposition method designed for nonlinear and non-stationary time series. It provides an adaptive, data driven, and complete decomposition of time series into slow and fast oscillations. An optimized version using Monte-Carlo-type noise assistance is used here. By displaying the results in a time-frequency space a characteristic frequency modulation is observed. This frequency modulation can be correlated with the onset of Pi2 pulsations. A basic algorithm to find the onset is presented. Finally, the results are compared to classical wavelet-based analysis. The use of different SMA stations furthermore allows the spatial analysis of Pi2 onset times. EMD mostly finds application in the fields of engineering and medicine. This work demonstrates the applicability of this method to geomagnetic time series.

Synthesis, characterization, thermal and explosive properties of potassium salts of trinitrophloroglucinol.

PubMed

Wang, Liqiong; Chen, Hongyan; Zhang, Tonglai; Zhang, Jianguo; Yang, Li

2007-08-17

Three different substituted potassium salts of trinitrophloroglucinol (H(3)TNPG) were prepared and characterized. The salts are all hydrates, and thermogravimetric analysis (TG) and elemental analysis confirmed that these salts contain crystal H2O and that the amount crystal H2O in potassium salts of H3TNPG is 1.0 hydrate for mono-substituted potassium salts of H3TNPG [K(H2TNPG)] and di-substituted potassium salt of H3TNPG [K2(HTNPG)], and 2.0 hydrate for tri-substituted potassium salt of H3TNPG [K3(TNPG)]. Their thermal decomposition mechanisms and kinetic parameters from 50 to 500 degrees C were studied under a linear heating rate by differential scanning calorimetry (DSC). Their thermal decomposition mechanisms undergo dehydration stage and intensive exothermic decomposition stage. FT-IR and TG studies verify that their final residua of decomposition are potassium cyanide or potassium carbonate. According to the onset temperature of the first exothermic decomposition process of dehydrated salts, the order of the thermal stability from low to high is from K(H2TNPG) and K2(HTNPG) to K3(TNPG), which is conform to the results of apparent activation energy calculated by Kissinger's and Ozawa-Doyle's method. Sensitivity test results showed that potassium salts of H3TNPG demonstrated higher sensitivity properties and had greater explosive probabilities.

Performance calculation and simulation system of high energy laser weapon

NASA Astrophysics Data System (ADS)

Wang, Pei; Liu, Min; Su, Yu; Zhang, Ke

2014-12-01

High energy laser weapons are ready for some of today's most challenging military applications. Based on the analysis of the main tactical/technical index and combating process of high energy laser weapon, a performance calculation and simulation system of high energy laser weapon was established. Firstly, the index decomposition and workflow of high energy laser weapon was proposed. The entire system was composed of six parts, including classical target, platform of laser weapon, detect sensor, tracking and pointing control, laser atmosphere propagation and damage assessment module. Then, the index calculation modules were designed. Finally, anti-missile interception simulation was performed. The system can provide reference and basis for the analysis and evaluation of high energy laser weapon efficiency.

Investigation of Prediction Method and Fundamental Thermo-decomposition Properties on Gasification of Woody Biomass

NASA Astrophysics Data System (ADS)

Morita, Akihiro

Recently, development of energy transfer technology based on woody biomass remarkably has been forwarding accompanied biomass boom for gasification and liquefaction. To elevate on yield of energy into biomass for transportation and exergy is extremely important for essential utilization and production of bio-fuels. Because, conversion to bio-fuel must be discussion in detail thermo-decomposition characteristics for biomass main composition formed on cellulose and hemicelluloses, lignin. In this research, we analyze thermo-decomposition characteristics of each biomass main composition on both active (air) and passive (N2) atmosphere. Especially, we suggest predict model of gasification based on change of atomic carbon ratio with thermo-decomposition. 1) Even if it heat-treats cedar chip by 473K, loss of energy hardly produces it. From this, it acquired that the substance contributed to weight reduction was a low ingredient of energy value. 2) If cedar chip is heated in the 473K around, it can be predicted that the substance with a low energy value like water or acetic acid has arisen by thermal decomposition. It suggested that the transportation performance of the biomass improved by choosing and eliminating these. 3) Each ingredient of hydrogen, nitrogen, and oxygen which dissipated in the gasification process acquired that it was direct proportion to the carbonaceous dissipation rate. 4) The action at the time of thermo-decomposition of (the carbon, hydrogen, nitrogen, oxygen which are) the main constituent factors of the biomass suggested a possibility of being predicted by a statistical method.

Influence of gamma-irradiation on the non-isothermal decomposition of calcium-gadolinium oxalate

NASA Astrophysics Data System (ADS)

Moharana, S. C.; Praharaj, J.; Bhatta, D.

Thermal decomposition of co-precipitated unirradiated and irradiated Ca-Gd oxalate has been studied by adopting differential thermal analysis (DTA) and thermogravimetric (TG) techniques. The reaction occurs through two stages corresponding to the decomposition of gadolinium oxalate (Gd-Ox) followed by that of calcium oxalate (Ca-Ox). The kinetic parameters for both the stages are calculated by using solid state reaction models and Coats-Redfern's equation. The co-precipitation as well as irradiation alter the DTA peak temperatures and the kinetic parameters of Ca-Ox. The decomposition of Gd-Ox follows the two dimensional Contracting area (R-2) mechanism, while that of Ca-Ox follows the Avrami-Erofeev (A(2)) mechanism (n =2), which are also exhibited by the co-precipitated and irradiated samples. Co-precipitation decreases the energy of activation and the pre-exponential factor of the individual components but the reverse phenomenon takes place upon irradiation of the co-precipitate. The mechanisms underlying the phenomena are explored.

High active nitrogen flux growth of GaN by plasma assisted molecular beam epitaxy

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

McSkimming, Brian M., E-mail: mcskimming@engineering.ucsb.edu; Speck, James S.; Chaix, Catherine

2015-09-15

In the present study, the authors report on a modified Riber radio frequency (RF) nitrogen plasma source that provides active nitrogen fluxes more than 30 times higher than those commonly used for plasma assisted molecular beam epitaxy (PAMBE) growth of gallium nitride (GaN) and thus a significantly higher growth rate than has been previously reported. GaN films were grown using N{sub 2} gas flow rates between 5 and 25 sccm while varying the plasma source's RF forward power from 200 to 600 W. The highest growth rate, and therefore the highest active nitrogen flux, achieved was ∼7.6 μm/h. For optimized growth conditions,more » the surfaces displayed a clear step-terrace structure with an average RMS roughness (3 × 3 μm) on the order of 1 nm. Secondary ion mass spectroscopy impurity analysis demonstrates oxygen and hydrogen incorporation of 1 × 10{sup 16} and ∼5 × 10{sup 17}, respectively. In addition, the authors have achieved PAMBE growth of GaN at a substrate temperature more than 150 °C greater than our standard Ga rich GaN growth regime and ∼100 °C greater than any previously reported PAMBE growth of GaN. This growth temperature corresponds to GaN decomposition in vacuum of more than 20 nm/min; a regime previously unattainable with conventional nitrogen plasma sources. Arrhenius analysis of the decomposition rate shows that samples with a flux ratio below stoichiometry have an activation energy greater than decomposition of GaN in vacuum while samples grown at or above stoichiometry have decreased activation energy. The activation energy of decomposition for GaN in vacuum was previously determined to be ∼3.1 eV. For a Ga/N flux ratio of ∼1.5, this activation energy was found to be ∼2.8 eV, while for a Ga/N flux ratio of ∼0.5, it was found to be ∼7.9 eV.« less

Degradation of Penicillin G by heat activated persulfate in aqueous solution.

PubMed

Norzaee, Samira; Taghavi, Mahmoud; Djahed, Babak; Kord Mostafapour, Ferdos

2018-06-01

We used Heat Activated of Persulfate (HAP) to decompose Penicillin G (PEN G) in aqueous solution. The effect of pH (3-11), temperature (313-353 K), and initial concentration of Sodium Persulfate (SPS) (0.05-0.5 mM) on the decomposition level of PEN G were investigated. The residue of PEN G was determined by spectrophotometry at the wavelength of 290 nm. Also, the Chemical Oxygen Demand (COD) was measured in each experiment. The Total Organic Carbon (TOC) analysis was utilized for surveying the mineralization of PEN G. In addition, based on Arrhenius equation, the activation energy of PEN G decomposition was calculated. The results indicated that the maximum PEN G removal rate was obtained at pH 5 and by increasing the doses of SPS from 0.05 to 0.5 mM, the PEN G decomposition was enhanced. It was found that an increase in temperature is accompanied by an increase in removal efficiency of PEN G. The activation energy of the studied process was determined to be 94.8 kJ mol -1 , suggesting that a moderate activation energy is required for PEN G decomposition. The TOC measurements indicate that the HAP can efficiently mineralize PEN G. Besides, the presence of the scavengers significantly suppressed the HAP process to remove the PEN G. Overall, the results of this study demonstrate that using HAP process can be a suitable method for decomposing of PEN G in aqueous solutions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Characterization and Thermal Decomposition of Nanometer 2,2', 4,4', 6,6'-Hexanitro-Stilbene and 1,3,5-Triamino-2,4,6-Trinitrobenzene Fabricated by a Mechanical Milling Method

NASA Astrophysics Data System (ADS)

Song, Xiaolan; Wang, Yi; Zhao, Shanshan; An, Chongwei; Wang, Jingyu; Zhang, Jinglin

2018-04-01

Nanometer 2,2', 4,4', 6,6'-hexanitro-stilbene (HNS) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) were fabricated on a high-energy ball mill. The particle sizes of nano-HNS and nano-TATB were 98.4 and 57.8 nm, respectively. An SEM analysis was employed to image the micron morphology of nano-explosives. The particle size distribution was calculated by measuring the size of 300 particles in SEM images. XRD, IR, and XPS analyses were used to confirm whether the crystal phase, molecule structure, and surface elements were changed by the milling process. Thermal decomposition of nano-HNS and nano-TATB was investigated by differential scanning calorimetry (DSC) and thermal-infrared spectrometry online (DSC-IR) analyses. Using DSC traces collected from different heating rates, the kinetic and thermodynamic parameters of thermolysis of raw and nano-explosives were calculated (activation energy (EK), pre-exponential factor (lnAK), rate constant (k), activation heat (ΔH≠), activation free energy (ΔG≠), activation entropy (ΔS≠), critical temperature of thermal explosion (Tb), and critical heating rate of thermal explosion (dT/dt)Tb). The results indicated that nano-explosives were of different kinetic and thermodynamic properties from starting explosives. In addition, the gas products for thermal decomposition of nano-HNS and nano-TATB were detected. Although HNS and TATB are both nitro explosives, the decomposition products of the two were different. A mechanism to explain the difference is proposed.

Mechanistic insight into the hydrazine decomposition on Rh(111): effect of reaction intermediate on catalytic activity.

PubMed

Deng, Zhigang; Lu, Xiaoqing; Wen, Zengqiang; Wei, Shuxian; Liu, Yunjie; Fu, Dianling; Zhao, Lianming; Guo, Wenyue

2013-10-14

Periodic density functional theory (DFT) calculations have been performed to systematically investigate the effect of reaction intermediate on catalytic activity for hydrazine (N2H4) decomposition on Rh(111). Reaction mechanisms via intramolecular and NH2-assisted N2H4 decompositions are comparatively analyzed, including adsorption configuration, reaction energy and barrier of elementary step, and reaction network. Our results show that the most favorable N2H4 decomposition pathway starts with the initial N-N bond scission to the NH2 intermediate, followed by stepwise H stripping from adsorbed N2Hx (x = 1-4) species, and finally forms the N2 and NH3 products. Comparatively, the stepwise intramolecular dehydrogenation via N2H4→ N2H3→ N2H2→ N2H → N2, and N2H4→ NH2→ NH → N with or without NH2 promotion effect, are unfavorable due to higher energy barriers encountered. Energy barrier analysis, reaction rate constants, and electronic structures are used to identify the crucial competitive route. The promotion effect of the NH2 intermediate is structurally reflected in the weakening of the N-H bond and strengthening of the N-N bond in N2Hx in the coadsorption system; it results intrinsically from the less structural deformation of the adsorbate, and weakening of the interaction between dehydrogenated fragment and departing H in transition state. Our results highlight the crucial effect of reaction intermediate on catalytic activity and provide a theoretical approach to analyze the effect.

Breast density evaluation using spectral mammography, radiologist reader assessment and segmentation techniques: a retrospective study based on left and right breast comparison

PubMed Central

Molloi, Sabee; Ding, Huanjun; Feig, Stephen

2015-01-01

Purpose The purpose of this study was to compare the precision of mammographic breast density measurement using radiologist reader assessment, histogram threshold segmentation, fuzzy C-mean segmentation and spectral material decomposition. Materials and Methods Spectral mammography images from a total of 92 consecutive asymptomatic women (50–69 years old) who presented for annual screening mammography were retrospectively analyzed for this study. Breast density was estimated using 10 radiologist reader assessment, standard histogram thresholding, fuzzy C-mean algorithm and spectral material decomposition. The breast density correlation between left and right breasts was used to assess the precision of these techniques to measure breast composition relative to dual-energy material decomposition. Results In comparison to the other techniques, the results of breast density measurements using dual-energy material decomposition showed the highest correlation. The relative standard error of estimate for breast density measurements from left and right breasts using radiologist reader assessment, standard histogram thresholding, fuzzy C-mean algorithm and dual-energy material decomposition was calculated to be 1.95, 2.87, 2.07 and 1.00, respectively. Conclusion The results indicate that the precision of dual-energy material decomposition was approximately factor of two higher than the other techniques with regard to better correlation of breast density measurements from right and left breasts. PMID:26031229

Reactivity of fluoroalkanes in reactions of coordinated molecular decomposition

NASA Astrophysics Data System (ADS)

Pokidova, T. S.; Denisov, E. T.

2017-08-01

Experimental results on the coordinated molecular decomposition of RF fluoroalkanes to olefin and HF are analyzed using the model of intersecting parabolas (IPM). The kinetic parameters are calculated to allow estimates of the activation energy ( E) and rate constant ( k) of these reactions, based on enthalpy and IPM algorithms. Parameters E and k are found for the first time for eight RF decomposition reactions. The factors that affect activation energy E of RF decomposition (the enthalpy of the reaction, the electronegativity of the atoms of reaction centers, and the dipole-dipole interaction of polar groups) are determined. The values of E and k for reverse reactions of addition are estimated.

Initial decomposition mechanism for the energy release from electronically excited energetic materials: FOX-7 (1,1-diamino-2,2-dinitroethene, C{sub 2}H{sub 4}N{sub 4}O{sub 4})

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

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

Decomposition of the energetic material FOX-7 (1,1-diamino-2,2-dinitroethylene, C{sub 2}H{sub 4}N{sub 4}O{sub 4}) is investigated both theoretically and experimentally. The NO molecule is observed as an initial decomposition product subsequent to electronic excitation. The observed NO product is rotationally cold (<35 K) and vibrationally hot (2800 K). The initial decomposition mechanism is explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. Electronically excited S{sub 2} FOX-7 can radiationlessly relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{submore » 1}/S{sub 0}){sub CI} conical intersections and undergo a nitro-nitrite isomerization to generate NO product on the S{sub 0} state. The theoretically predicted mechanism is consistent with the experimental results. As FOX-7 decomposes on the ground electronic state, thus, the vibrational energy of the NO product from FOX-7 is high. The observed rotational energy distribution for NO is consistent with the final transition state structure on the S{sub 0} state. Ground state FOX-7 decomposition agrees with previous work: the nitro-nitrite isomerization has the lowest average energy barrier, the C–NH{sub 2} bond cleavage is unlikely under the given excitation conditions, and HONO formation on the ground state surface is energy accessible but not the main process.« less

A theoretical investigation of symmetry-origin unidirectional energy gradient in light-harvesting dendrimers.

PubMed

Koda, Shin-ichi

2016-03-21

We theoretically investigate a possibility that the symmetry of the repetitively branched structure of light-harvesting dendrimers creates the energy gradient descending toward inner generations (layers of pigment molecules) of the dendrimers. In the first half of this paper, we define a model system using the Frenkel exciton Hamiltonian that focuses only on the topology of dendrimers and numerically show that excitation energy tends to gather at inner generations of the model system at a thermal equilibrium state. This indicates that an energy gradient is formed in the model system. In the last half, we attribute this result to the symmetry of the model system and propose two symmetry-origin mechanisms creating the energy gradient. The present analysis and proposition are based on the theory of the linear chain (LC) decomposition [S. Koda, J. Chem. Phys. 142, 204112 (2015)], which equivalently transforms the model system into a set of one-dimensional systems on the basis of the symmetry of dendrimers. In the picture of the LC decomposition, we find that energy gradient is formed both in each linear chain and among linear chains, and these two mechanisms explain the numerical results well.

A theoretical investigation of symmetry-origin unidirectional energy gradient in light-harvesting dendrimers

NASA Astrophysics Data System (ADS)

Koda, Shin-ichi

2016-03-01

We theoretically investigate a possibility that the symmetry of the repetitively branched structure of light-harvesting dendrimers creates the energy gradient descending toward inner generations (layers of pigment molecules) of the dendrimers. In the first half of this paper, we define a model system using the Frenkel exciton Hamiltonian that focuses only on the topology of dendrimers and numerically show that excitation energy tends to gather at inner generations of the model system at a thermal equilibrium state. This indicates that an energy gradient is formed in the model system. In the last half, we attribute this result to the symmetry of the model system and propose two symmetry-origin mechanisms creating the energy gradient. The present analysis and proposition are based on the theory of the linear chain (LC) decomposition [S. Koda, J. Chem. Phys. 142, 204112 (2015)], which equivalently transforms the model system into a set of one-dimensional systems on the basis of the symmetry of dendrimers. In the picture of the LC decomposition, we find that energy gradient is formed both in each linear chain and among linear chains, and these two mechanisms explain the numerical results well.

Postmortem validation of breast density using dual-energy mammography

PubMed Central

Molloi, Sabee; Ducote, Justin L.; Ding, Huanjun; Feig, Stephen A.

2014-01-01

Purpose: Mammographic density has been shown to be an indicator of breast cancer risk and also reduces the sensitivity of screening mammography. Currently, there is no accepted standard for measuring breast density. Dual energy mammography has been proposed as a technique for accurate measurement of breast density. The purpose of this study is to validate its accuracy in postmortem breasts and compare it with other existing techniques. Methods: Forty postmortem breasts were imaged using a dual energy mammography system. Glandular and adipose equivalent phantoms of uniform thickness were used to calibrate a dual energy basis decomposition algorithm. Dual energy decomposition was applied after scatter correction to calculate breast density. Breast density was also estimated using radiologist reader assessment, standard histogram thresholding and a fuzzy C-mean algorithm. Chemical analysis was used as the reference standard to assess the accuracy of different techniques to measure breast composition. Results: Breast density measurements using radiologist reader assessment, standard histogram thresholding, fuzzy C-mean algorithm, and dual energy were in good agreement with the measured fibroglandular volume fraction using chemical analysis. The standard error estimates using radiologist reader assessment, standard histogram thresholding, fuzzy C-mean, and dual energy were 9.9%, 8.6%, 7.2%, and 4.7%, respectively. Conclusions: The results indicate that dual energy mammography can be used to accurately measure breast density. The variability in breast density estimation using dual energy mammography was lower than reader assessment rankings, standard histogram thresholding, and fuzzy C-mean algorithm. Improved quantification of breast density is expected to further enhance its utility as a risk factor for breast cancer. PMID:25086548

Energy-Based Wavelet De-Noising of Hydrologic Time Series

PubMed Central

Sang, Yan-Fang; Liu, Changming; Wang, Zhonggen; Wen, Jun; Shang, Lunyu

2014-01-01

De-noising is a substantial issue in hydrologic time series analysis, but it is a difficult task due to the defect of methods. In this paper an energy-based wavelet de-noising method was proposed. It is to remove noise by comparing energy distribution of series with the background energy distribution, which is established from Monte-Carlo test. Differing from wavelet threshold de-noising (WTD) method with the basis of wavelet coefficient thresholding, the proposed method is based on energy distribution of series. It can distinguish noise from deterministic components in series, and uncertainty of de-noising result can be quantitatively estimated using proper confidence interval, but WTD method cannot do this. Analysis of both synthetic and observed series verified the comparable power of the proposed method and WTD, but de-noising process by the former is more easily operable. The results also indicate the influences of three key factors (wavelet choice, decomposition level choice and noise content) on wavelet de-noising. Wavelet should be carefully chosen when using the proposed method. The suitable decomposition level for wavelet de-noising should correspond to series' deterministic sub-signal which has the smallest temporal scale. If too much noise is included in a series, accurate de-noising result cannot be obtained by the proposed method or WTD, but the series would show pure random but not autocorrelation characters, so de-noising is no longer needed. PMID:25360533

Computational study of An-X bonding (An = Th, U; X = p-block-based ligands) in pyrrolic macrocycle-supported complexes from the quantum theory of atoms in molecules and bond energy decomposition analysis.

PubMed

O'Brien, Kieran T P; Kaltsoyannis, Nikolas

2017-01-17

A systematic computational study of organoactinide complexes of the form [LAnX] n+ has been carried out using density functional theory, the quantum theory of atoms in molecules (QTAIM) and Ziegler-Rauk energy decomposition analysis (EDA) methods. The systems studied feature L = trans-calix[2]benzene[2]pyrrolide, An = Th(iv), Th(iii), U(iii) and X = BH 4 , BO 2 C 2 H 4 , Me, N(SiH 3 ) 2 , OPh, CH 3 , NH 2 , OH, F, SiH 3 , PH 2 , SH, Cl, CH 2 Ph, NHPh, OPh, SiH 2 Ph, PHPh 2 , SPh, CPh 3 , NPh 2 , OPh, SiPh 3 PPh 2 , SPh. The PBE0 hybrid functional proved most suitable for geometry optimisations based on comparisons with available experimental data. An-X bond critical point electron densities, energy densities and An-X delocalisation indices, calculated with the PBE functional at the PBE0 geometries, are correlated with An-X bond energies, enthalpies and with the terms in the EDA. Good correlations are found between energies and QTAIM metrics, particularly for the orbital interaction term, provided the X ligand is part of an isoelectronic series and the number of open shell electrons is low (i.e. for the present Th(iv) and Th(iii) systems).

Nonstationary Dynamics Data Analysis with Wavelet-SVD Filtering

NASA Technical Reports Server (NTRS)

Brenner, Marty; Groutage, Dale; Bessette, Denis (Technical Monitor)

2001-01-01

Nonstationary time-frequency analysis is used for identification and classification of aeroelastic and aeroservoelastic dynamics. Time-frequency multiscale wavelet processing generates discrete energy density distributions. The distributions are processed using the singular value decomposition (SVD). Discrete density functions derived from the SVD generate moments that detect the principal features in the data. The SVD standard basis vectors are applied and then compared with a transformed-SVD, or TSVD, which reduces the number of features into more compact energy density concentrations. Finally, from the feature extraction, wavelet-based modal parameter estimation is applied.

Energy Decomposition Analysis Based on Absolutely Localized Molecular Orbitals for Large-Scale Density Functional Theory Calculations in Drug Design.

PubMed

Phipps, M J S; Fox, T; Tautermann, C S; Skylaris, C-K

2016-07-12

We report the development and implementation of an energy decomposition analysis (EDA) scheme in the ONETEP linear-scaling electronic structure package. Our approach is hybrid as it combines the localized molecular orbital EDA (Su, P.; Li, H. J. Chem. Phys., 2009, 131, 014102) and the absolutely localized molecular orbital EDA (Khaliullin, R. Z.; et al. J. Phys. Chem. A, 2007, 111, 8753-8765) to partition the intermolecular interaction energy into chemically distinct components (electrostatic, exchange, correlation, Pauli repulsion, polarization, and charge transfer). Limitations shared in EDA approaches such as the issue of basis set dependence in polarization and charge transfer are discussed, and a remedy to this problem is proposed that exploits the strictly localized property of the ONETEP orbitals. Our method is validated on a range of complexes with interactions relevant to drug design. We demonstrate the capabilities for large-scale calculations with our approach on complexes of thrombin with an inhibitor comprised of up to 4975 atoms. Given the capability of ONETEP for large-scale calculations, such as on entire proteins, we expect that our EDA scheme can be applied in a large range of biomolecular problems, especially in the context of drug design.

Particle image and acoustic Doppler velocimetry analysis of a cross-flow turbine wake

NASA Astrophysics Data System (ADS)

Strom, Benjamin; Brunton, Steven; Polagye, Brian

2017-11-01

Cross-flow turbines have advantageous properties for converting kinetic energy in wind and water currents to rotational mechanical energy and subsequently electrical power. A thorough understanding of cross-flow turbine wakes aids understanding of rotor flow physics, assists geometric array design, and informs control strategies for individual turbines in arrays. In this work, the wake physics of a scale model cross-flow turbine are investigated experimentally. Three-component velocity measurements are taken downstream of a two-bladed turbine in a recirculating water channel. Time-resolved stereoscopic particle image and acoustic Doppler velocimetry are compared for planes normal to and distributed along the turbine rotational axis. Wake features are described using proper orthogonal decomposition, dynamic mode decomposition, and the finite-time Lyapunov exponent. Consequences for downstream turbine placement are discussed in conjunction with two-turbine array experiments.

Defect Detection in Textures through the Use of Entropy as a Means for Automatically Selecting the Wavelet Decomposition Level.

PubMed

Navarro, Pedro J; Fernández-Isla, Carlos; Alcover, Pedro María; Suardíaz, Juan

2016-07-27

This paper presents a robust method for defect detection in textures, entropy-based automatic selection of the wavelet decomposition level (EADL), based on a wavelet reconstruction scheme, for detecting defects in a wide variety of structural and statistical textures. Two main features are presented. One of the new features is an original use of the normalized absolute function value (NABS) calculated from the wavelet coefficients derived at various different decomposition levels in order to identify textures where the defect can be isolated by eliminating the texture pattern in the first decomposition level. The second is the use of Shannon's entropy, calculated over detail subimages, for automatic selection of the band for image reconstruction, which, unlike other techniques, such as those based on the co-occurrence matrix or on energy calculation, provides a lower decomposition level, thus avoiding excessive degradation of the image, allowing a more accurate defect segmentation. A metric analysis of the results of the proposed method with nine different thresholding algorithms determined that selecting the appropriate thresholding method is important to achieve optimum performance in defect detection. As a consequence, several different thresholding algorithms depending on the type of texture are proposed.

Revealing driving factors of China's PM2.5 pollution

NASA Astrophysics Data System (ADS)

Zheng, Y.; Zhao, H.; Zhang, Q.; Geng, G.; Tong, D.; Peng, L.; He, K.

2017-12-01

China's rapid economic development and intensive energy consumption are deteriorating the air quality significantly. Understanding the key driving factors behind China's growing emissions of air pollutants and the accompanying PM2.5 pollution is critical for the development of China's clean air policies and also provides insight into how other emerging economies may develop a clear sky future. Here we reveal the socioeconomic drivers of the variations of China's PM2.5 concentrations during 2002-2012 by using an interdisciplinary framework that integrates an emission inventory model, an index decomposition analysis model, and a regional air quality model. The decomposition results demostrate that the improvements in emission efficiency and energy efficiency failed to offset the increased emissions of both primary PM2.5 and gaseous PM2.5 precursors (including SO2 NOx, and volatile organic compounds) triggered by the surging economic growth during 2002-2012. During the same time, the effects of energy structure, production structure and population growth were relatively less significant to all pollutants, which indicates the potential of large emission abatements through energy structure and production structure adjustment. Sensitivity simulations by the air quality model based on the provincial decomposition results also show that the economic growth have outpaced efficiency improvements in the increments of PM2.5 concentrations during the study years. As China continues to develop rapidly, future policies should promote further improvements in efficiency and accelerate the adjustments toward clean energy and production structures, which are critical for reducing China's emissions and alleviating the severe PM2.5 pollution.

Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

PubMed

Ren, Xiu'e; Chen, Jianbiao; Li, Gang; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

2018-08-01

The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.

Succession of Phylogeny and Function During Plant Litter Decomposition (2013 DOE JGI Genomics of Energy and Environment 8th Annual User Meeting)

ScienceCinema

Brodie, Eoin

2018-04-26

Eoin Brodie of Berkeley Lab on "Succession of phylogeny and function during plant litter decomposition" at the 8th Annual Genomics of Energy & Environment Meeting on March 27, 2013 in Walnut Creek, CA.

Succession of Phylogeny and Function During Plant Litter Decomposition (2013 DOE JGI Genomics of Energy and Environment 8th Annual User Meeting)

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

Brodie, Eoin

2013-03-01

Eoin Brodie of Berkeley Lab on "Succession of phylogeny and function during plant litter decomposition" at the 8th Annual Genomics of Energy & Environment Meeting on March 27, 2013 in Walnut Creek, CA.

Kinetic study of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7

NASA Astrophysics Data System (ADS)

Yang, Hee-Chul; Kim, Hyung-Ju; Lee, Si-Young; Yang, In-Hwan; Chung, Dong-Yong

2017-06-01

The thermochemical properties of uranium compounds have attracted much interest in relation to thermochemical treatments and the safe disposal of radioactive waste bearing uranium compounds. The characteristics of the thermal decomposition of uranium metaphosphate, U(PO3)4, into uranium pyrophosphate, UP2O7, have been studied from the view point of reaction kinetics and acting mechanisms. A mixture of U(PO3)4 and UP2O7 was prepared from the pyrolysis residue of uranium-bearing spent TBP. A kinetic analysis of the reaction of U(PO3)4 into UP2O7 was conducted using an isoconversional method and a master plot method on the basis of data from a non-isothermal thermogravimetric analysis. The thermal decomposition of U(PO3)4 into UP2O7 followed a single-step reaction with an activation energy of 175.29 ± 1.58 kJ mol-1. The most probable kinetic model was determined as a type of nucleation and nuclei-growth models, the Avrami-Erofeev model (A3), which describes that there are certain restrictions on nuclei growth of UP2O7 during the solid-state decomposition of U(PO3)4.

Acid and alkali effects on the decomposition of HMX molecule: a computational study.

PubMed

Zhang, Chaoyang; Li, Yuzhen; Xiong, Ying; Wang, Xiaolin; Zhou, Mingfei

2011-11-03

The stored and wasted explosives are usually in an acid or alkali environment, leading to the importance of exploring the acid and alkali effects on the decomposition mechanism of explosives. The acid and alkali effects on the decomposition of HMX molecule in gaseous state and in aqueous solution at 298 K are studied using quantum chemistry and molecular force field calculations. The results show that both H(+) and OH(-) make the decomposition in gaseous state energetically favorable. However, the effect of H(+) is much different from that of OH(-) in aqueous solution: OH(-) can accelerate the decomposition but H(+) cannot. The difference is mainly caused by the large aqueous solvation energy difference between H(+) and OH(-). The results confirm that the dissociation of HMX is energetically favored only in the base solutions, in good agreement with previous HMX base hydrolysis experimental observations. The different acid and alkali effects on the HMX decomposition are dominated by the large aqueous solvation energy difference between H(+) and OH(-).

Plasma-catalyst hybrid reactor with CeO2/γ-Al2O3 for benzene decomposition with synergetic effect and nano particle by-product reduction.

PubMed

Mao, Lingai; Chen, Zhizong; Wu, Xinyue; Tang, Xiujuan; Yao, Shuiliang; Zhang, Xuming; Jiang, Boqiong; Han, Jingyi; Wu, Zuliang; Lu, Hao; Nozaki, Tomohiro

2018-04-05

A dielectric barrier discharge (DBD) catalyst hybrid reactor with CeO 2 /γ-Al 2 O 3 catalyst balls was investigated for benzene decomposition at atmospheric pressure and 30 °C. At an energy density of 37-40 J/L, benzene decomposition was as high as 92.5% when using the hybrid reactor with 5.0wt%CeO 2 /γ-Al 2 O 3 ; while it was 10%-20% when using a normal DBD reactor without a catalyst. Benzene decomposition using the hybrid reactor was almost the same as that using an O 3 catalyst reactor with the same CeO 2 /γ-Al 2 O 3 catalyst, indicating that O 3 plays a key role in the benzene decomposition. Fourier transform infrared spectroscopy analysis showed that O 3 adsorption on CeO 2 /γ-Al 2 O 3 promotes the production of adsorbed O 2 - and O 2 2‒ , which contribute benzene decomposition over heterogeneous catalysts. Nano particles as by-products (phenol and 1,4-benzoquinone) from benzene decomposition can be significantly reduced using the CeO 2 /γ-Al 2 O 3 catalyst. H 2 O inhibits benzene decomposition; however, it improves CO 2 selectivity. The deactivated CeO 2 /γ-Al 2 O 3 catalyst can be regenerated by performing discharges at 100 °C and 192-204 J/L. The decomposition mechanism of benzene over CeO 2 /γ-Al 2 O 3 catalyst was proposed. Copyright © 2017 Elsevier B.V. All rights reserved.

EKC Analysis and Decomposition of Influencing Factors in Building Energy Consumption of Three Municipalities in China

NASA Astrophysics Data System (ADS)

Zhong, X. Y.; Gao, J. X.; Ren, H.; Cai, W. G.

2018-04-01

The acceleration of the urbanization process has brought new opportunities for China’s development. With the rapid economic development and people’s living standards improving, building energy consumption also showed a rigid growth trend. With the continuous improvement of the level of industrialization, industrial energy-saving potential declines. The construction industry to bear the task of energy-saving emission reduction will face more severe challenges. As the three municipalities of China, Beijing, Shanghai and Chongqing have significant radiation effects in the economy, urbanization level and construction industry development of the region. Therefore, it is of great significance to study the building energy consumption in the three regions with the change of urbanization level and the key factors. Based on the data of Beijing, Shanghai and Chongqing from 2001 to 2015, this paper attempts to find out whether the EKC curve of building energy consumption exists. At the same time, based on the results of the model, the data of the three regions are divided into three periods. The exponential decomposition method (LMDI) is used to find out the factors that have the greatest impact on the energy consumption of buildings in different stages. Moreover, analyzes the policy background of each stage and puts forward some policy suggestions on this basis.

Decomposition of L a2 -xS rxCu O4 into several L a2O3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

NASA Astrophysics Data System (ADS)

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet; Yu, Guichuan; Sasagawa, Takao; Greven, Martin; Mkhoyan, K. Andre

2018-05-01

We report the decomposition of L a2 -xS rxCu O4 into L a2O3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150 °C and is considerably expedited in the temperature range of 350 °C-450 °C. Two major resultant solid phases are identified as metallic Cu and L a2O3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, L a2O3 phases are further identified to be derivatives of a fluorite structure—fluorite, pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and La M4 ,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and L a2O3 phases remain unchanged after cooling to room temperature.

The Fourier decomposition method for nonlinear and non-stationary time series analysis.

PubMed

Singh, Pushpendra; Joshi, Shiv Dutt; Patney, Rakesh Kumar; Saha, Kaushik

2017-03-01

for many decades, there has been a general perception in the literature that Fourier methods are not suitable for the analysis of nonlinear and non-stationary data. In this paper, we propose a novel and adaptive Fourier decomposition method (FDM), based on the Fourier theory, and demonstrate its efficacy for the analysis of nonlinear and non-stationary time series. The proposed FDM decomposes any data into a small number of 'Fourier intrinsic band functions' (FIBFs). The FDM presents a generalized Fourier expansion with variable amplitudes and variable frequencies of a time series by the Fourier method itself. We propose an idea of zero-phase filter bank-based multivariate FDM (MFDM), for the analysis of multivariate nonlinear and non-stationary time series, using the FDM. We also present an algorithm to obtain cut-off frequencies for MFDM. The proposed MFDM generates a finite number of band-limited multivariate FIBFs (MFIBFs). The MFDM preserves some intrinsic physical properties of the multivariate data, such as scale alignment, trend and instantaneous frequency. The proposed methods provide a time-frequency-energy (TFE) distribution that reveals the intrinsic structure of a data. Numerical computations and simulations have been carried out and comparison is made with the empirical mode decomposition algorithms.

The Fourier decomposition method for nonlinear and non-stationary time series analysis

PubMed Central

Joshi, Shiv Dutt; Patney, Rakesh Kumar; Saha, Kaushik

2017-01-01

for many decades, there has been a general perception in the literature that Fourier methods are not suitable for the analysis of nonlinear and non-stationary data. In this paper, we propose a novel and adaptive Fourier decomposition method (FDM), based on the Fourier theory, and demonstrate its efficacy for the analysis of nonlinear and non-stationary time series. The proposed FDM decomposes any data into a small number of ‘Fourier intrinsic band functions’ (FIBFs). The FDM presents a generalized Fourier expansion with variable amplitudes and variable frequencies of a time series by the Fourier method itself. We propose an idea of zero-phase filter bank-based multivariate FDM (MFDM), for the analysis of multivariate nonlinear and non-stationary time series, using the FDM. We also present an algorithm to obtain cut-off frequencies for MFDM. The proposed MFDM generates a finite number of band-limited multivariate FIBFs (MFIBFs). The MFDM preserves some intrinsic physical properties of the multivariate data, such as scale alignment, trend and instantaneous frequency. The proposed methods provide a time–frequency–energy (TFE) distribution that reveals the intrinsic structure of a data. Numerical computations and simulations have been carried out and comparison is made with the empirical mode decomposition algorithms. PMID:28413352

Lumley decomposition of turbulent boundary layer at high Reynolds numbers

NASA Astrophysics Data System (ADS)

Tutkun, Murat; George, William K.

2017-02-01

The decomposition proposed by Lumley in 1966 is applied to a high Reynolds number turbulent boundary layer. The experimental database was created by a hot-wire rake of 143 probes in the Laboratoire de Mécanique de Lille wind tunnel. The Reynolds numbers based on momentum thickness (Reθ) are 9800 and 19 100. Three-dimensional decomposition is performed, namely, proper orthogonal decomposition (POD) in the inhomogeneous and bounded wall-normal direction, Fourier decomposition in the homogeneous spanwise direction, and Fourier decomposition in time. The first POD modes in both cases carry nearly 50% of turbulence kinetic energy when the energy is integrated over Fourier dimensions. The eigenspectra always peak near zero frequency and most of the large scale, energy carrying features are found at the low end of the spectra. The spanwise Fourier mode which has the largest amount of energy is the first spanwise mode and its symmetrical pair. Pre-multiplied eigenspectra have only one distinct peak and it matches the secondary peak observed in the log-layer of pre-multiplied velocity spectra. Energy carrying modes obtained from the POD scale with outer scaling parameters. Full or partial reconstruction of turbulent velocity signal based only on energetic modes or non-energetic modes revealed the behaviour of urms in distinct regions across the boundary layer. When urms is based on energetic reconstruction, there exists (a) an exponential decay from near wall to log-layer, (b) a constant layer through the log-layer, and (c) another exponential decay in the outer region. The non-energetic reconstruction reveals that urms has (a) an exponential decay from the near-wall to the end of log-layer and (b) a constant layer in the outer region. Scaling of urms using the outer parameters is best when both energetic and non-energetic profiles are combined.

TU-CD-207-01: Characterization of Breast Tissue Composition Using Spectral Mammography

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

Ding, H; Cho, H; Kumar, N

Purpose: To investigate the feasibility of characterizing the chemical composition of breast tissue, in terms of water and lipid, by using spectral mammography in simulation and postmortem studies. Methods: Analytical simulations were performed to obtain low- and high-energy signals of breast tissue based on previously reported water, lipid, and protein contents. Dual-energy decomposition was used to characterize the simulated breast tissue into water and lipid basis materials and the measured water density was compared to the known value. In experimental studies, postmortem breasts were imaged with a spectral mammography system based on a scanning multi-slit Si strip photon-counting detector. Low-more » and high-energy images were acquired simultaneously from a single exposure by sorting the recorded photons into the corresponding energy bins. Dual-energy material decomposition of the low- and high-energy images yielded individual pixel measurements of breast tissue composition in terms of water and lipid thicknesses. After imaging, each postmortem breast was chemically decomposed into water, lipid and protein. The water density calculated from chemical analysis was used as the reference gold standard. Correlation of the water density measurements between spectral mammography and chemical analysis was analyzed using linear regression. Results: Both simulation and postmortem studies showed good linear correlation between the decomposed water thickness using spectral mammography and chemical analysis. The slope of the linear fitting function in the simulation and postmortem studies were 1.15 and 1.21, respectively. Conclusion: The results indicate that breast tissue composition, in terms of water and lipid, can be accurately measured using spectral mammography. Quantitative breast tissue composition can potentially be used to stratify patients according to their breast cancer risk.« less

Optimization of design parameters of low-energy buildings

NASA Astrophysics Data System (ADS)

Vala, Jiří; Jarošová, Petra

2017-07-01

Evaluation of temperature development and related consumption of energy required for heating, air-conditioning, etc. in low-energy buildings requires the proper physical analysis, covering heat conduction, convection and radiation, including beam and diffusive components of solar radiation, on all building parts and interfaces. The system approach and the Fourier multiplicative decomposition together with the finite element technique offers the possibility of inexpensive and robust numerical and computational analysis of corresponding direct problems, as well as of the optimization ones with several design variables, using the Nelder-Mead simplex method. The practical example demonstrates the correlation between such numerical simulations and the time series of measurements of energy consumption on a small family house in Ostrov u Macochy (35 km northern from Brno).

Dual-energy x-ray image decomposition by independent component analysis

NASA Astrophysics Data System (ADS)

Jiang, Yifeng; Jiang, Dazong; Zhang, Feng; Zhang, Dengfu; Lin, Gang

2001-09-01

The spatial distributions of bone and soft tissue in human body are separated by independent component analysis (ICA) of dual-energy x-ray images. It is because of the dual energy imaging modelí-s conformity to the ICA model that we can apply this method: (1) the absorption in body is mainly caused by photoelectric absorption and Compton scattering; (2) they take place simultaneously but are mutually independent; and (3) for monochromatic x-ray sources the total attenuation is achieved by linear combination of these two absorption. Compared with the conventional method, the proposed one needs no priori information about the accurate x-ray energy magnitude for imaging, while the results of the separation agree well with the conventional one.

The analysis of energy consumption of the transport and manipulation process of Fanuc AM100iB robot

NASA Astrophysics Data System (ADS)

Cholewa, A.; Świder, J.; Zbilski, A.

2017-08-01

This article describes test results of energy consumption of Fanuc ArcMate 100iB robot during realization of the transport and manipulation process. The energy consumption test involved the acquisition of values of angular positions of the robot’s encoder shafts and values of tensions and expansions of the electrical currents in three phases of each engine. Based on the simulation results, the analysis of energy consumption was carried out, which specified the tested palletizing process using the set of complete and partial decompositions of the energy consumption of all these factors, which in significant degree impacted the amount of energy taken during the process. Quality of the data provided by the analysis of energy consumption was assessed through validation of results, which involved direct comparison of corresponding parameters, which values were measured and calculated. With regards to the developed analysis of energy consumption, computerized techniques were used to determine the impact of all material factors on the total energy consumption of the machine. The work presents the most significant results of the obtained outcomes.

Resonant electron capture by aspartame and aspartic acid molecules.

PubMed

Muftakhov, M V; Shchukin, P V

2016-12-30

The processes for dissociative electron capture are the key mechanisms for decomposition of biomolecules, proteins in particular, under interaction with low-energy electrons. Molecules of aspartic acid and aspartame, i.e. modified dipeptides, were studied herein to define the impact of the side functional groups on peptide chain decomposition in resonant electron-molecular reactions. The processes of formation and decomposition of negative ions of both aspartame and aspartic acid were studied by mass spectrometry of negative ions under resonant electron capture. The obtained mass spectra were interpreted under thermochemical analysis by quantum chemical calculations. Main channels of negative molecular ions fragmentation were found and characteristic fragment ions were identified. The СООН fragment of the side chain in aspartic acid is shown to play a key role like the carboxyl group in amino acids and aliphatic oligopeptides. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

New solution decomposition and minimization schemes for Poisson-Boltzmann equation in calculation of biomolecular electrostatics

NASA Astrophysics Data System (ADS)

Xie, Dexuan

2014-10-01

The Poisson-Boltzmann equation (PBE) is one widely-used implicit solvent continuum model in the calculation of electrostatic potential energy for biomolecules in ionic solvent, but its numerical solution remains a challenge due to its strong singularity and nonlinearity caused by its singular distribution source terms and exponential nonlinear terms. To effectively deal with such a challenge, in this paper, new solution decomposition and minimization schemes are proposed, together with a new PBE analysis on solution existence and uniqueness. Moreover, a PBE finite element program package is developed in Python based on the FEniCS program library and GAMer, a molecular surface and volumetric mesh generation program package. Numerical tests on proteins and a nonlinear Born ball model with an analytical solution validate the new solution decomposition and minimization schemes, and demonstrate the effectiveness and efficiency of the new PBE finite element program package.

Effect of fast neutron, gamma-ray and combined radiations on the thermal decomposition of ammonium perchlorate single crystals

NASA Technical Reports Server (NTRS)

Herley, P. J.; Wang, C. S.; Varsi, G.; Levy, P. W.

1974-01-01

The thermal decomposition kinetics have been determined for ammonium perchlorate crystals subjected to a fast neutron irradiation or to a fast neutron irradiation followed by a gamma-ray irradiation. Qualitatively, the radiation induced changes are similar to those obtained in this and in previous studies, with samples exposed only to gamma rays. The induction period is shortened and the rate constants, obtained from an Avrami-Erofeyev kinetic analysis, are modified. The acceleratory period constant increases and the decay period constant decreases. When compared on an equal deposited energy basis, the fast neutron induced changes are appreciably larger than the gamma-ray induced changes. Some, or all, of the fast neutron induced effects might be attributable to the introduction of localized regions of concentrated radiation damage ('spikes') by lattice atom recoils which become thermal decomposition sites when the crystals are heated.

TH-CD-202-03: Enhancing Soft-Tissue CT Contrast for Radiation Therapy Using Mono-Energetic Decompositions of Dual Energy CT

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

Noid, G; Tai, A; Liu, Y

Purpose: It is desirable to increase CT soft-tissue contrast to improve delineation of tumor target and/or surrounding organs at risk (OAR) in RT planning and delivery guidance. The purpose of this work is to investigate the use of monoenergetic decompositions obtained from dual energy (DE) CT to improve soft-tissue contrast. Methods: CT data were acquired for 5 prostate and 5 pancreas patients and a phantom with a CT Scanner (Definition AS Open, Siemens) using both sequential DE protocols and standard protocols. For the DE protocols, the scanner rapidly performs two acquisitions at 80 kVp and 140 kVp. The CT numbersmore » of soft tissue inserts in the phantom (CTED/Gammex) were measured across the spectrum of available monoenergetic decompositions (40 to 140 keV) and compared to the standard protocol (120 kVp, 0.6 pitch, 18 mGy CTDIvol). Contrast, defined as the difference in the average CT number between target and OAR, was measured for all subjects and compared between the DE and standard protocols. Results: Mono-energetic decompositions of the phantom demonstrate an enhancement of soft-tissue contrast as the energy is decreased. For instance, relative to the 120 kVp scans the Liver ED insert increased in CT number by 25 HU while the adipose ED insert decreased by 50 HU. The lowest energy decompositions featured the highest contrast between target and OAR. For every patient, the contrast increased by decomposing at 40 keV. The average increase in contrast relative to a 120 kVp scan for prostate patients at 40 keV was 25.05±17.28 HU while for pancreas patients it was 19.21±17.39 HU. Conclusion: Low energy monoenergetic decompositions from dual-energy CT substantially increase soft-tissue contrast. At the lowest achievable monoenergetic decompositions the maximum soft-tissue contrast is achieved and the delineation of target and OAR is improved. Thus it is beneficial to use DECT in radiation oncology. Supported by Siemens.« less

Adaptive Fourier decomposition based ECG denoising.

PubMed

Wang, Ze; Wan, Feng; Wong, Chi Man; Zhang, Liming

2016-10-01

A novel ECG denoising method is proposed based on the adaptive Fourier decomposition (AFD). The AFD decomposes a signal according to its energy distribution, thereby making this algorithm suitable for separating pure ECG signal and noise with overlapping frequency ranges but different energy distributions. A stop criterion for the iterative decomposition process in the AFD is calculated on the basis of the estimated signal-to-noise ratio (SNR) of the noisy signal. The proposed AFD-based method is validated by the synthetic ECG signal using an ECG model and also real ECG signals from the MIT-BIH Arrhythmia Database both with additive Gaussian white noise. Simulation results of the proposed method show better performance on the denoising and the QRS detection in comparing with major ECG denoising schemes based on the wavelet transform, the Stockwell transform, the empirical mode decomposition, and the ensemble empirical mode decomposition. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electron energy-loss spectroscopy of single nanocrystals: mapping of tin allotropes.

PubMed

Roesgaard, Søren; Ramasse, Quentin; Chevallier, Jacques; Fyhn, Mogens; Julsgaard, Brian

2018-05-25

Using monochromated electron energy-loss spectroscopy (EELS), we are able to map different allotropes in Sn-nanocrystals embedded in Si. It is demonstrated that α-Sn and β-Sn, as well as an interface related plasmon, can be distinguished in embedded Sn-nanostructures. The EELS data is interpreted by standard non-negative matrix factorization followed by a manual Lorentzian decomposition. The decomposition allows for a more physical understanding of the EELS mapping without reducing the level of information. Extending the analysis from a reference system to smaller nanocrystals demonstrates that allotrope determination in nanoscale systems down below 5 nm is possible. Such local information proves the use of monochromated EELS mapping as a powerful technique to study nanoscale systems. This possibility enables investigation of small nanostructures that cannot be investigated through other means, allowing for a better understanding and thus leading to realizations that can result in nanomaterials with improved properties.

Electron energy-loss spectroscopy of single nanocrystals: mapping of tin allotropes

NASA Astrophysics Data System (ADS)

Roesgaard, Søren; Ramasse, Quentin; Chevallier, Jacques; Fyhn, Mogens; Julsgaard, Brian

2018-05-01

Using monochromated electron energy-loss spectroscopy (EELS), we are able to map different allotropes in Sn-nanocrystals embedded in Si. It is demonstrated that α-Sn and β-Sn, as well as an interface related plasmon, can be distinguished in embedded Sn-nanostructures. The EELS data is interpreted by standard non-negative matrix factorization followed by a manual Lorentzian decomposition. The decomposition allows for a more physical understanding of the EELS mapping without reducing the level of information. Extending the analysis from a reference system to smaller nanocrystals demonstrates that allotrope determination in nanoscale systems down below 5 nm is possible. Such local information proves the use of monochromated EELS mapping as a powerful technique to study nanoscale systems. This possibility enables investigation of small nanostructures that cannot be investigated through other means, allowing for a better understanding and thus leading to realizations that can result in nanomaterials with improved properties.

Thermal characterization and model free kinetics of aged epoxies and foams using TGA and DSC methods.

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

Cordaro, Joseph Gabriel; Kruizenga, Alan Michael; Nissen, April

2013-10-01

Two classes of materials, poly(methylene diphenyl diisocyanate) or PMDI foam, and cross-linked epoxy resins, were characterized using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), to help understand the effects of aging and %E2%80%9Cbake-out%E2%80%9D. The materials were evaluated for mass loss and the onset of decomposition. In some experiments, volatile materials released during heating were analyzed via mass spectroscopy. In all, over twenty materials were evaluated to compare the mass loss and onset temperature for decomposition. Model free kinetic (MFK) measurements, acquired using variable heating rate TGA experiments, were used to calculate the apparent activation energy of thermal decomposition.more » From these compiled data the effects of aging, bake-out, and sample history on the thermal stability of materials were compared. No significant differences between aged and unaged materials were detected. Bake-out did slightly affect the onset temperature of decomposition but only at the highest bake-out temperatures. Finally, some recommendations for future handling are made.« less

Atomic decomposition of the protein solvation free energy and its application to amyloid-beta protein in water

NASA Astrophysics Data System (ADS)

Chong, Song-Ho; Ham, Sihyun

2011-07-01

We report the development of an atomic decomposition method of the protein solvation free energy in water, which ascribes global change in the solvation free energy to local changes in protein conformation as well as in hydration structure. So far, empirical decomposition analyses based on simple continuum solvation models have prevailed in the study of protein-protein interactions, protein-ligand interactions, as well as in developing scoring functions for computer-aided drug design. However, the use of continuum solvation model suffers serious drawbacks since it yields the protein free energy landscape which is quite different from that of the explicit solvent model and since it does not properly account for the non-polar hydrophobic effects which play a crucial role in biological processes in water. Herein, we develop an exact and general decomposition method of the solvation free energy that overcomes these hindrances. We then apply this method to elucidate the molecular origin for the solvation free energy change upon the conformational transitions of 42-residue amyloid-beta protein (Aβ42) in water, whose aggregation has been implicated as a primary cause of Alzheimer's disease. We address why Aβ42 protein exhibits a great propensity to aggregate when transferred from organic phase to aqueous phase.

Energy Diagram for the Catalytic Decomposition of Hydrogen Peroxide

ERIC Educational Resources Information Center

Tatsuoka, Tomoyuki; Koga, Nobuyoshi

2013-01-01

Drawing a schematic energy diagram for the decomposition of H[subscript 2]O[subscript 2] catalyzed by MnO[subscript 2] through a simple thermometric measurement outlined in this study is intended to integrate students' understanding of thermochemistry and kinetics of chemical reactions. The reaction enthalpy, delta[subscript r]H, is…

Time-frequency analysis : mathematical analysis of the empirical mode decomposition.

DOT National Transportation Integrated Search

2009-01-01

Invented over 10 years ago, empirical mode : decomposition (EMD) provides a nonlinear : time-frequency analysis with the ability to successfully : analyze nonstationary signals. Mathematical : Analysis of the Empirical Mode Decomposition : is a...

A LABORATORY STUDY TO INVESTIGATE GASEOUS EMISSIONS AND SOLIDS DECOMPOSITION DURING COMPOSTING OF MUNICIPAL SOLID WASTE

EPA Science Inventory

The report gives results of a materials flow analysis performed for composting municipal solid waste (MSW) and specific biodegradable organic components of MSW. (NOTE: This work is part of an overall U.S. EPA project providing cost, energy, and materials flow information on diffe...

Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species

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

Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo

2015-12-21

Quantitative analysis of desorption and decomposition kinetics of formic acid (HCOOH) on Cu(111) was performed by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy, and time-resolved infrared reflection absorption spectroscopy. The activation energy for desorption is estimated to be 53–75 kJ/mol by the threshold TPD method as a function of coverage. Vibrational spectra of the first layer HCOOH at 155.3 K show that adsorbed molecules form a polymeric structure via the hydrogen bonding network. Adsorbed HCOOH molecules are dissociated gradually into monodentate formate species. The activation energy for the dissociation into monodentate formate species is estimated to be 65.0 kJ/mol atmore » a submonolayer coverage (0.26 molecules/surface Cu atom). The hydrogen bonding between adsorbed HCOOH species plays an important role in the stabilization of HCOOH on Cu(111). The monodentate formate species are stabilized at higher coverages, because of the lack of vacant sites for the bidentate formation.« less

Thermochemical generation of hydrogen and carbon dioxide

NASA Technical Reports Server (NTRS)

Lawson, Daniel D. (Inventor); England, Christopher (Inventor)

1984-01-01

Mixing of carbon in the form of high sulfur coal with sulfuric acid reduces the temperature of sulfuric acid decomposition from 830.degree. C. to between 300.degree. C. and 400.degree. C. The low temperature sulfuric acid decomposition is particularly useful in thermal chemical cycles for splitting water to produce hydrogen. Carbon dioxide is produced as a commercially desirable byproduct. Lowering of the temperature for the sulfuric acid decomposition or oxygen release step simplifies equipment requirements, lowers thermal energy input and reduces corrosion problems presented by sulfuric acid at conventional cracking temperatures. Use of high sulfur coal as the source of carbon for the sulfuric acid decomposition provides an environmentally safe and energy efficient utilization of this normally polluting fuel.

Insight into the novel inhibition mechanism of apigenin to Pneumolysin by molecular modeling

NASA Astrophysics Data System (ADS)

Niu, Xiaodi; Yang, Yanan; Song, Meng; Wang, Guizhen; Sun, Lin; Gao, Yawen; Wang, Hongsu

2017-11-01

In this study, the mechanism of apigenin inhibition was explored using molecular modelling, binding energy calculation, and mutagenesis assays. Energy decomposition analysis indicated that apigenin binds in the gap between domains 3 and 4 of PLY. Using principal component analysis, we found that binding of apigenin to PLY weakens the motion of domains 3 and 4. Consequently, these domains cannot complete the transition from monomer to oligomer, thereby blocking oligomerisation of PLY and counteracting its haemolytic activity. This inhibitory mechanism was confirmed by haemolysis assays, and these findings will promote the future development of an antimicrobial agent.

Initial mechanisms for the unimolecular decomposition of electronically excited bisfuroxan based energetic materials.

PubMed

Yuan, Bing; Bernstein, Elliot R

2017-01-07

Unimolecular decomposition of energetic molecules, 3,3'-diamino-4,4'-bisfuroxan (labeled as A) and 4,4'-diamino-3,3'-bisfuroxan (labeled as B), has been explored via 226/236 nm single photon laser excitation/decomposition. These two energetic molecules, subsequent to UV excitation, create NO as an initial decomposition product at the nanosecond excitation energies (5.0-5.5 eV) with warm vibrational temperature (1170 ± 50 K for A, 1400 ± 50 K for B) and cold rotational temperature (<55 K). Initial decomposition mechanisms for these two electronically excited, isolated molecules are explored at the complete active space self-consistent field (CASSCF(12,12)/6-31G(d)) level with and without MP2 correction. Potential energy surface calculations illustrate that conical intersections play an essential role in the calculated decomposition mechanisms. Based on experimental observations and theoretical calculations, NO product is released through opening of the furoxan ring: ring opening can occur either on the S 1 excited or S 0 ground electronic state. The reaction path with the lowest energetic barrier is that for which the furoxan ring opens on the S 1 state via the breaking of the N1-O1 bond. Subsequently, the molecule moves to the ground S 0 state through related ring-opening conical intersections, and an NO product is formed on the ground state surface with little rotational excitation at the last NO dissociation step. For the ground state ring opening decomposition mechanism, the N-O bond and C-N bond break together in order to generate dissociated NO. With the MP2 correction for the CASSCF(12,12) surface, the potential energies of molecules with dissociated NO product are in the range from 2.04 to 3.14 eV, close to the theoretical result for the density functional theory (B3LYP) and MP2 methods. The CASMP2(12,12) corrected approach is essential in order to obtain a reasonable potential energy surface that corresponds to the observed decomposition behavior of these molecules. Apparently, highly excited states are essential for an accurate representation of the kinetics and dynamics of excited state decomposition of both of these bisfuroxan energetic molecules. The experimental vibrational temperatures of NO products of A and B are about 800-1000 K lower than previously studied energetic molecules with NO as a decomposition product.

Energy index decomposition methodology at the plant level

NASA Astrophysics Data System (ADS)

Kumphai, Wisit

Scope and method of study. The dissertation explores the use of a high level energy intensity index as a facility-level energy performance monitoring indicator with a goal of developing a methodology for an economically based energy performance monitoring system that incorporates production information. The performance measure closely monitors energy usage, production quantity, and product mix and determines the production efficiency as a part of an ongoing process that would enable facility managers to keep track of and, in the future, be able to predict when to perform a recommissioning process. The study focuses on the use of the index decomposition methodology and explored several high level (industry, sector, and country levels) energy utilization indexes, namely, Additive Log Mean Divisia, Multiplicative Log Mean Divisia, and Additive Refined Laspeyres. One level of index decomposition is performed. The indexes are decomposed into Intensity and Product mix effects. These indexes are tested on a flow shop brick manufacturing plant model in three different climates in the United States. The indexes obtained are analyzed by fitting an ARIMA model and testing for dependency between the two decomposed indexes. Findings and conclusions. The results concluded that the Additive Refined Laspeyres index decomposition methodology is suitable to use on a flow shop, non air conditioned production environment as an energy performance monitoring indicator. It is likely that this research can be further expanded in to predicting when to perform a recommissioning process.

An efficient computational approach to model statistical correlations in photon counting x-ray detectors

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

Faby, Sebastian; Maier, Joscha; Sawall, Stefan

2016-07-15

Purpose: To introduce and evaluate an increment matrix approach (IMA) describing the signal statistics of energy-selective photon counting detectors including spatial–spectral correlations between energy bins of neighboring detector pixels. The importance of the occurring correlations for image-based material decomposition is studied. Methods: An IMA describing the counter increase patterns in a photon counting detector is proposed. This IMA has the potential to decrease the number of required random numbers compared to Monte Carlo simulations by pursuing an approach based on convolutions. To validate and demonstrate the IMA, an approximate semirealistic detector model is provided, simulating a photon counting detector inmore » a simplified manner, e.g., by neglecting count rate-dependent effects. In this way, the spatial–spectral correlations on the detector level are obtained and fed into the IMA. The importance of these correlations in reconstructed energy bin images and the corresponding detector performance in image-based material decomposition is evaluated using a statistically optimal decomposition algorithm. Results: The results of IMA together with the semirealistic detector model were compared to other models and measurements using the spectral response and the energy bin sensitivity, finding a good agreement. Correlations between the different reconstructed energy bin images could be observed, and turned out to be of weak nature. These correlations were found to be not relevant in image-based material decomposition. An even simpler simulation procedure based on the energy bin sensitivity was tested instead and yielded similar results for the image-based material decomposition task, as long as the fact that one incident photon can increase multiple counters across neighboring detector pixels is taken into account. Conclusions: The IMA is computationally efficient as it required about 10{sup 2} random numbers per ray incident on a detector pixel instead of an estimated 10{sup 8} random numbers per ray as Monte Carlo approaches would need. The spatial–spectral correlations as described by IMA are not important for the studied image-based material decomposition task. Respecting the absolute photon counts and thus the multiple counter increases by a single x-ray photon, the same material decomposition performance could be obtained with a simpler detector description using the energy bin sensitivity.« less

Intuitive Density Functional Theory-Based Energy Decomposition Analysis for Protein-Ligand Interactions.

PubMed

Phipps, M J S; Fox, T; Tautermann, C S; Skylaris, C-K

2017-04-11

First-principles quantum mechanical calculations with methods such as density functional theory (DFT) allow the accurate calculation of interaction energies between molecules. These interaction energies can be dissected into chemically relevant components such as electrostatics, polarization, and charge transfer using energy decomposition analysis (EDA) approaches. Typically EDA has been used to study interactions between small molecules; however, it has great potential to be applied to large biomolecular assemblies such as protein-protein and protein-ligand interactions. We present an application of EDA calculations to the study of ligands that bind to the thrombin protein, using the ONETEP program for linear-scaling DFT calculations. Our approach goes beyond simply providing the components of the interaction energy; we are also able to provide visual representations of the changes in density that happen as a result of polarization and charge transfer, thus pinpointing the functional groups between the ligand and protein that participate in each kind of interaction. We also demonstrate with this approach that we can focus on studying parts (fragments) of ligands. The method is relatively insensitive to the protocol that is used to prepare the structures, and the results obtained are therefore robust. This is an application to a real protein drug target of a whole new capability where accurate DFT calculations can produce both energetic and visual descriptors of interactions. These descriptors can be used to provide insights for tailoring interactions, as needed for example in drug design.

[EMD Time-Frequency Analysis of Raman Spectrum and NIR].

PubMed

Zhao, Xiao-yu; Fang, Yi-ming; Tan, Feng; Tong, Liang; Zhai, Zhe

2016-02-01

This paper analyzes the Raman spectrum and Near Infrared Spectrum (NIR) with time-frequency method. The empirical mode decomposition spectrum becomes intrinsic mode functions, which the proportion calculation reveals the Raman spectral energy is uniform distributed in each component, while the NIR's low order intrinsic mode functions only undertakes fewer primary spectroscopic effective information. Both the real spectrum and numerical experiments show that the empirical mode decomposition (EMD) regard Raman spectrum as the amplitude-modulated signal, which possessed with high frequency adsorption property; and EMD regards NIR as the frequency-modulated signal, which could be preferably realized high frequency narrow-band demodulation during first-order intrinsic mode functions. The first-order intrinsic mode functions Hilbert transform reveals that during the period of empirical mode decomposes Raman spectrum, modal aliasing happened. Through further analysis of corn leaf's NIR in time-frequency domain, after EMD, the first and second orders components of low energy are cut off, and reconstruct spectral signal by using the remaining intrinsic mode functions, the root-mean-square error is 1.001 1, and the correlation coefficient is 0.981 3, both of these two indexes indicated higher accuracy in re-construction; the decomposition trend term indicates the absorbency is ascending along with the decreasing to wave length in the near-infrared light wave band; and the Hilbert transform of characteristic modal component displays, 657 cm⁻¹ is the specific frequency by the corn leaf stress spectrum, which could be regarded as characteristic frequency for identification.

Laser augmented decomposition. II. D/sub 3/BPF/sub 3/. [Deuterium effects

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

Chien, K.R.; Bauer, S.H.

1976-06-17

The study of the accelerated decomposition of H/sub 3/BPF/sub 3/ induced by laser radiation (930-950 cm/sup -1/ was extended to the fully deuterated species. While in all essential respects the kinetics of the ir photolysis for the two compounds are identical, the few differences which were uncovered proved crucial in pointing to interesting features of the mechanism. These verified predictions were based on a normal mode analysis for the distribution of potential energy among the internal coordinates. For the laser augmented decomposition, E/sub a//sup L/ = 3.5 +- 1 kcal/mol, compared with E/sub a//sup th/ = 29.3 kcal/mol for themore » thermal process. The quantum efficiency is low, approximately 4 x 10/sup 4/ photons/molecule decomposed. The rates of decomposition depend on the isotopic content and are sensitively dependent on the frequency of the irradiating line. For example, with P(24) large fractionation ratios were found for D/sub 3/BPF/sub 3/ vs. H/sub 3/BPF/sub 3/, and small differences for D/sub 3//sup 11/BPF/sub 3/ vs. D/sub 3//sup 10/BPF/sub 3/. The levels of decomposition induced by the sequential three-photon absorption have been semiquantitatively accounted for.« less

Experimental and DFT simulation study of a novel felodipine cocrystal: Characterization, dissolving properties and thermal decomposition kinetics.

PubMed

Yang, Caiqin; Guo, Wei; Lin, Yulong; Lin, Qianqian; Wang, Jiaojiao; Wang, Jing; Zeng, Yanli

2018-05-30

In this study, a new cocrystal of felodipine (Fel) and glutaric acid (Glu) with a high dissolution rate was developed using the solvent ultrasonic method. The prepared cocrystal was characterized using X-ray powder diffraction, differential scanning calorimetry, thermogravimetric (TG) analysis, and infrared (IR) spectroscopy. To provide basic information about the optimization of pharmaceutical preparations of Fel-based cocrystals, this work investigated the thermal decomposition kinetics of the Fel-Glu cocrystal through non-isothermal thermogravimetry. Density functional theory (DFT) simulations were also performed on the Fel monomer and the trimolecular cocrystal compound for exploring the mechanisms underlying hydrogen bonding formation and thermal decomposition. Combined results of IR spectroscopy and DFT simulation verified that the Fel-Glu cocrystal formed via the NH⋯OC and CO⋯HO hydrogen bonds between Fel and Glu at the ratio of 1:2. The TG/derivative TG curves indicated that the thermal decomposition of the Fel-Glu cocrystal underwent a two-step process. The apparent activation energy (E a ) and pre-exponential factor (A) of the thermal decomposition for the first stage were 84.90 kJ mol -1 and 7.03 × 10 7  min -1 , respectively. The mechanism underlying thermal decomposition possibly involved nucleation and growth, with the integral mechanism function G(α) of α 3/2 . DFT calculation revealed that the hydrogen bonding between Fel and Glu weakened the terminal methoxyl, methyl, and ethyl groups in the Fel molecule. As a result, these groups were lost along with the Glu molecule in the first thermal decomposition. In conclusion, the formed cocrystal exhibited different thermal decomposition kinetics and showed different E a , A, and shelf life from the intact active pharmaceutical ingredient. Copyright © 2018 Elsevier B.V. All rights reserved.

Impact during equine locomotion: techniques for measurement and analysis.

PubMed

Burn, J F; Wilson, A; Nason, G P

1997-05-01

Impact is implicated in the development of several types of musculoskeletal injury in the horse. Characterisation of impact experienced during strenuous exercise is an important first step towards understanding the mechanism for injury. Measurement and analysis of large, short duration impacts is difficult. The measurement system must be able to record transient peaks and high frequencies accurately. The analysis technique must be able to characterise the impact signal in time and frequency. This paper presents a measurement system and analysis technique for the characterisation of large impacts. A piezo-electric accelerometer was securely mounted on the dorsal surface of the horses hoof. Saddle mounted charge amplifiers and a 20 m coaxial cable transferred these data to a PC based logging system. Data were down-loaded onto a UNIX workstation and analysed using a proprietary statistics package. The values of parameters calculated from the time series data were comparable to those of other authors. A wavelet decomposition showed that the frequency profile of the signal changed with time. While most spectral energy was seen at impact, a significant amount of energy was contained in the signal immediately following impact. Over 99% of this energy was contained in frequencies less than 1250 Hz. The sampling rate and the frequency response of a measurement system for recording impact should be chosen carefully to prevent loss or corruption of data. Time scale analysis using a wavelet decomposition is a powerful technique which can be used to characterise impact data. The use of contour plots provides a highly visual representation of the time and frequency localisation of power during impact.

Ferrocene Orientation Determined Intramolecular Interactions Using Energy Decomposition Analysis.

PubMed

Wang, Feng; Islam, Shawkat; Vasilyev, Vladislav

2015-11-16

Two very different quantum mechanically based energy decomposition analyses (EDA) schemes are employed to study the dominant energy differences between the eclipsed and staggered ferrocene conformers. One is the extended transition state (ETS) based on the Amsterdam Density Functional (ADF) package and the other is natural EDA (NEDA) based in the General Atomic and Molecular Electronic Structure System (GAMESS) package. It reveals that in addition to the model (theory and basis set), the fragmentation channels more significantly affect the interaction energy terms (Δ E ) between the conformers. It is discovered that such an interaction energy can be absorbed into the pre-partitioned fragment channels so that to affect the interaction energies in a particular conformer of Fc. To avoid this, the present study employs a complete fragment channel-the fragments of ferrocene are individual neutral atoms. It therefore discovers that the major difference between the ferrocene conformers is due to the quantum mechanical Pauli repulsive energy and orbital attractive energy, leading to the eclipsed ferrocene the energy preferred structure. The NEDA scheme further indicates that the sum of attractive (negative) polarization (POL) and charge transfer (CL) energies prefers the eclipsed ferrocene. The repulsive (positive) deformation (DEF) energy, which is dominated by the cyclopentadienyle (Cp) rings, prefers the staggered ferrocene. Again, the cancellation results in a small energy residue in favour of the eclipsed ferrocene, in agreement with the ETS scheme. Further Natural Bond Orbital (NBO) analysis indicates that all NBO energies, total Lewis (no Fe) and lone pair (LP) deletion all prefer the eclipsed Fc conformer. The most significant energy preferring the eclipsed ferrocene without cancellation is the interactions between the donor lone pairs (LP) of the Fe atom and the acceptor antibond (BD*) NBOs of all C-C and C-H bonds in the ligand, LP(Fe)-BD*(C-C & C-H), which strongly stabilizes the eclipsed (D 5h ) conformation by -457.6 kcal·mol -1 .

Retrospective and Prospective Decomposition Analysis of Chinese Manufacturing Energy Use, 1995-2020

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

Hasanbeigi, Ali; Price, Lynn; Fino-Chen, Cecilia

In 2010, China was responsible for nearly 20 percent of global energy use and 25 percent of energy-related carbon dioxide (CO 2) emissions. Unlike most countries, China’s energy consumption pattern is unique because the industrial sector dominates the country’s total energy consumption, accounting for about 70 percent of energy use and 72 percent of CO 2 emissions in 2010. For this reason, the development path of China’s industrial sector will greatly affect future energy demand and dynamics of not only China, but the entire world. A number of analyses of historical trends have been conducted, but careful projections of themore » key factors affecting China’s industry sector energy use over the next decade are scarce. This study analyzes industrial energy use and the economic structure of the Chinese manufacturing sector in detail. First, the study analyzes the energy use of and output from 18 industry sub-sectors. Then, retrospective (1995-2010) and prospective (2010-2020) decomposition analyses are conducted for these industrial sectors in order to show how different factors (production growth, structural change, and energy intensity change) influenced industrial energy use trends in China over the last 15 years and how they will do so over the next 10 years. The results of this study will allow policy makers to quantitatively compare the level of structural change in the past and in the years to come and adjust their policies if needed to move towards the target of less energy-intensive industries. The scenario analysis shows the structural change achieved through different paths and helps to understand the consequences of supporting or limiting the growth of certain manufacturing subsectors from the point of view of energy use and structural change. The results point out the industries that have the largest influence in such structural change« less

Hydrogen and carbon nanotube production via catalytic decomposition of methane

NASA Astrophysics Data System (ADS)

Deniz, Cansu; Karatepe, Nilgün

2013-09-01

The future energy demand is expected to increase significantly due to an increasing world population and demands for higher standards of living and better air quality. Hydrogen is considered as an energy carrier because of its high conversion efficiency and low pollutant emissions. It can be produced from various sources and transformed into electricity and other energy forms with a low pollution. The catalytic decomposition of hydrocarbon has been seen as a really useful method for production of pure hydrogen and for the environmental concern. The objective of this study was to assess the impact of catalyst composition and processing parameters on COx-free hydrogen production and to produce an available solid form of co-product carbon as carbon nanotubes via catalytic decomposition of methane. The optimum experimental conditions for methane decomposition have been investigated. Fe, Co and Ni are used as catalysts (nano materials) over different substrates as SiO2 and MgO to produce hydrogen at optimum temperatures.

Time-frequency analysis of time-varying modulated signals based on improved energy separation by iterative generalized demodulation

NASA Astrophysics Data System (ADS)

Feng, Zhipeng; Chu, Fulei; Zuo, Ming J.

2011-03-01

Energy separation algorithm is good at tracking instantaneous changes in frequency and amplitude of modulated signals, but it is subject to the constraints of mono-component and narrow band. In most cases, time-varying modulated vibration signals of machinery consist of multiple components, and have so complicated instantaneous frequency trajectories on time-frequency plane that they overlap in frequency domain. For such signals, conventional filters fail to obtain mono-components of narrow band, and their rectangular decomposition of time-frequency plane may split instantaneous frequency trajectories thus resulting in information loss. Regarding the advantage of generalized demodulation method in decomposing multi-component signals into mono-components, an iterative generalized demodulation method is used as a preprocessing tool to separate signals into mono-components, so as to satisfy the requirements by energy separation algorithm. By this improvement, energy separation algorithm can be generalized to a broad range of signals, as long as the instantaneous frequency trajectories of signal components do not intersect on time-frequency plane. Due to the good adaptability of energy separation algorithm to instantaneous changes in signals and the mono-component decomposition nature of generalized demodulation, the derived time-frequency energy distribution has fine resolution and is free from cross term interferences. The good performance of the proposed time-frequency analysis is illustrated by analyses of a simulated signal and the on-site recorded nonstationary vibration signal of a hydroturbine rotor during a shut-down transient process, showing that it has potential to analyze time-varying modulated signals of multi-components.

Compositional partitioning during the spinodal decomposition in Cu-Ni-Sn alloy

NASA Astrophysics Data System (ADS)

Basak, C. B.; Poswal, A. K.

2018-05-01

Spinodal decomposition in Cu-9.4at%Ni-3.1at%Sn alloy was elucidated with the new insight from the experimental EXAFS analysis supported by ab initio total energy calculations suggesting the strong influence of the first near-neighbour atoms. Enthalpy of mixing was calculated for all crystallographically unique first near-neighbour configurations and finally an average positive enthalpy of mixing of 1604 J/mol was obtained. Combination of ab initio results, XRD and EXAFS analysis indicate that one of the daughter phase becomes rich in Ni and Sn than the other phase; in contrary to the earlier proposition that Cu/Ni ratio remains constant in both daughter phases. It is also shown that the present thermodynamic description requires further refinement to extend the miscibility gap towards lower Ni content in Cu-Ni-Sn system.

Analysis of coals and biomass pyrolysis using the distributed activation energy model.

PubMed

Li, Zhengqi; Liu, Chunlong; Chen, Zhichao; Qian, Juan; Zhao, Wei; Zhu, Qunyi

2009-01-01

The thermal decomposition of coals and biomass was studied using thermogravimetric analysis with the distributed activation energy model. The integral method resulted in Datong bituminous coal conversions of 3-73% at activation energies of 100-486 kJ/mol. The corresponding frequency factors were e(19.5)-e(59.0)s(-1). Jindongnan lean coal conversions were 8-52% at activation energies of 100-462 kJ/mol. Their corresponding frequency factors were e(13.0)-e(55.8)s(-1). The conversion of corn-stalk skins were 1-84% at activation energies of 62-169 kJ/mol with frequency factors of e(10.8)-e(26.5)s(-1). Datong bituminous coal, Jindongnan lean coal and corn-stalk skins had approximate Gaussian distribution functions with linear ln k(0) to E relationships.

Molecular properties of metal difluorides and their interactions with CO2 and H2O molecules: a DFT investigation.

PubMed

Arokiyanathan, Agnes Lincy; Lakshmipathi, Senthilkumar

2017-11-18

A computational study of metal difluorides (MF 2 ; M = Ca to Zn) and their interactions with carbon dioxide and water molecules was performed. The structural parameter values obtained and the results of AIM analysis and energy decomposition analysis indicated that the Ca-F bond is weaker and less ionic than the bonds in the transition metal difluorides. A deformation density plot revealed the stablizing influence of the Jahn-Teller effect in nonlinear MF 2 molecules (e.g., where M= Sc, Ti, Cr). An anaysis of the metal K-edge peaks of the difluorides showed that shifts in the edge energy were due to the combined effects of the ionicity, effective nuclear charge, and the spin state of the metal. The interactions of CO 2 with ScF 2 (Scc3 geometry) and TiF 2 (Tic2 geometry) caused CO 2 to shift from its usual linear geometry to a bent geometry (η 2 (C=O) binding mode), while it retained its linear geometry (η 1 (O) binding mode) when it interacted with the other metal difluorides. Energy decomposition analysis showed that, among the various geometries considered, the Scc3 and Tic2 geometries possessed the highest interaction energies and orbital interaction energies. Heavier transition metal difluorides showed stronger affinities for H 2 O, whereas the lighter transition metal (Sc and Ti) difluorides preferred CO 2 . Overall, the results of this study suggest that fluorides of lighter transition metals with partially filled d orbitals (e.g., Sc and Ti) could be used for CO 2 capture under moist conditions. Graphical abstract Interaction of metal difluorides with carbon dioxide and water.

The role of axis embedding on rigid rotor decomposition analysis of variational rovibrational wave functions.

PubMed

Szidarovszky, Tamás; Fábri, Csaba; Császár, Attila G

2012-05-07

Approximate rotational characterization of variational rovibrational wave functions via the rigid rotor decomposition (RRD) protocol is developed for Hamiltonians based on arbitrary sets of internal coordinates and axis embeddings. An efficient and general procedure is given that allows employing the Eckart embedding with arbitrary polyatomic Hamiltonians through a fully numerical approach. RRD tables formed by projecting rotational-vibrational wave functions into products of rigid-rotor basis functions and previously determined vibrational eigenstates yield rigid-rotor labels for rovibrational eigenstates by selecting the largest overlap. Embedding-dependent RRD analyses are performed, up to high energies and rotational excitations, for the H(2) (16)O isotopologue of the water molecule. Irrespective of the embedding chosen, the RRD procedure proves effective in providing unambiguous rotational assignments at low energies and J values. Rotational labeling of rovibrational states of H(2) (16)O proves to be increasingly difficult beyond about 10,000 cm(-1), close to the barrier to linearity of the water molecule. For medium energies and excitations the Eckart embedding yields the largest RRD coefficients, thus providing the largest number of unambiguous rotational labels.

Mechanisms of SN2 reactions: insights from a nearside/farside analysis.

PubMed

Hennig, Carsten; Schmatz, Stefan

2015-10-28

A nearside/farside analysis of differential cross sections has been performed for the complex-forming SN2 reaction Cl(-) + CH3Br → ClCH3 + Br(-). It is shown that for low rotational quantum numbers a direct "nearside" reaction mechanism plays an important role and leads to anisotropic differential cross sections. For high rotational quantum numbers, indirect mechanisms via a long-lived intermediate complex are prevalent (independent of a nearside/farside configuration), leading to isotropic cross sections. Quantum mechanical interference can be significant at specific energies or angles. Averaging over energies and angles reveals that the nearside/farside decomposition in a semiclassical interpretation can reasonably account for the analysis of the reaction mechanism.

A New Method for Nonlinear and Nonstationary Time Series Analysis and Its Application to the Earthquake and Building Response Records

NASA Technical Reports Server (NTRS)

Huang, Norden E.

1999-01-01

A new method for analyzing nonlinear and nonstationary data has been developed. The key part of the method is the Empirical Mode Decomposition method with which any complicated data set can be decomposed into a finite and often small number of Intrinsic Mode Functions (IMF). An IMF is defined as any function having the same numbers of zero-crossing and extrema, and also having symmetric envelopes defined by the local maxima and minima respectively. The IMF also admits well-behaved Hilbert transform. This decomposition method is adaptive, and, therefore, highly efficient. Since the decomposition is based on the local characteristic time scale of the data, it is applicable to nonlinear and nonstationary processes. With the Hilbert transform, the Intrinsic Mode Functions yield instantaneous frequencies as functions of time that give sharp identifications of imbedded structures. The final presentation of the results is an energy-frequency-time distribution, designated as the Hilbert Spectrum, Example of application of this method to earthquake and building response will be given. The results indicate those low frequency components, totally missed by the Fourier analysis, are clearly identified by the new method. Comparisons with Wavelet and window Fourier analysis show the new method offers much better temporal and frequency resolutions.

Empirical projection-based basis-component decomposition method

NASA Astrophysics Data System (ADS)

Brendel, Bernhard; Roessl, Ewald; Schlomka, Jens-Peter; Proksa, Roland

2009-02-01

Advances in the development of semiconductor based, photon-counting x-ray detectors stimulate research in the domain of energy-resolving pre-clinical and clinical computed tomography (CT). For counting detectors acquiring x-ray attenuation in at least three different energy windows, an extended basis component decomposition can be performed in which in addition to the conventional approach of Alvarez and Macovski a third basis component is introduced, e.g., a gadolinium based CT contrast material. After the decomposition of the measured projection data into the basis component projections, conventional filtered-backprojection reconstruction is performed to obtain the basis-component images. In recent work, this basis component decomposition was obtained by maximizing the likelihood-function of the measurements. This procedure is time consuming and often unstable for excessively noisy data or low intrinsic energy resolution of the detector. Therefore, alternative procedures are of interest. Here, we introduce a generalization of the idea of empirical dual-energy processing published by Stenner et al. to multi-energy, photon-counting CT raw data. Instead of working in the image-domain, we use prior spectral knowledge about the acquisition system (tube spectra, bin sensitivities) to parameterize the line-integrals of the basis component decomposition directly in the projection domain. We compare this empirical approach with the maximum-likelihood (ML) approach considering image noise and image bias (artifacts) and see that only moderate noise increase is to be expected for small bias in the empirical approach. Given the drastic reduction of pre-processing time, the empirical approach is considered a viable alternative to the ML approach.

Effect of urea additive on the thermal decomposition kinetics of flame retardant greige cotton nonwoven fabric

Treesearch

Sunghyun Nam; Brian D. Condon; Robert H. White; Qi Zhao; Fei Yao; Michael Santiago Cintrón

2012-01-01

Urea is well known to have a synergistic action with phosphorus-based flame retardants (FRs) in enhancing the FR performance of cellulosic materials, but the effect of urea on the thermal decomposition kinetics has not been thoroughly studied. In this study, the activation energy (Ea) for the thermal decomposition of greige...

Activation Strain Analysis of SN2 Reactions at C, N, O, and F Centers

PubMed Central

2017-01-01

Fundamental principles that determine chemical reactivity and reaction mechanisms are the very foundation of chemistry and many related fields of science. Bimolecular nucleophilic substitutions (SN2) are among the most common and therefore most important reaction types. In this report, we examine the trends in the SN2 reactions with respect to increasing electronegativity of the reaction center by comparing the well-studied backside SN2 Cl– + CH3Cl with similar Cl– substitutions on the isoelectronic series with the second period elements N, O, and F in place of C. Relativistic (ZORA) DFT calculations are used to construct the gas phase reaction potential energy surfaces (PES), and activation strain analysis, which allows decomposition of the PES into the geometrical strain and interaction energy, is employed to analyze the observed trends. We find that SN2@N and SN2@O have similar PES to the prototypical SN2@C, with the well-defined reaction complex (RC) local minima and a central barrier, but all stationary points are, respectively, increasingly stable in energy. The SN2@F, by contrast, exhibits only a single-well PES with no barrier. Using the activation strain model, we show that the trends are due to the interaction energy and originate mainly from the decreasing energy of the empty acceptor orbital (σ*A–Cl) on the reaction center A in the order of C, N, O, and F. The decreasing steric congestion around the central atom is also a likely contributor to this trend. Additional decomposition of the interaction energy using Kohn–Sham molecular orbital (KS-MO) theory provides further support for this explanation, as well as suggesting electrostatic energy as the primary reason for the distinct single-well PES profile for the FCl reaction. PMID:28045531

Activation Strain Analysis of SN2 Reactions at C, N, O, and F Centers.

PubMed

Kubelka, Jan; Bickelhaupt, F Matthias

2017-02-02

Fundamental principles that determine chemical reactivity and reaction mechanisms are the very foundation of chemistry and many related fields of science. Bimolecular nucleophilic substitutions (S N 2) are among the most common and therefore most important reaction types. In this report, we examine the trends in the S N 2 reactions with respect to increasing electronegativity of the reaction center by comparing the well-studied backside S N 2 Cl - + CH 3 Cl with similar Cl - substitutions on the isoelectronic series with the second period elements N, O, and F in place of C. Relativistic (ZORA) DFT calculations are used to construct the gas phase reaction potential energy surfaces (PES), and activation strain analysis, which allows decomposition of the PES into the geometrical strain and interaction energy, is employed to analyze the observed trends. We find that S N 2@N and S N 2@O have similar PES to the prototypical S N 2@C, with the well-defined reaction complex (RC) local minima and a central barrier, but all stationary points are, respectively, increasingly stable in energy. The S N 2@F, by contrast, exhibits only a single-well PES with no barrier. Using the activation strain model, we show that the trends are due to the interaction energy and originate mainly from the decreasing energy of the empty acceptor orbital (σ* A-Cl ) on the reaction center A in the order of C, N, O, and F. The decreasing steric congestion around the central atom is also a likely contributor to this trend. Additional decomposition of the interaction energy using Kohn-Sham molecular orbital (KS-MO) theory provides further support for this explanation, as well as suggesting electrostatic energy as the primary reason for the distinct single-well PES profile for the FCl reaction.

Catalytic decomposition of nitrous oxide monopropellant for hybrid motor ignition

NASA Astrophysics Data System (ADS)

Wilson, Matthew

Nitrous oxide (N2O) is an inexpensive and readily available non-toxic rocket motor oxidizer. It is the most commonly used oxidizer for hybrid bipropellant rocket systems, and several bipropellant liquid rocket designs have also used nitrous oxide. In liquid form, N2O is highly stable, but in vapor form it has the potential to decompose exothermically, releasing up to 1865 Joules per gram of vapor as it dissociates into nitrogen and oxygen. Consequently, it has long been considered as a potential "green" replacement for existing highly toxic and dangerous monopropellants. This project investigates the feasibility of using the nitrous oxide decomposition reaction as a monopropellant energy source for igniting liquid bipropellant and hybrid rockets that already use nitrous oxide as the primary oxidizer. Because nitrous oxide is such a stable propellant, the energy barrier to dissociation is quite high; normal thermal decomposition of the vapor phase does not occur until temperatures are above 800 C. The use of a ruthenium catalyst decreases the activation energy for this reaction to allow rapid decomposition below 400 C. This research investigates the design for a prototype device that channels the energy of dissociation to ignite a laboratory scale hybrid rocket motor.

Effect of CaO on the selectivity of N2O decomposition products: A combined experimental and DFT study

NASA Astrophysics Data System (ADS)

Wu, Lingnan; Hu, Xiaoying; Qin, Wu; Gao, Pan; Dong, Changqing; Yang, Yongping

2016-09-01

The effect of CaO on N2O decomposition and the selectivity of its decomposition products (NO and N2) was investigated using a fixed-bed flow reactor with varying temperatures from 317 °C to 947 °C. The selectivity of NO from CaO-catalyzed N2O decomposition is much lower than the N2 selectivity with the N2/NO products ratio greater than 12.1. Compared to N2O homogeneous decomposition with the minimum N2/NO products ratio of 6.2 at 718 °C, CaO also decreases the NO selectivity from 718 °C to 947 °C. Density functional theory calculations provide possible N2O decomposition routes on the CaO (1 0 0) surface considering both N2 and NO as N2O decomposition products. The N2 formation route is more favorable than the NO formation route in terms of energy barrier and reaction energy, and NO formation on the CaO (1 0 0) surface is likely to proceed via N2O + Osurf2- → N2 + O2 , surf2- and N2O + O2 , surf2- → 2NO + Osurf2-.

Eigenvector decomposition of full-spectrum x-ray computed tomography.

PubMed

Gonzales, Brian J; Lalush, David S

2012-03-07

Energy-discriminated x-ray computed tomography (CT) data were projected onto a set of basis functions to suppress the noise in filtered back-projection (FBP) reconstructions. The x-ray CT data were acquired using a novel x-ray system which incorporated a single-pixel photon-counting x-ray detector to measure the x-ray spectrum for each projection ray. A matrix of the spectral response of different materials was decomposed using eigenvalue decomposition to form the basis functions. Projection of FBP onto basis functions created a de facto image segmentation of multiple contrast agents. Final reconstructions showed significant noise suppression while preserving important energy-axis data. The noise suppression was demonstrated by a marked improvement in the signal-to-noise ratio (SNR) along the energy axis for multiple regions of interest in the reconstructed images. Basis functions used on a more coarsely sampled energy axis still showed an improved SNR. We conclude that the noise-resolution trade off along the energy axis was significantly improved using the eigenvalue decomposition basis functions.

Possibility of H2O2 decomposition in thin liquid films on Mars

NASA Astrophysics Data System (ADS)

Kereszturi, Akos; Gobi, Sandor

2014-11-01

In this work the pathways and possibilities of H2O2 decomposition on Mars in microscopic liquid interfacial water were analyzed by kinetic calculations. Thermal and photochemical driven decomposition, just like processes catalyzed by various metal oxides, is too slow compared to the annual duration while such microscopic liquid layers exist on Mars today, to produce substantial decomposition. The most effective analyzed process is catalyzed by Fe ions, which could decompose H2O2 under pH<4.5 with a half life of 1-2 days. This process might be important during volcanically influenced periods when sulfur release produces acidic pH, and rotational axis tilt change driven climatic changes also influence the volatile circulation and spatial occurrence just like the duration of thin liquid layer. Under current conditions, using the value of 200 K as the temperature in interfacial water (at the southern hemisphere), and applying Phoenix lander's wet chemistry laboratory results, the pH is not favorable for Fe mobility and this kind of decomposition. Despite current conditions (especially pH) being unfavorable for H2O2 decomposition, microscopic scale interfacial liquid water still might support the process. By the reaction called heterogeneous catalysis, without acidic pH and mobile Fe, but with minerals surfaces containing Fe decomposition of H2O2 with half life of 20 days can happen. This duration is still longer but not several orders than the existence of springtime interfacial liquid water on Mars today. This estimation is relevant for activation energy controlled reaction rates. The other main parameter that may influence the reaction rate is the diffusion speed. Although the available tests and theoretical calculations do not provide firm values for the diffusion speed in such a “2-dimensional” environment, using relevant estimations this parameter in the interfacial liquid layer is smaller than in bulk water. But the 20 days' duration mentioned above is still relevant, as the activation energy driven reaction rate is the main limiting factor in the decomposition and not the diffusion speed. The duration of dozen(s) days is still longer but not with orders of magnitude than the expected duration for the existence of springtime interfacial liquid water on Mars today. The results suggest such decomposition may happen today, however, because of our limited knowledge on chemical processes in thin interfacial liquid layers, this possibility waits for confirmation - and also points to the importance of conducting laboratory tests to validate the possible process. Although some tests were already realized for diffusion in an almost 2-dimensional liquid, the same is not true for activation energy, where only the value from the “normal” measurements was applied. Even if H2O2 decomposition is too slow today, the analysis of such a process is important, as under volcanic influence more effective decomposition might take place in thin interfacial liquids close to the climate of today if released sulfur produces pH<4.5. Large quantity and widespread occurrence of bulk liquid phase are not expected in the Amazonian period, but interfacial liquid water probably appeared regularly, and its locations, especially during volcanically active periods, might make certain sites than others more interesting for astrobiology with the lower concentration of oxidizing H2O2.

Decomposition of L a 2 – x S r x Cu O 4 into several L a 2 O 3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

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

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet

Here, we report the decomposition of La 2–xSr xCuO 4 into La 2O 3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150°C and is considerably expedited in the temperature range of 350°C–450°C. Two major resultant solid phases are identified as metallic Cu and La 2O 3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, La 2O 3 phases are further identified to be derivatives of a fluorite structure—fluorite,more » pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and LaM 4,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and La 2O 3 phases remain unchanged after cooling to room temperature.« less

Decomposition of L a 2 – x S r x Cu O 4 into several L a 2 O 3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

DOE PAGES

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet; ...

2018-05-15

Here, we report the decomposition of La 2–xSr xCuO 4 into La 2O 3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150°C and is considerably expedited in the temperature range of 350°C–450°C. Two major resultant solid phases are identified as metallic Cu and La 2O 3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, La 2O 3 phases are further identified to be derivatives of a fluorite structure—fluorite,more » pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and LaM 4,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and La 2O 3 phases remain unchanged after cooling to room temperature.« less

Ab initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5-Dinitrobiuret

DTIC Science & Technology

2016-03-14

Journal Article 3. DATES COVERED (From - To) Feb 2015-May 2015 4. TITLE AND SUBTITLE Ab initio Kinetics and Thermal Decomposition Mechanism of 5a...tetrazole-free, nitrogen-rich, energetic compounds. For the first time, the thermal decomposition mechanisms of MNB and DNB have been investigated...potential energy surfaces for thermal decomposition of MNB and DNB were characterized at the RCCSD(T)/cc-pV∞Z//M06-2X/aug- cc-pVTZ level of theory

A Review of Study on Thermal Energy Transport System by Synthesis and Decomposition Reactions of Methanol

NASA Astrophysics Data System (ADS)

Liu, Qiusheng; Yabe, Akira; Kajiyama, Shiro; Fukuda, Katsuya

The study on thermal energy transport system by synthesis and decomposition reactions of methanol was reviewed. To promote energy conservation and global environment protection, a two-step liquid-phase methanol synthesis process, which starts with carbonylation of methanol to methyl formate, then followed by the hydrogenolysis of the formate, was studied to recover wasted or unused discharged heat from industrial sources for the thermal energy demands of residential and commercial areas by chemical reactions. The research and development of the system were focused on the following three points. (1) Development of low-temperature decomposition and synthetic catalysts, (2) Development of liquid phase reactor (heat exchanger accompanying chemical reaction), (3) Simulation of the energy transport efficiency of entire system which contains heat recovery and supply sections. As the result of the development of catalyst, promising catalysts which agree with the development purposes for the methyl formate decomposition reaction and the synthetic reaction are being developed though some studies remain for the methanol decomposition and synthetic reactions. In the fundamental development of liquid phase reactor, the solubilities of CO and H2 gases in methanol and methyl formate were measured by the method of total pressure decrease due to absorption under pressures up to 1500kPa and temperatures up to 140°C. The diffusivity of CO gas in methanol was determined by measuring the diameter and solution time of single CO bubbles in methanol. The chemical reaction rate of methanol synthesis by hydrogenolysis of methyl formate was measured using a plate-type of Raney copper catalyst in a reactor with rectangular channel and in an autoclave reactor. The reaction characteristics were investigated by carrying out the experiments at various temperatures, flow rates and at various catalyst development conditions. We focused on the effect of Raney copper catalyst thickness on the liquid-phase chemical reaction by varying the development time of the catalyst. Investigation results of the catalyst such as surface area, pore radius, lattice size, and photographs of scanning electron microscope (SEM) were also given. In the simulation of energy transport efficiency of this system, by simulating the energy transfer system using two-step liquid phase methanol decomposition and synthetic reactions, and comparing with the technology so far, it can be expected that an innovative energy transfer system is possible to realize.

S-matrix decomposition, natural reaction channels, and the quantum transition state approach to reactive scattering

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

Manthe, Uwe, E-mail: uwe.manthe@uni-bielefeld.de; Ellerbrock, Roman, E-mail: roman.ellerbrock@uni-bielefeld.de

2016-05-28

A new approach for the quantum-state resolved analysis of polyatomic reactions is introduced. Based on the singular value decomposition of the S-matrix, energy-dependent natural reaction channels and natural reaction probabilities are defined. It is shown that the natural reaction probabilities are equal to the eigenvalues of the reaction probability operator [U. Manthe and W. H. Miller, J. Chem. Phys. 99, 3411 (1993)]. Consequently, the natural reaction channels can be interpreted as uniquely defined pathways through the transition state of the reaction. The analysis can efficiently be combined with reactive scattering calculations based on the propagation of thermal flux eigenstates. Inmore » contrast to a decomposition based straightforwardly on thermal flux eigenstates, it does not depend on the choice of the dividing surface separating reactants from products. The new approach is illustrated studying a prototypical example, the H + CH{sub 4} → H{sub 2} + CH{sub 3} reaction. The natural reaction probabilities and the contributions of the different vibrational states of the methyl product to the natural reaction channels are calculated and discussed. The relation between the thermal flux eigenstates and the natural reaction channels is studied in detail.« less

Objective research of auscultation signals in Traditional Chinese Medicine based on wavelet packet energy and support vector machine.

PubMed

Yan, Jianjun; Shen, Xiaojing; Wang, Yiqin; Li, Fufeng; Xia, Chunming; Guo, Rui; Chen, Chunfeng; Shen, Qingwei

2010-01-01

This study aims at utilising Wavelet Packet Transform (WPT) and Support Vector Machine (SVM) algorithm to make objective analysis and quantitative research for the auscultation in Traditional Chinese Medicine (TCM) diagnosis. First, Wavelet Packet Decomposition (WPD) at level 6 was employed to split more elaborate frequency bands of the auscultation signals. Then statistic analysis was made based on the extracted Wavelet Packet Energy (WPE) features from WPD coefficients. Furthermore, the pattern recognition was used to distinguish mixed subjects' statistical feature values of sample groups through SVM. Finally, the experimental results showed that the classification accuracies were at a high level.

Generalized first-order kinetic model for biosolids decomposition and oxidation during hydrothermal treatment.

PubMed

Shanableh, A

2005-01-01

The main objective of this study was to develop generalized first-order kinetic models to represent hydrothermal decomposition and oxidation of biosolids within a wide range of temperatures (200-450 degrees C). A lumping approach was used in which oxidation of the various organic ingredients was characterized by the chemical oxygen demand (COD), and decomposition was characterized by the particulate (i.e., nonfilterable) chemical oxygen demand (PCOD). Using the Arrhenius equation (k = k(o)e(-Ea/RT)), activation energy (Ea) levels were derived from 42 continuous-flow hydrothermal treatment experiments conducted at temperatures in the range of 200-450 degrees C. Using predetermined values for k(o) in the Arrhenius equation, the activation energies of the various organic ingredients were separated into 42 values for oxidation and a similar number for decomposition. The activation energy values were then classified into levels representing the relative ease at which the organic ingredients of the biosolids were oxidized or decomposed. The resulting simple first-order kinetic models adequately represented, within the experimental data range, hydrothermal decomposition of the organic particles as measured by PCOD and oxidation of the organic content as measured by COD. The modeling approach presented in the paper provide a simple and general framework suitable for assessing the relative reaction rates of the various organic ingredients of biosolids.

Spectral Diffusion: An Algorithm for Robust Material Decomposition of Spectral CT Data

PubMed Central

Clark, Darin P.; Badea, Cristian T.

2014-01-01

Clinical successes with dual energy CT, aggressive development of energy discriminating x-ray detectors, and novel, target-specific, nanoparticle contrast agents promise to establish spectral CT as a powerful functional imaging modality. Common to all of these applications is the need for a material decomposition algorithm which is robust in the presence of noise. Here, we develop such an algorithm which uses spectrally joint, piece-wise constant kernel regression and the split Bregman method to iteratively solve for a material decomposition which is gradient sparse, quantitatively accurate, and minimally biased. We call this algorithm spectral diffusion because it integrates structural information from multiple spectral channels and their corresponding material decompositions within the framework of diffusion-like denoising algorithms (e.g. anisotropic diffusion, total variation, bilateral filtration). Using a 3D, digital bar phantom and a material sensitivity matrix calibrated for use with a polychromatic x-ray source, we quantify the limits of detectability (CNR = 5) afforded by spectral diffusion in the triple-energy material decomposition of iodine (3.1 mg/mL), gold (0.9 mg/mL), and gadolinium (2.9 mg/mL) concentrations. We then apply spectral diffusion to the in vivo separation of these three materials in the mouse kidneys, liver, and spleen. PMID:25296173

Spectral diffusion: an algorithm for robust material decomposition of spectral CT data.

PubMed

Clark, Darin P; Badea, Cristian T

2014-11-07

Clinical successes with dual energy CT, aggressive development of energy discriminating x-ray detectors, and novel, target-specific, nanoparticle contrast agents promise to establish spectral CT as a powerful functional imaging modality. Common to all of these applications is the need for a material decomposition algorithm which is robust in the presence of noise. Here, we develop such an algorithm which uses spectrally joint, piecewise constant kernel regression and the split Bregman method to iteratively solve for a material decomposition which is gradient sparse, quantitatively accurate, and minimally biased. We call this algorithm spectral diffusion because it integrates structural information from multiple spectral channels and their corresponding material decompositions within the framework of diffusion-like denoising algorithms (e.g. anisotropic diffusion, total variation, bilateral filtration). Using a 3D, digital bar phantom and a material sensitivity matrix calibrated for use with a polychromatic x-ray source, we quantify the limits of detectability (CNR = 5) afforded by spectral diffusion in the triple-energy material decomposition of iodine (3.1 mg mL(-1)), gold (0.9 mg mL(-1)), and gadolinium (2.9 mg mL(-1)) concentrations. We then apply spectral diffusion to the in vivo separation of these three materials in the mouse kidneys, liver, and spleen.

TG-MS analysis and kinetic study for thermal decomposition of six representative components of municipal solid waste under steam atmosphere.

PubMed

Zhang, Jinzhi; Chen, Tianju; Wu, Jingli; Wu, Jinhu

2015-09-01

Thermal decomposition of six representative components of municipal solid waste (MSW, including lignin, printing paper, cotton, rubber, polyvinyl chloride (PVC) and cabbage) was investigated by thermogravimetric-mass spectroscopy (TG-MS) under steam atmosphere. Compared with TG and derivative thermogravimetric (DTG) curves under N2 atmosphere, thermal decomposition of MSW components under steam atmosphere was divided into pyrolysis and gasification stages. In the pyrolysis stage, the shapes of TG and DTG curves under steam atmosphere were almost the same with those under N2 atmosphere. In the gasification stage, the presence of steam led to a greater mass loss because of the steam partial oxidation of char residue. The evolution profiles of H2, CH4, CO and CO2 were well consistent with DTG curves in terms of appearance of peaks and relevant stages in the whole temperature range, and the steam partial oxidation of char residue promoted the generation of more gas products in high temperature range. The multi-Gaussian distributed activation energy model (DAEM) was proved plausible to describe thermal decomposition behaviours of MSW components under steam atmosphere. Copyright © 2015 Elsevier Ltd. All rights reserved.

In situ characterization of the decomposition behavior of Mg(BH4)2 by X-ray Raman scattering spectroscopy.

PubMed

Sahle, Christoph J; Kujawski, Simon; Remhof, Arndt; Yan, Yigang; Stadie, Nicholas P; Al-Zein, Ali; Tolan, Metin; Huotari, Simo; Krisch, Michael; Sternemann, Christian

2016-02-21

We present an in situ study of the thermal decomposition of Mg(BH4)2 in a hydrogen atmosphere of up to 4 bar and up to 500 °C using X-ray Raman scattering spectroscopy at the boron K-edge and the magnesium L2,3-edges. The combination of the fingerprinting analysis of both edges yields detailed quantitative information on the reaction products during decomposition, an issue of crucial importance in determining whether Mg(BH4)2 can be used as a next-generation hydrogen storage material. This work reveals the formation of reaction intermediate(s) at 300 °C, accompanied by a significant hydrogen release without the occurrence of stable boron compounds such as amorphous boron or MgB12H12. At temperatures between 300 °C and 400 °C, further hydrogen release proceeds via the formation of higher boranes and crystalline MgH2. Above 400 °C, decomposition into the constituting elements takes place. Therefore, at moderate temperatures, Mg(BH4)2 is shown to be a promising high-density hydrogen storage material with great potential for reversible energy storage applications.

Direct and Indirect Effects of UV-B Exposure on Litter Decomposition: A Meta-Analysis

PubMed Central

Song, Xinzhang; Peng, Changhui; Jiang, Hong; Zhu, Qiuan; Wang, Weifeng

2013-01-01

Ultraviolet-B (UV-B) exposure in the course of litter decomposition may have a direct effect on decomposition rates via changing states of photodegradation or decomposer constitution in litter while UV-B exposure during growth periods may alter chemical compositions and physical properties of plants. Consequently, these changes will indirectly affect subsequent litter decomposition processes in soil. Although studies are available on both the positive and negative effects (including no observable effects) of UV-B exposure on litter decomposition, a comprehensive analysis leading to an adequate understanding remains unresolved. Using data from 93 studies across six biomes, this introductory meta-analysis found that elevated UV-B directly increased litter decomposition rates by 7% and indirectly by 12% while attenuated UV-B directly decreased litter decomposition rates by 23% and indirectly increased litter decomposition rates by 7%. However, neither positive nor negative effects were statistically significant. Woody plant litter decomposition seemed more sensitive to UV-B than herbaceous plant litter except under conditions of indirect effects of elevated UV-B. Furthermore, levels of UV-B intensity significantly affected litter decomposition response to UV-B (P<0.05). UV-B effects on litter decomposition were to a large degree compounded by climatic factors (e.g., MAP and MAT) (P<0.05) and litter chemistry (e.g., lignin content) (P<0.01). Results suggest these factors likely have a bearing on masking the important role of UV-B on litter decomposition. No significant differences in UV-B effects on litter decomposition were found between study types (field experiment vs. laboratory incubation), litter forms (leaf vs. needle), and decay duration. Indirect effects of elevated UV-B on litter decomposition significantly increased with decay duration (P<0.001). Additionally, relatively small changes in UV-B exposure intensity (30%) had significant direct effects on litter decomposition (P<0.05). The intent of this meta-analysis was to improve our understanding of the overall effects of UV-B on litter decomposition. PMID:23818993

New mechanism for autocatalytic decomposition of H2CO3 in the vapor phase.

PubMed

Ghoshal, Sourav; Hazra, Montu K

2014-04-03

In this article, we present high level ab initio calculations investigating the energetics of a new autocatalytic decomposition mechanism for carbonic acid (H2CO3) in the vapor phase. The calculation have been performed at the MP2 level of theory in conjunction with aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(3df,3pd) basis sets as well as at the CCSD(T)/aug-cc-pVTZ level. The present study suggests that this new decomposition mechanism is effectively a near-barrierless process at room temperature and makes vapor phase of H2CO3 unstable even in the absence of water molecules. Our calculation at the MP2/aug-cc-pVTZ level predicts that the effective barrier, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, is nearly zero for the autocatalytic decomposition mechanism. The results at the CCSD(T)/aug-cc-pVTZ level of calculations suggest that the effective barrier, as defined above, is sensitive to some extent to the levels of calculations used, nevertheless, we find that the effective barrier height predicted at the CCSD(T)/aug-cc-pVTZ level is very small or in other words the autocatalytic decomposition mechanism presented in this work is a near-barrierless process as mentioned above. Thus, we suggest that this new autocatalytic decomposition mechanism has to be considered as the primary mechanism for the decomposition of carbonic acid, especially at its source, where the vapor phase concentration of H2CO3 molecules reaches its highest levels.

Effect of dry torrefaction on kinetics of catalytic pyrolysis of sugarcane bagasse

NASA Astrophysics Data System (ADS)

Daniyanto, Sutijan, Deendarlianto, Budiman, Arief

2015-12-01

Decreasing world reserve of fossil resources (i.e. petroleum oil, coal and natural gas) encourage discovery of renewable resources as subtitute for fossil resources. Biomass is one of the main natural renewable resources which is promising resource as alternate resources to meet the world's energy needs and raw material to produce chemical platform. Conversion of biomass, as source of energy, fuel and biochemical, is conducted using thermochemical process such as pyrolysis-gasification process. Pyrolysis step is an important step in the mechanism of pyrolysis - gasification of biomass. The objective of this study is to obtain the kinetic reaction of catalytic pyrolysis of dry torrified sugarcane bagasse which used Ca and Mg as catalysts. The model of kinetic reaction is interpreted using model n-order of single reaction equation of biomass. Rate of catalytic pyrolysis reaction depends on the weight of converted biomass into char and volatile matters. Based on TG/DTA analysis, rate of pyrolysis reaction is influenced by the composition of biomass (i.e. hemicellulose, cellulose and lignin) and inorganic component especially alkali and alkaline earth metallic (AAEM). From this study, it has found two equations rate of reaction of catalytic pyrolysis in sugarcane bagasse using catalysts Ca and Mg. First equation is equation of pyrolysis reaction in rapid zone of decomposition and the second equation is slow zone of decomposition. Value of order reaction for rapid decomposition is n > 1 and for slow decomposition is n<1. Constant and order of reactions for catalytic pyrolysis of dry-torrified sugarcane bagasse with presence of Ca tend to higher than that's of presence of Mg.

Comparative analysis of polychlorinated biphenyl decomposition processes in air or argon (+oxygen) thermal plasma.

PubMed

Kostic, Z G; Stefanovic, P L; Pavlović, P B

2000-07-10

Thermal plasmas may solve one of the biggest toxic waste disposal problems. The disposal of polychlorinated biphenyls (PCBs) is a long standing problem which will get worse in the coming years, when 180000 tons of PCB-containing wastes are expected to accumulate in Europe (Hot ions break down toxic chemicals, New Scientist, 16 April 1987, p. 24.). The combustion of PCBs in ordinary incinerators (at temperature T approximately 1100 K, as measured near the inner wall of the combustion chamber (European Parliament and Council Directive on Incineration of Waste (COM/99/330), Europe energy, 543, Sept. 17, 1999, 1-23.)) can cause more problems than it solves, because highly toxic dioxins and dibenzofurans are formed if the combustion temperature is too low (T<1400 K). The paper presents a thermodynamic consideration and comparative analysis of PCB decomposition processes in air or argon (+oxygen) thermal plasmas.

Resident Load Influence Analysis Method for Price Based on Non-intrusive Load Monitoring and Decomposition Data

NASA Astrophysics Data System (ADS)

Jiang, Wenqian; Zeng, Bo; Yang, Zhou; Li, Gang

2018-01-01

In the non-invasive load monitoring mode, the load decomposition can reflect the running state of each load, which will help the user reduce unnecessary energy costs. With the demand side management measures of time of using price, a resident load influence analysis method for time of using price (TOU) based on non-intrusive load monitoring data are proposed in the paper. Relying on the current signal of the resident load classification, the user equipment type, and different time series of self-elasticity and cross-elasticity of the situation could be obtained. Through the actual household load data test with the impact of TOU, part of the equipment will be transferred to the working hours, and users in the peak price of electricity has been reduced, and in the electricity at the time of the increase Electrical equipment, with a certain regularity.

[Decomposition model of energy-related carbon emissions in tertiary industry for China].

PubMed

Lu, Yuan-Qing; Shi, Jun

2012-07-01

Tertiary industry has been developed in recent years. And it is very important to find the factors influenced the energy-related carbon emissions in tertiary industry. A decomposition model of energy-related carbon emissions for China is set up by adopting logarithmic mean weight Divisia method based on the identity of carbon emissions. The model is adopted to analyze the influence of energy structure, energy efficiency, tertiary industry structure and economic output to energy-related carbon emissions in China from 2000 to 2009. Results show that the contribution rate of economic output and energy structure to energy-related carbon emissions increases year by year. Either is the contribution rate of energy efficiency or the tertiary industry restraining to energy-related carbon emissions. However, the restrain effect is weakening.

Theoretical study of the decomposition pathways and products of C5- perfluorinated ketone (C5 PFK)

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

Fu, Yuwei; Wang, Xiaohua, E-mail: xhw@mail.xjtu.edu.cn, E-mail: mzrong@mail.xjtu.edu.cn; Li, Xi

Due to the high global warming potential (GWP) and increasing environmental concerns, efforts on searching the alternative gases to SF{sub 6}, which is predominantly used as insulating and interrupting medium in high-voltage equipment, have become a hot topic in recent decades. Overcoming the drawbacks of the existing candidate gases, C5- perfluorinated ketone (C5 PFK) was reported as a promising gas with remarkable insulation capacity and the low GWP of approximately 1. Experimental measurements of the dielectric strength of this novel gas and its mixtures have been carried out, but the chemical decomposition pathways and products of C5 PFK during breakdownmore » are still unknown, which are the essential factors in evaluating the electric strength of this gas in high-voltage equipment. Therefore, this paper is devoted to exploring all the possible decomposition pathways and species of C5 PFK by density functional theory (DFT). The structural optimizations, vibrational frequency calculations and energy calculations of the species involved in a considered pathway were carried out with DFT-(U)B3LYP/6-311G(d,p) method. Detailed potential energy surface was then investigated thoroughly by the same method. Lastly, six decomposition pathways of C5 PFK decomposition involving fission reactions and the reactions with a transition states were obtained. Important intermediate products were also determined. Among all the pathways studied, the favorable decomposition reactions of C5 PFK were found, involving C-C bond ruptures producing Ia and Ib in pathway I, followed by subsequent C-C bond ruptures and internal F atom transfers in the decomposition of Ia and Ib presented in pathways II + III and IV + V, respectively. Possible routes were pointed out in pathway III and lead to the decomposition of IIa, which is the main intermediate product found in pathway II of Ia decomposition. We also investigated the decomposition of Ib, which can undergo unimolecular reactions to give the formation of IV a, IV b and products of CF{sub 3} + CF-CF{sub 3} in pathway IV. Although IV a is dominant to a lesser extent due to its relative high energy barrier, its complicated decomposition pathway V was also studied and CF{sub 3}, C = CF{sub 2} as well as C-CF{sub 3} species were found as the ultimate products. To complete the decomposition of C5 PFK, pathway V I of Ic decomposition was fully explored and the final products were obtained. Therefore, the integrate decomposition scheme of C5 PFK was proposed, which contains six pathways and forty-eight species (including all the reactants, products and transition states). This work is hopeful to lay a theoretical basis for the insulating properties of C5 PFK.« less

Quantization of liver tissue in dual kVp computed tomography using linear discriminant analysis

NASA Astrophysics Data System (ADS)

Tkaczyk, J. Eric; Langan, David; Wu, Xiaoye; Xu, Daniel; Benson, Thomas; Pack, Jed D.; Schmitz, Andrea; Hara, Amy; Palicek, William; Licato, Paul; Leverentz, Jaynne

2009-02-01

Linear discriminate analysis (LDA) is applied to dual kVp CT and used for tissue characterization. The potential to quantitatively model both malignant and benign, hypo-intense liver lesions is evaluated by analysis of portal-phase, intravenous CT scan data obtained on human patients. Masses with an a priori classification are mapped to a distribution of points in basis material space. The degree of localization of tissue types in the material basis space is related to both quantum noise and real compositional differences. The density maps are analyzed with LDA and studied with system simulations to differentiate these factors. The discriminant analysis is formulated so as to incorporate the known statistical properties of the data. Effective kVp separation and mAs relates to precision of tissue localization. Bias in the material position is related to the degree of X-ray scatter and partial-volume effect. Experimental data and simulations demonstrate that for single energy (HU) imaging or image-based decomposition pixel values of water-like tissues depend on proximity to other iodine-filled bodies. Beam-hardening errors cause a shift in image value on the scale of that difference sought between in cancerous and cystic lessons. In contrast, projection-based decomposition or its equivalent when implemented on a carefully calibrated system can provide accurate data. On such a system, LDA may provide novel quantitative capabilities for tissue characterization in dual energy CT.

Structural, optical, electron paramagnetic, thermal and dielectric characterization of chalcopyrite.

PubMed

Prameena, B; Anbalagan, G; Gunasekaran, S; Ramkumaar, G R; Gowtham, B

2014-03-25

Chalcopyrite (CuFeS2) a variety of pyrite minerals was investigated through spectroscopic techniques and thermal analysis. The morphology and elemental analysis of the chalcopyrite have been done by high resolution SEM with EDAX. The lattice parameters were from the powder diffraction data (a=5.3003±0.0089 Å, c=10.3679±0.0289 Å; the volume of the unit cell=291.266 Å(3) with space group I42d (122)). The thermal decomposition behavior of chalcopyrite was studied by means of thermogravimetric analysis at three different heating rates 10, 15 and 20 °C/min. The values of effective activation energy (Ea), pre-exponential factor (ln A) for thermal decomposition have been measured at three different heating rates by employing Kissinger, Kim-Park and Flynn-Wall methods. Dielectric studies at different temperatures have also been carried out and it was found that both dielectric constant and dielectric loss decreases with the increase of frequency. Copyright © 2013 Elsevier B.V. All rights reserved.

Solid-state stability studies of 13-cis-retinoic acid and all-trans-retinoic acid using microcalorimetry and HPLC analysis.

PubMed

Tan, X; Meltzer, N; Lindebaum, S

1992-09-01

The solid-state stabilities of 13-cis-retinoic acid and all-trans-retinoic acid in the presence and absence of oxygen were investigated. The samples were first evaluated using microcalorimetry. The rate laws of different samples under different conditions were deduced from the shapes of the heat flow curves, and the activation energies of the reactions were determined from Arrhenius plots. Under an air atmosphere, the decomposition of 13-cis-retinoic acid is an autocatalytic reaction, while all-trans-retinoic acid undergoes a zero-order process. The degradation of the two compounds at a selected elevated temperature was also determined utilizing HPLC analysis. This technique confirmed the decomposition kinetics. Hence, their half-lives and shelf lives at room temperature could be calculated. Under a nitrogen atmosphere, the microcalorimetric experiment showed a first-order phenomenon for both samples, but HPLC analysis showed no degradation, suggesting that the two samples, in the absence of oxygen, undergo only a physical change.

Validating the performance of one-time decomposition for fMRI analysis using ICA with automatic target generation process.

PubMed

Yao, Shengnan; Zeng, Weiming; Wang, Nizhuan; Chen, Lei

2013-07-01

Independent component analysis (ICA) has been proven to be effective for functional magnetic resonance imaging (fMRI) data analysis. However, ICA decomposition requires to optimize the unmixing matrix iteratively whose initial values are generated randomly. Thus the randomness of the initialization leads to different ICA decomposition results. Therefore, just one-time decomposition for fMRI data analysis is not usually reliable. Under this circumstance, several methods about repeated decompositions with ICA (RDICA) were proposed to reveal the stability of ICA decomposition. Although utilizing RDICA has achieved satisfying results in validating the performance of ICA decomposition, RDICA cost much computing time. To mitigate the problem, in this paper, we propose a method, named ATGP-ICA, to do the fMRI data analysis. This method generates fixed initial values with automatic target generation process (ATGP) instead of being produced randomly. We performed experimental tests on both hybrid data and fMRI data to indicate the effectiveness of the new method and made a performance comparison of the traditional one-time decomposition with ICA (ODICA), RDICA and ATGP-ICA. The proposed method demonstrated that it not only could eliminate the randomness of ICA decomposition, but also could save much computing time compared to RDICA. Furthermore, the ROC (Receiver Operating Characteristic) power analysis also denoted the better signal reconstruction performance of ATGP-ICA than that of RDICA. Copyright © 2013 Elsevier Inc. All rights reserved.

A study of the effect of gamma and laser irradiation on the thermal, optical and structural properties of CR-39 nuclear track detector

NASA Astrophysics Data System (ADS)

Nouh, S. A.; Atta, M. R.; El-Melleegy, W. M.

2004-08-01

A comparative study of the effect of gamma and laser irradiation on the thermal, optical and structural properties of the CR-39 diglycol carbonate solid state nuclear track detector has been carried out. Samples from CR-39 polymer were classified into two main groups: the first group was irradiated by gamma rays with doses at levels between 20 and 300 kGy, whereas the second group was exposed to infrared laser radiation with energy fluences at levels between 0.71 and 8.53 J/cm(2). Non-isothermal studies were carried out using thermogravimetry, differential thermogravimetry and differential thermal analysis to obtain activation energy of decomposition and transition temperatures for the non-irradiated and all irradiated CR-39 samples. In addition, optical and structural property studies were performed on non-irradiated and irradiated CR-39 samples using refractive index and X-ray diffraction measurements. Variation in the onset temperature of decomposition T-o, activation energy of decomposition E-a, melting temperature T-m, refractive index n and the mass fraction of the amorphous phase after gamma and laser irradiation were studied. It was found that many changes in the thermal, optical and structural properties of the CR-39 polymer could be produced by gamma irradiation via degradation and cross-linking mechanisms. Also, the gamma dose has an advantage of increasing the correlation between thermal stability of the CR-39 polymer and bond formation created by the ionizing effect of gamma radiation. On the other hand, higher laser-energy fluences in the range 4.27-8.53 J/cm(2) decrease the melting temperature of the CR-39 polymer and this is most suitable for applications requiring molding of the polymer at lower temperatures.

Calculation of excitation energies from the CC2 linear response theory using Cholesky decomposition

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

Baudin, Pablo, E-mail: baudin.pablo@gmail.com; qLEAP – Center for Theoretical Chemistry, Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C; Marín, José Sánchez

2014-03-14

A new implementation of the approximate coupled cluster singles and doubles CC2 linear response model is reported. It employs a Cholesky decomposition of the two-electron integrals that significantly reduces the computational cost and the storage requirements of the method compared to standard implementations. Our algorithm also exploits a partitioning form of the CC2 equations which reduces the dimension of the problem and avoids the storage of doubles amplitudes. We present calculation of excitation energies of benzene using a hierarchy of basis sets and compare the results with conventional CC2 calculations. The reduction of the scaling is evaluated as well asmore » the effect of the Cholesky decomposition parameter on the quality of the results. The new algorithm is used to perform an extrapolation to complete basis set investigation on the spectroscopically interesting benzylallene conformers. A set of calculations on medium-sized molecules is carried out to check the dependence of the accuracy of the results on the decomposition thresholds. Moreover, CC2 singlet excitation energies of the free base porphin are also presented.« less

Density functional theory study of HfCl4, ZrCl4, and Al(CH3)3 decomposition on hydroxylated SiO2: Initial stage of high-k atomic layer deposition

NASA Astrophysics Data System (ADS)

Jeloaica, L.; Estève, A.; Djafari Rouhani, M.; Estève, D.

2003-07-01

The initial stage of atomic layer deposition of HfO2, ZrO2, and Al2O3 high-k films, i.e., the decomposition of HfCl4, ZrCl4, and Al(CH3)3 precursor molecules on an OH-terminated SiO2 surface, is investigated within density functional theory. The energy barriers are determined using artificial activation of vibrational normal modes. For all precursors, reaction proceeds through the formation of intermediate complexes that have equivalent formation energies (˜-0.45 eV), and results in HCl and CH4 formation with activation energies of 0.88, 0.91, and 1.04 eV for Hf, Zr, and Al based precursors, respectively. The reaction product of Al(CH3)3 decomposition is found to be more stable (by -1.45 eV) than the chemisorbed intermediate complex compared to the endothermic decomposition of HfCl4 and ZrCl4 chemisorbed precursors (0.26 and 0.29 eV, respectively).

Renewable energy in electric utility capacity planning: a decomposition approach with application to a Mexican utility

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

Staschus, K.

1985-01-01

In this dissertation, efficient algorithms for electric-utility capacity expansion planning with renewable energy are developed. The algorithms include a deterministic phase that quickly finds a near-optimal expansion plan using derating and a linearized approximation to the time-dependent availability of nondispatchable energy sources. A probabilistic second phase needs comparatively few computer-time consuming probabilistic simulation iterations to modify this solution towards the optimal expansion plan. For the deterministic first phase, two algorithms, based on a Lagrangian Dual decomposition and a Generalized Benders Decomposition, are developed. The probabilistic second phase uses a Generalized Benders Decomposition approach. Extensive computational tests of the algorithms aremore » reported. Among the deterministic algorithms, the one based on Lagrangian Duality proves fastest. The two-phase approach is shown to save up to 80% in computing time as compared to a purely probabilistic algorithm. The algorithms are applied to determine the optimal expansion plan for the Tijuana-Mexicali subsystem of the Mexican electric utility system. A strong recommendation to push conservation programs in the desert city of Mexicali results from this implementation.« less

Theoretical study of the decomposition mechanism of environmentally friendly insulating medium C3F7CN in the presence of H2O in a discharge

NASA Astrophysics Data System (ADS)

Zhang, Xiaoxing; Li, Yi; Xiao, Song; Tian, Shuangshuang; Deng, Zaitao; Tang, Ju

2017-08-01

C3F7CN has been the focus of the alternative gas research field over the past two years because of its excellent insulation properties and environmental characteristics. Experimental studies on its insulation performance have made many achievements. However, few studies on the formation mechanism of the decomposition components exist. A discussion of the decomposition characteristics of insulating media will provide guidance for scientific experimental research and the work that must be completed before further engineering application. In this study, the decomposition mechanism of C3F7CN in the presence of trace H2O under discharge was calculated based on the density functional theory and transition state theory. The reaction heat, Gibbs free energy, and activation energy of different decomposition pathways were investigated. The ionization parameters and toxicity of C3F7CN and various decomposition products were analyzed from the molecular structure perspective. The formation mechanism of the C3F7CN discharge decomposition components and the influence of trace water were evaluated. This paper confirms that C3F7CN has excellent decomposition characteristics, which provide theoretical support for later experiments and related engineering applications. However, the existence of trace water has a negative impact on C3F7CN’s insulation performance. Thus, strict trace water content standards should be developed to ensure dielectric insulation and the safety of maintenance personnel.

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.

Development of a New Methodology for Computing Surface Sensible Heat Fluxes using Thermal Imagery

NASA Astrophysics Data System (ADS)

Morrison, T. J.; Calaf, M.; Fernando, H. J.; Price, T. A.; Pardyjak, E.

2017-12-01

Current numerical weather predication models utilize similarity to characterize momentum, moisture, and heat fluxes. Such formulations are only valid under the ideal assumptions of spatial homogeneity, statistical stationary, and zero subsidence. However, recent surface temperature measurements from the Mountain Terrain Atmospheric Modeling and Observations (MATERHORN) Program on the Salt Flats of Utah's West desert, show that even under the most a priori ideal conditions, heterogeneity of the aforementioned variables exists. We present a new method to extract spatially-distributed measurements of surface sensible heat flux from thermal imagery. The approach consists of using a surface energy budget, where the ground heat flux is easily computed from limited measurements using a force-restore-type methodology, the latent heat fluxes are neglected, and the energy storage is computed using a lumped capacitance model. Preliminary validation of the method is presented using experimental data acquired from a nearby sonic anemometer during the MATERHORN campaign. Additional evaluation is required to confirm the method's validity. Further decomposition analysis of on-site instrumentation (thermal camera, cold-hotwire probes, and sonic anemometers) using Proper Orthogonal Decomposition (POD), and wavelet analysis, reveals time scale similarity between the flow and surface fluctuations.

A characterization of the two-step reaction mechanism of phenol decomposition by a Fenton reaction

NASA Astrophysics Data System (ADS)

Valdés, Cristian; Alzate-Morales, Jans; Osorio, Edison; Villaseñor, Jorge; Navarro-Retamal, Carlos

2015-11-01

Phenol is one of the worst contaminants at date, and its degradation has been a crucial task over years. Here, the decomposition process of phenol, in a Fenton reaction, is described. Using scavengers, it was observed that decomposition of phenol was mainly influenced by production of hydroxyl radicals. Experimental and theoretical activation energies (Ea) for phenol oxidation intermediates were calculated. According to these Ea, phenol decomposition is a two-step reaction mechanism mediated predominantly by hydroxyl radicals, producing a decomposition yield order given as hydroquinone > catechol > resorcinol. Furthermore, traces of reaction derived acids were detected by HPLC and GS-MS.

Distribution of apparent activation energy counterparts during thermo - And thermo-oxidative degradation of Aronia melanocarpa (black chokeberry).

PubMed

Janković, Bojan; Marinović-Cincović, Milena; Janković, Marija

2017-09-01

Kinetics of degradation for Aronia melanocarpa fresh fruits in argon and air atmospheres were investigated. The investigation was based on probability distributions of apparent activation energy of counterparts (ε a ). Isoconversional analysis results indicated that the degradation process in an inert atmosphere was governed by decomposition reactions of esterified compounds. Also, based on same kinetics approach, it was assumed that in an air atmosphere, the primary compound in degradation pathways could be anthocyanins, which undergo rapid chemical reactions. A new model of reactivity demonstrated that, under inert atmospheres, expectation values for ε a occured at levels of statistical probability. These values corresponded to decomposition processes in which polyphenolic compounds might be involved. ε a values obeyed laws of binomial distribution. It was established that, for thermo-oxidative degradation, Poisson distribution represented a very successful approximation for ε a values where there was additional mechanistic complexity and the binomial distribution was no longer valid. Copyright © 2017 Elsevier Ltd. All rights reserved.

Formation of bisphenol A by thermal degradation of poly(bisphenol A carbonate).

PubMed

Kitahara, Yuki; Takahashi, Seiji; Tsukagoshi, Masamichi; Fujii, Toshihiro

2010-09-01

The thermal decomposition of poly(bisphenol A carbonate) (PoC) results in the formation of the endocrine disruptor bisphenol A (BPA). In the present work, we investigated the kinetics of the thermal decomposition of PoC, and the subsequent decomposition of BPA, under pyrolysis conditions and in the presence of oxygen by using infrared image furnace-ion attachment mass spectrometry. The decomposition of PoC obeyed Arrhenius kinetics, which allowed us to determine the activation energy (E(a)) for thermal decomposition to BPA from Arrhenius plots. From the selected ion monitoring curves for BPA, E(a) for thermal decomposition in a nitrogen atmosphere was calculated to be 133.2 kcal mol(-1), whereas E(a) for oxidative thermal decomposition was calculated to be approximately 35% lower (86.5 kcal mol(-1)). Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Representing energy efficiency diagnosis strategies in cognitive work analysis.

PubMed

Hilliard, Antony; Jamieson, Greg A

2017-03-01

This article describes challenges encountered in applying Jens Rasmussen's Cognitive Work Analysis (CWA) framework to the practice of energy efficiency Monitoring & Targeting (M&T). Eight theoretic issues encountered in the analysis are described with respect to Rasmussen's work and the modeling solutions we adopted. We grappled with how to usefully apply Work Domain Analysis (WDA) to analyze categories of domains with secondary purposes and no ideal grain of decomposition. This difficulty encouraged us to pursue Control Task (ConTA) and Strategies (StrA) analysis, which are under-explored as bases for interface design. In ConTA we found M&T was best represented by two interlinked work functions; one controlling energy, the other maintaining knowledge representations. From StrA, we identified a popular representation-dependent strategy and inferred information required to diagnose faults in system performance and knowledge representation. This article presents and discusses excerpts from our analysis, and outlines their application to diagnosis support tools. Copyright © 2015 Elsevier Ltd. All rights reserved.

Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

PubMed

Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

2016-05-18

PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

Computer modeling of adsorption and decomposition pathways of boundary-layer lubricants on clean aluminum(111) surface, and adhesive metal transfer at the aluminum/steel interface: The ab-initio study

NASA Astrophysics Data System (ADS)

Zhong, Jun

Density functional theory (DFT) is employed to study lubricant adsorption and decomposition pathways, and adhesive metal transfer on clean aluminum surfaces. In this dissertation, density functional theory (DFT-GGA) is used to investigate the optimal adsorption geometries and binding energies of vinyl-phosphonic and ethanoic acids on an A1(111) surface. Tri-bridged, bi-bridged and uni-dentate coordinations for adsorbates are examined to determine the optimal binding sites on the surface. An analysis of the charge density of states (DOS) of oxygen involved in reacting with aluminum ions reveals changes in the atomic bonding configuration. For these acid molecules, the favorable decomposition pathways lead to fragments of vinyl- and alkylchains bonding to the Al(111) surface with phosphorous and carbon ions. Final optimal decomposition geometries and binding energies for various decomposition stages are also discussed. In addition, ab-initio molecular dynamics (AIMD) is carried out to explore collisions of aliphatic lubricants like butanol-alcohol and butanoic-acid with the Al(111) surface. Simulation results indicate that functional oxygen groups on these molecules could react with the "islands of nascent aluminum" and oxidize the surface. Favorable decomposition pieces on the surface, which were corroborated with experiment and DFT calculations, are found to contribute to the effectiveness of a particular molecule for boundary thinfilm lubrication to reduce the wear of aluminum. Finally, ab-initio molecular dynamics is also applied to investigations of the interaction between aluminum and hematite surfaces with and without a vinyl-phosphonic acid (VPA) lubricant. Without the lubricant, hematite is found to react with Al strongly (thermit reaction). This removes relatively large fragments from the surface of the aluminum substrate when this substrate is rubbed with a harder steel-roller under an external shock contact-load exceeding the ability of the substrate to support the aluminum-oxide film. Adhesive wear is found to significantly raise the temperature of system. Addition of VPA lubricant is found to retard the reaction of hematite with aluminum by forming an effective barrier between the two surfaces.

Effect of composting on the thermal decomposition behavior and kinetic parameters of pig manure-derived solid waste.

PubMed

Dhyani, Vaibhav; Kumar Awasthi, Mukesh; Wang, Quan; Kumar, Jitendra; Ren, Xiuna; Zhao, Junchao; Chen, Hongyu; Wang, Meijing; Bhaskar, Thallada; Zhang, Zengqiang

2018-03-01

In this work, the influence of composting on the thermal decomposition behavior and decomposition kinetics of pig manure-derived solid wastes was analyzed using thermogravimetry. Wheat straw, biochar, zeolite, and wood vinegar were added to pig manure during composting. The composting was done in the 130 L PVC reactors with 100 L effective volume for 50 days. The activation energy of pyrolysis of samples before and after composting was calculated using Friedman's method, while the pre-exponential factor was calculated using Kissinger's equation. It was observed that composting decreased the volatile content of all the samples. The additives when added together in pig manure lead to a reduction in the activation energy of decomposition, advocating the presence of simpler compounds in the compost material in comparison with the complex feedstock. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Factors Affecting Regional Per-Capita Carbon Emissions in China Based on an LMDI Factor Decomposition Model

PubMed Central

Dong, Feng; Long, Ruyin; Chen, Hong; Li, Xiaohui; Yang, Qingliang

2013-01-01

China is considered to be the main carbon producer in the world. The per-capita carbon emissions indicator is an important measure of the regional carbon emissions situation. This study used the LMDI factor decomposition model–panel co-integration test two-step method to analyze the factors that affect per-capita carbon emissions. The main results are as follows. (1) During 1997, Eastern China, Central China, and Western China ranked first, second, and third in the per-capita carbon emissions, while in 2009 the pecking order changed to Eastern China, Western China, and Central China. (2) According to the LMDI decomposition results, the key driver boosting the per-capita carbon emissions in the three economic regions of China between 1997 and 2009 was economic development, and the energy efficiency was much greater than the energy structure after considering their effect on restraining increased per-capita carbon emissions. (3) Based on the decomposition, the factors that affected per-capita carbon emissions in the panel co-integration test showed that Central China had the best energy structure elasticity in its regional per-capita carbon emissions. Thus, Central China was ranked first for energy efficiency elasticity, while Western China was ranked first for economic development elasticity. PMID:24353753

Factors affecting regional per-capita carbon emissions in China based on an LMDI factor decomposition model.

PubMed

Dong, Feng; Long, Ruyin; Chen, Hong; Li, Xiaohui; Yang, Qingliang

2013-01-01

China is considered to be the main carbon producer in the world. The per-capita carbon emissions indicator is an important measure of the regional carbon emissions situation. This study used the LMDI factor decomposition model-panel co-integration test two-step method to analyze the factors that affect per-capita carbon emissions. The main results are as follows. (1) During 1997, Eastern China, Central China, and Western China ranked first, second, and third in the per-capita carbon emissions, while in 2009 the pecking order changed to Eastern China, Western China, and Central China. (2) According to the LMDI decomposition results, the key driver boosting the per-capita carbon emissions in the three economic regions of China between 1997 and 2009 was economic development, and the energy efficiency was much greater than the energy structure after considering their effect on restraining increased per-capita carbon emissions. (3) Based on the decomposition, the factors that affected per-capita carbon emissions in the panel co-integration test showed that Central China had the best energy structure elasticity in its regional per-capita carbon emissions. Thus, Central China was ranked first for energy efficiency elasticity, while Western China was ranked first for economic development elasticity.

Low-rank canonical-tensor decomposition of potential energy surfaces: application to grid-based diagrammatic vibrational Green's function theory

NASA Astrophysics Data System (ADS)

Rai, Prashant; Sargsyan, Khachik; Najm, Habib; Hermes, Matthew R.; Hirata, So

2017-09-01

A new method is proposed for a fast evaluation of high-dimensional integrals of potential energy surfaces (PES) that arise in many areas of quantum dynamics. It decomposes a PES into a canonical low-rank tensor format, reducing its integral into a relatively short sum of products of low-dimensional integrals. The decomposition is achieved by the alternating least squares (ALS) algorithm, requiring only a small number of single-point energy evaluations. Therefore, it eradicates a force-constant evaluation as the hotspot of many quantum dynamics simulations and also possibly lifts the curse of dimensionality. This general method is applied to the anharmonic vibrational zero-point and transition energy calculations of molecules using the second-order diagrammatic vibrational many-body Green's function (XVH2) theory with a harmonic-approximation reference. In this application, high dimensional PES and Green's functions are both subjected to a low-rank decomposition. Evaluating the molecular integrals over a low-rank PES and Green's functions as sums of low-dimensional integrals using the Gauss-Hermite quadrature, this canonical-tensor-decomposition-based XVH2 (CT-XVH2) achieves an accuracy of 0.1 cm-1 or higher and nearly an order of magnitude speedup as compared with the original algorithm using force constants for water and formaldehyde.

Study on Kinetic Mechanism of Bastnaesite Concentrates Decomposition Using Calcium Hydroxide

NASA Astrophysics Data System (ADS)

Cen, Peng; Wu, Wenyuan; Bian, Xue

2018-06-01

The thermal decomposition of bastnaesite concentrates using calcium hydroxide was studied. Calcium hydroxide can effectively inhibit the emission of fluorine during roasting by transforming it to calcium fluoride. The decomposition rate increased with increasing reaction temperature and amount of calcium hydroxide. The decomposition kinetics were investigated. The decomposition reaction was determined to be a heterogeneous gas-solid reaction, and it followed an unreacted shrinking core model. By means of the integrated rate equation method, the reaction was proven to be kinetically first order. Different reaction models were fit to the experimental data to determine the reaction control process. The chemical reaction at the phase interface controlled the reaction rate in the temperatures ranging from 673 K to 773 K (400 °C to 500 °C) with an apparent activation energy of 82.044 kJ·mol-1. From 773 K to 973 K (500 °C to 700 °C), diffusion through the solid product's layer became the determining step, with a lower activation energy of 15.841 kJ·mol-1.

Hydrogen production by photoelectrolytic decomposition of H2O using solar energy

NASA Technical Reports Server (NTRS)

Rauh, R. D.; Alkaitis, S. A.; Buzby, J. M.; Schiff, R.

1980-01-01

Photoelectrochemical systems for the efficient decomposition of water are discussed. Semiconducting d band oxides which would yield the combination of stability, low electron affinity, and moderate band gap essential for an efficient photoanode are sought. The materials PdO and Fe-xRhxO3 appear most likely. Oxygen evolution yields may also be improved by mediation of high energy oxidizing agents, such as CO3(-). Examination of several p type semiconductors as photocathodes revealed remarkable stability for p-GaAs, and also indicated p-CdTe as a stable H2 photoelectrode. Several potentially economical schemes for photoelectrochemical decomposition of water were examined, including photoelectrochemical diodes and two stage, four photon processes.

Ab initio kinetics of gas phase decomposition reactions.

PubMed

Sharia, Onise; Kuklja, Maija M

2010-12-09

The thermal and kinetic aspects of gas phase decomposition reactions can be extremely complex due to a large number of parameters, a variety of possible intermediates, and an overlap in thermal decomposition traces. The experimental determination of the activation energies is particularly difficult when several possible reaction pathways coexist in the thermal decomposition. Ab initio calculations intended to provide an interpretation of the experiment are often of little help if they produce only the activation barriers and ignore the kinetics of the decomposition process. To overcome this ambiguity, a theoretical study of a complete picture of gas phase thermo-decomposition, including reaction energies, activation barriers, and reaction rates, is illustrated with the example of the β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) molecule by means of quantum-chemical calculations. We study three types of major decomposition reactions characteristic of nitramines: the HONO elimination, the NONO rearrangement, and the N-NO(2) homolysis. The reaction rates were determined using the conventional transition state theory for the HONO and NONO decompositions and the variational transition state theory for the N-NO(2) homolysis. Our calculations show that the HMX decomposition process is more complex than it was previously believed to be and is defined by a combination of reactions at any given temperature. At all temperatures, the direct N-NO(2) homolysis prevails with the activation barrier at 38.1 kcal/mol. The nitro-nitrite isomerization and the HONO elimination, with the activation barriers at 46.3 and 39.4 kcal/mol, respectively, are slow reactions at all temperatures. The obtained conclusions provide a consistent interpretation for the reported experimental data.

Ab initio calculations of the effects of H+ and NH4+ on the initial decomposition of HMX.

PubMed

Wang, Luoxin; Tuo, Xinlin; Yi, Changhai; Wang, Xiaogong

2008-10-01

In this work, the effects of H(+) and NH(4)(+) on the initial decomposition of HMX were investigated on the basis of the B3P86/6-31G** and B3LYP/6-31G* calculations. Three initial decomposition pathways including the N-NO(2) bond fission, HONO elimination and C-N bond dissociation were considered for the complexes formed by HMX with H(+) (PHMX1 and PHMX2) or with NH(4)(+) (AHMX). We found that H(+) and NH(4)(+) did not evidently induce the HMX to trigger the N-NO(2) heterolysis because the energy barrier of N-NO(2) heterolysis was found to be higher than the bond dissociation energy of N-NO(2) homolytic cleavage. Meanwhile, the transition state barriers of the HONO elimination from the complexes were found to be similar to that from the isolated HMX, which means that the HONO elimination reaction of HMX was not affected by the H(+) and NH(4)(+). As for the ring-opening reaction of HMX due to the C-N bond dissociation, the calculated potential energy profile showed that the energy of the complex (AHMX) went uphill along the C-N bond length and no transition state existed on the curve. However, the transition state energy barriers of C-N bond dissociation were calculated to be only 5.0 kcal/mol and 5.5 kcal/mol for the PHMX1 and PHMX2 complexes, respectively, which were much lower than the C-N bond dissociation energy of isolated HMX. Moreover, among the three initial decomposition reactions, the C-N bond dissociation was also the most energetically favorable pathway for the PHMX1 and PHMX2. Our calculation results showed that the H(+) can significantly promote the initial thermal decomposition of C-N bond of HMX, which, however, is influenced by NH(4)(+) slightly.

A TV-constrained decomposition method for spectral CT

NASA Astrophysics Data System (ADS)

Guo, Xiaoyue; Zhang, Li; Xing, Yuxiang

2017-03-01

Spectral CT is attracting more and more attention in medicine, industrial nondestructive testing and security inspection field. Material decomposition is an important issue to a spectral CT to discriminate materials. Because of the spectrum overlap of energy channels, as well as the correlation of basis functions, it is well acknowledged that decomposition step in spectral CT imaging causes noise amplification and artifacts in component coefficient images. In this work, we propose materials decomposition via an optimization method to improve the quality of decomposed coefficient images. On the basis of general optimization problem, total variance minimization is constrained on coefficient images in our overall objective function with adjustable weights. We solve this constrained optimization problem under the framework of ADMM. Validation on both a numerical dental phantom in simulation and a real phantom of pig leg on a practical CT system using dual-energy imaging is executed. Both numerical and physical experiments give visually obvious better reconstructions than a general direct inverse method. SNR and SSIM are adopted to quantitatively evaluate the image quality of decomposed component coefficients. All results demonstrate that the TV-constrained decomposition method performs well in reducing noise without losing spatial resolution so that improving the image quality. The method can be easily incorporated into different types of spectral imaging modalities, as well as for cases with energy channels more than two.

Thermal Dissociation and Roaming Isomerization of Nitromethane: Experiment and Theory.

PubMed

Annesley, Christopher J; Randazzo, John B; Klippenstein, Stephen J; Harding, Lawrence B; Jasper, Ahren W; Georgievskii, Yuri; Ruscic, Branko; Tranter, Robert S

2015-07-16

The thermal decomposition of nitromethane provides a classic example of the competition between roaming mediated isomerization and simple bond fission. A recent theoretical analysis suggests that as the pressure is increased from 2 to 200 Torr the product distribution undergoes a sharp transition from roaming dominated to bond-fission dominated. Laser schlieren densitometry is used to explore the variation in the effect of roaming on the density gradients for CH3NO2 decomposition in a shock tube for pressures of 30, 60, and 120 Torr at temperatures ranging from 1200 to 1860 K. A complementary theoretical analysis provides a novel exploration of the effects of roaming on the thermal decomposition kinetics. The analysis focuses on the roaming dynamics in a reduced dimensional space consisting of the rigid-body motions of the CH3 and NO2 radicals. A high-level reduced-dimensionality potential energy surface is developed from fits to large-scale multireference ab initio calculations. Rigid body trajectory simulations coupled with master equation kinetics calculations provide high-level a priori predictions for the thermal branching between roaming and dissociation. A statistical model provides a qualitative/semiquantitative interpretation of the results. Modeling efforts explore the relation between the predicted roaming branching and the observed gradients. Overall, the experiments are found to be fairly consistent with the theoretically proposed branching ratio, but they are also consistent with a no-roaming scenario and the underlying reasons are discussed. The theoretical predictions are also compared with prior theoretical predictions, with a related statistical model, and with the extant experimental data for the decomposition of CH3NO2, and for the reaction of CH3 with NO2.

Thermochemical and kinetic analysis of the thermal decomposition of monomethylhydrazine: an elementary reaction mechanism.

PubMed

Sun, Hongyan; Law, Chung K

2007-05-17

The reaction kinetics for the thermal decomposition of monomethylhydrazine (MMH) was studied with quantum Rice-Ramsperger-Kassel (QRRK) theory and a master equation analysis for pressure falloff. Thermochemical properties were determined by ab initio and density functional calculations. The entropies, S degrees (298.15 K), and heat capacities, Cp degrees (T) (0 < or = T/K < or = 1500), from vibrational, translational, and external rotational contributions were calculated using statistical mechanics based on the vibrational frequencies and structures obtained from the density functional study. Potential barriers for internal rotations were calculated at the B3LYP/6-311G(d,p) level, and hindered rotational contributions to S degrees (298.15 K) and Cp degrees (T) were calculated by solving the Schrödinger equation with free rotor wave functions, and the partition coefficients were treated by direct integration over energy levels of the internal rotation potentials. Enthalpies of formation, DeltafH degrees (298.15 K), for the parent MMH (CH3NHNH2) and its corresponding radicals CH3N*NH2, CH3NHN*H, and C*H2NHNH2 were determined to be 21.6, 48.5, 51.1, and 62.8 kcal mol(-1) by use of isodesmic reaction analysis and various ab initio methods. The kinetic analysis of the thermal decomposition, abstraction, and substitution reactions of MMH was performed at the CBS-QB3 level, with those of N-N and C-N bond scissions determined by high level CCSD(T)/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) calculations. Rate constants of thermally activated MMH to dissociation products were calculated as functions of pressure and temperature. An elementary reaction mechanism based on the calculated rate constants, thermochemical properties, and literature data was developed to model the experimental data on the overall MMH thermal decomposition rate. The reactions of N-N and C-N bond scission were found to be the major reaction paths for the modeling of MMH homogeneous decomposition at atmospheric conditions.

Thermogravimetric characteristics and kinetics of scrap tyre and Juglans regia shell co-pyrolysis.

PubMed

Uzun, B B; Yaman, E

2014-10-01

The degradation kinetics of Juglans regia shell, scrap tyre and their blends were investigated using a thermogravimetric analysis method. Experiments were performed under dynamic conditions and a nitrogen atmosphere in the range 293 to 973 K at different heating rates. During pyrolysis of J. regia shell three mass loss zones were specified as removal of water, decomposition of hemicelluloses and cellulose, and decomposition of lignin. The degradation curves of scrap tyre showed merely one stage which was due to decomposition of styrene butadiene rubber. The kinetic parameters were calculated using both Arrhenius and Coats-Redfern methods. By adopting the Arrhenius method, the average value of activation energies of J. regia shell, scrap tyre and their 1 : 1 blends were found to be 69.22, 71.48 and 47.03 kJ mol(-1), respectively. Additionally, by using the Coats-Redfern method, the average value of activation energies of J. regia shell, scrap tyre and their 1 : 1 blend were determined as 99.85, 78.72 and 63.81 kJ mol(-1), respectively. The addition of J. regia shell to scrap tyre caused a reduction in the activation energies. The difference of weight loss was measured to examine interactions between raw materials. The maximum difference between experimental and theoretical mass loss was 5% at about 648 K with a heating rate of 20 K min(-1). These results indicated a significant synergistic effect was available during co-pyrolysis of J. regia shell and scrap tyre in the high temperature region. © The Author(s) 2014.

Intramolecular energy transfer and mode-specific effects in unimolecular reactions of 1,2-difluoroethane

NASA Astrophysics Data System (ADS)

Raff, Lionel M.

1989-06-01

The unimolecular decomposition reactions of 1,2-difluoroethane upon mode-specific excitation to a total internal energy of 7.5 eV are investigated using classical trajectory methods and a previously formulated empirical potential-energy surface. The decomposition channels for 1,2-difluoroethane are, in order of importance, four-center HF elimination, C-C bond rupture, and hydrogen-atom dissociation. This order is found to be independent of the particular vibrational mode excited. Neither fluorine-atom nor F2 elimination reactions are ever observed even though these dissociation channels are energetically open. For four-center HF elimination, the average fraction of the total energy partitioned into internal HF motion varies between 0.115-0.181 depending upon the particular vibrational mode initially excited. The internal energy of the fluoroethylene product lies in the range 0.716-0.776. Comparison of the present results with those previously obtained for a random distribution of the initial 1,2-difluoroethane internal energy [J. Phys. Chem. 92, 5111 (1988)], shows that numerous mode-specific effects are present in these reactions in spite of the fact that intramolecular energy transfer rates for this system are 5.88-25.5 times faster than any of the unimolecular reaction rates. Mode-specific excitation always leads to a total decomposition rate significantly larger than that obtained for a random distribution of the internal energy. Excitation of different 1,2-difluoroethane vibrational modes is found to produce as much as a 51% change in the total decomposition rate. Mode-specific effects are also seen in the product energy partitioning. The rate coefficients for decomposition into the various channels are very sensitive to the particular mode excited. A comparison of the calculated mode-specific effects with the previously determined mode-to-mode energy transfer rate coefficients [J. Chem. Phys. 89, 5680 (1988)] shows that, to some extent, the presence of mode-specific chemistry is correlated with the magnitude of the energy transfer rate. However, the particular pathways for energy flow seem to be more important than the magnitude of the rate coefficients. It is suggested that the propensity for the energy to remain isolated in small subset of modes, such as the CH2F deformation modes or the rocking modes, is primarily responsible for the observation of mode-specific chemistry. The results clearly demonstrate that an intramolecular energy transfer rate that is fast relative to the unimolecular reaction rate is not a sufficient condition to ensure the absence of mode-specific chemical effects.

Density functional theory studies of HCOOH decomposition on Pd(111)

DOE PAGES

Scaranto, Jessica; Mavrikakis, Manos

2015-12-02

Here, the investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO 2 + H 2 and dehydration to CO + H 2O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easiermore » than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.« less

Density functional theory studies of HCOOH decomposition on Pd(111)

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

Scaranto, Jessica; Mavrikakis, Manos

Here, the investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO 2 + H 2 and dehydration to CO + H 2O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easiermore » than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.« less

A practical material decomposition method for x-ray dual spectral computed tomography.

PubMed

Hu, Jingjing; Zhao, Xing

2016-03-17

X-ray dual spectral CT (DSCT) scans the measured object with two different x-ray spectra, and the acquired rawdata can be used to perform the material decomposition of the object. Direct calibration methods allow a faster material decomposition for DSCT and can be separated in two groups: image-based and rawdata-based. The image-based method is an approximative method, and beam hardening artifacts remain in the resulting material-selective images. The rawdata-based method generally obtains better image quality than the image-based method, but this method requires geometrically consistent rawdata. However, today's clinical dual energy CT scanners usually measure different rays for different energy spectra and acquire geometrically inconsistent rawdata sets, and thus cannot meet the requirement. This paper proposes a practical material decomposition method to perform rawdata-based material decomposition in the case of inconsistent measurement. This method first yields the desired consistent rawdata sets from the measured inconsistent rawdata sets, and then employs rawdata-based technique to perform material decomposition and reconstruct material-selective images. The proposed method was evaluated by use of simulated FORBILD thorax phantom rawdata and dental CT rawdata, and simulation results indicate that this method can produce highly quantitative DSCT images in the case of inconsistent DSCT measurements.

Dynamics of phase separation of binary fluids

NASA Technical Reports Server (NTRS)

Ma, Wen-Jong; Maritan, Amos; Banavar, Jayanth R.; Koplik, Joel

1992-01-01

The results of molecular-dynamics studies of surface-tension-dominated spinodal decomposition of initially well-mixed binary fluids in the absence and presence of gravity are presented. The growth exponent for the domain size and the decay exponent of the potential energy of interaction between the two species with time are found to be 0.6 +/- 0.1, inconsistent with scaling arguments based on dimensional analysis.

Effects of calibration methods on quantitative material decomposition in photon-counting spectral computed tomography using a maximum a posteriori estimator.

PubMed

Curtis, Tyler E; Roeder, Ryan K

2017-10-01

Advances in photon-counting detectors have enabled quantitative material decomposition using multi-energy or spectral computed tomography (CT). Supervised methods for material decomposition utilize an estimated attenuation for each material of interest at each photon energy level, which must be calibrated based upon calculated or measured values for known compositions. Measurements using a calibration phantom can advantageously account for system-specific noise, but the effect of calibration methods on the material basis matrix and subsequent quantitative material decomposition has not been experimentally investigated. Therefore, the objective of this study was to investigate the influence of the range and number of contrast agent concentrations within a modular calibration phantom on the accuracy of quantitative material decomposition in the image domain. Gadolinium was chosen as a model contrast agent in imaging phantoms, which also contained bone tissue and water as negative controls. The maximum gadolinium concentration (30, 60, and 90 mM) and total number of concentrations (2, 4, and 7) were independently varied to systematically investigate effects of the material basis matrix and scaling factor calibration on the quantitative (root mean squared error, RMSE) and spatial (sensitivity and specificity) accuracy of material decomposition. Images of calibration and sample phantoms were acquired using a commercially available photon-counting spectral micro-CT system with five energy bins selected to normalize photon counts and leverage the contrast agent k-edge. Material decomposition of gadolinium, calcium, and water was performed for each calibration method using a maximum a posteriori estimator. Both the quantitative and spatial accuracy of material decomposition were most improved by using an increased maximum gadolinium concentration (range) in the basis matrix calibration; the effects of using a greater number of concentrations were relatively small in magnitude by comparison. The material basis matrix calibration was more sensitive to changes in the calibration methods than the scaling factor calibration. The material basis matrix calibration significantly influenced both the quantitative and spatial accuracy of material decomposition, while the scaling factor calibration influenced quantitative but not spatial accuracy. Importantly, the median RMSE of material decomposition was as low as ~1.5 mM (~0.24 mg/mL gadolinium), which was similar in magnitude to that measured by optical spectroscopy on the same samples. The accuracy of quantitative material decomposition in photon-counting spectral CT was significantly influenced by calibration methods which must therefore be carefully considered for the intended diagnostic imaging application. © 2017 American Association of Physicists in Medicine.

Renewable Energy Supply for Power Dominated, Energy Intense Production Processes - A Systematic Conversion Approach for the Anodizing Process

NASA Astrophysics Data System (ADS)

>D Stollenwerk, T Kuvarakul, I Kuperjans,

2013-06-01

European countries are highly dependent on energy imports. To lower this import dependency effectively, renewable energies will take a major role in future energy supply systems. To assist the national and inter-European efforts, extensive changes towards a renewable energy supply, especially on the company level, will be unavoidable. To conduct this conversion in the most effective way, the methodology developed in this paper can support the planning procedure. It is applied to the energy intense anodizing production process, where the electrical demand is the governing factor for the energy system layout. The differences between the classical system layout based on the current energy procurement and an approach with a detailed load-time-curve analysis, using process decomposition besides thermodynamic optimization, are discussed. The technical effects on the resulting energy systems are shown besides the resulting energy supply costs which will be determined by hourly discrete simulation.

A hydrogen energy carrier. Volume 2: Systems analysis

NASA Technical Reports Server (NTRS)

Savage, R. L. (Editor); Blank, L. (Editor); Cady, T. (Editor); Cox, K. (Editor); Murray, R. (Editor); Williams, R. D. (Editor)

1973-01-01

A systems analysis of hydrogen as an energy carrier in the United States indicated that it is feasible to use hydrogen in all energy use areas, except some types of transportation. These use areas are industrial, residential and commercial, and electric power generation. Saturation concept and conservation concept forecasts of future total energy demands were made. Projected costs of producing hydrogen from coal or from nuclear heat combined with thermochemical decomposition of water are in the range $1.00 to $1.50 per million Btu of hydrogen produced. Other methods are estimated to be more costly. The use of hydrogen as a fuel will require the development of large-scale transmission and storage systems. A pipeline system similar to the existing natural gas pipeline system appears practical, if design factors are included to avoid hydrogen environment embrittlement of pipeline metals. Conclusions from the examination of the safety, legal, environmental, economic, political and societal aspects of hydrogen fuel are that a hydrogen energy carrier system would be compatible with American values and the existing energy system.

Dissociation mechanisms of HFO-1336mzz(Z) on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces: A density functional theory study

NASA Astrophysics Data System (ADS)

Huo, Erguang; Liu, Chao; Xu, Xiaoxiao; Li, Qibin; Dang, Chaobin

2018-06-01

The catalytic effect of Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces on the decomposition of HFO-1336mzz(Z) have been investigated by using Density Functional Theory (DFT) calculations. On the basis of adsorption energy analysis, the most stable adsorption energies of HFO-1336mzz(Z) and relevant products on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces were studied, respectively, and the co-adsorption structures of relevant species were obtained. Finally, four initiation decomposition reactions of HFO-1336mzz(Z) on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces were proposed and investigated, respectively. At the same time, the four similar homolytic reactions of free HFO-1336mzz(Z) molecular were calculated to compare with the dissociation reactions occurred on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces and illuminate the catalytic effect of Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces on the HFO-1336mzz(Z) decomposition. The results indicated that Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces had a good catalytic effect on the decomposition of HFO-1336mzz(Z). The fracture reactions of Cdbnd C bonds on Cu(1 1 1), Cu(1 1 0) and Cu(1 0 0) surfaces were easier to occur than that of other reactions. Cu(1 0 0) surface had the highest catalytic activity and the lowest for Cu(1 1 1) surface.

Parallel Decomposition of the Fictitious Lagrangian Algorithm and its Accuracy for Molecular Dynamics Simulations of Semiconductors.

NASA Astrophysics Data System (ADS)

Yeh, Mei-Ling

We have performed a parallel decomposition of the fictitious Lagrangian method for molecular dynamics with tight-binding total energy expression into the hypercube computer. This is the first time in literature that the dynamical simulation of semiconducting systems containing more than 512 silicon atoms has become possible with the electrons treated as quantum particles. With the utilization of the Intel Paragon system, our timing analysis predicts that our code is expected to perform realistic simulations on very large systems consisting of thousands of atoms with time requirements of the order of tens of hours. Timing results and performance analysis of our parallel code are presented in terms of calculation time, communication time, and setup time. The accuracy of the fictitious Lagrangian method in molecular dynamics simulation is also investigated, especially the energy conservation of the total energy of ions. We find that the accuracy of the fictitious Lagrangian scheme in small silicon cluster and very large silicon system simulations is good for as long as the simulations proceed, even though we quench the electronic coordinates to the Born-Oppenheimer surface only in the beginning of the run. The kinetic energy of electrons does not increase as time goes on, and the energy conservation of the ionic subsystem remains very good. This means that, as far as the ionic subsystem is concerned, the electrons are on the average in the true quantum ground states. We also tie up some odds and ends regarding a few remaining questions about the fictitious Lagrangian method, such as the difference between the results obtained from the Gram-Schmidt and SHAKE method of orthonormalization, and differences between simulations where the electrons are quenched to the Born -Oppenheimer surface only once compared with periodic quenching.

Input of easily available organic C and N stimulates microbial decomposition of soil organic matter in arctic permafrost soil

PubMed Central

Wild, Birgit; Schnecker, Jörg; Alves, Ricardo J. Eloy; Barsukov, Pavel; Bárta, Jiří; Čapek, Petr; Gentsch, Norman; Gittel, Antje; Guggenberger, Georg; Lashchinskiy, Nikolay; Mikutta, Robert; Rusalimova, Olga; Šantrůčková, Hana; Shibistova, Olga; Urich, Tim; Watzka, Margarete; Zrazhevskaya, Galina; Richter, Andreas

2014-01-01

Rising temperatures in the Arctic can affect soil organic matter (SOM) decomposition directly and indirectly, by increasing plant primary production and thus the allocation of plant-derived organic compounds into the soil. Such compounds, for example root exudates or decaying fine roots, are easily available for microorganisms, and can alter the decomposition of older SOM (“priming effect”). We here report on a SOM priming experiment in the active layer of a permafrost soil from the central Siberian Arctic, comparing responses of organic topsoil, mineral subsoil, and cryoturbated subsoil material (i.e., poorly decomposed topsoil material subducted into the subsoil by freeze–thaw processes) to additions of 13C-labeled glucose, cellulose, a mixture of amino acids, and protein (added at levels corresponding to approximately 1% of soil organic carbon). SOM decomposition in the topsoil was barely affected by higher availability of organic compounds, whereas SOM decomposition in both subsoil horizons responded strongly. In the mineral subsoil, SOM decomposition increased by a factor of two to three after any substrate addition (glucose, cellulose, amino acids, protein), suggesting that the microbial decomposer community was limited in energy to break down more complex components of SOM. In the cryoturbated horizon, SOM decomposition increased by a factor of two after addition of amino acids or protein, but was not significantly affected by glucose or cellulose, indicating nitrogen rather than energy limitation. Since the stimulation of SOM decomposition in cryoturbated material was not connected to microbial growth or to a change in microbial community composition, the additional nitrogen was likely invested in the production of extracellular enzymes required for SOM decomposition. Our findings provide a first mechanistic understanding of priming in permafrost soils and suggest that an increase in the availability of organic carbon or nitrogen, e.g., by increased plant productivity, can change the decomposition of SOM stored in deeper layers of permafrost soils, with possible repercussions on the global climate. PMID:25089062

Theoretical study of the reaction mechanism of CH₃NO₂ with NO₂, NO and CO: the bimolecular reactions that cannot be ignored.

PubMed

Zhang, Ji-Dong; Kang, Li-Hua; Cheng, Xin-Lu

2015-01-01

The intriguing decompositions of nitro-containing explosives have been attracting interest. While theoretical investigations have long been concentrated mainly on unimolecular decompositions, bimolecular reactions have received little theoretical attention. In this paper, we investigate theoretically the bimolecular reactions between nitromethane (CH3NO2)-the simplest nitro-containing explosive-and its decomposition products, such as NO2, NO and CO, that are abundant during the decomposition process of CH3NO2. The structures and potential energy surface (PES) were explored at B3LYP/6-31G(d), B3P86/6-31G(d) and MP2/6-311 + G(d,p) levels, and energies were refined using CCSD(T)/cc-pVTZ methods. Quantum chemistry calculations revealed that the title reactions possess small barriers that can be comparable to, or smaller than, that of the initial decomposition reactions of CH3NO2. Considering that their reactants are abundant in the decomposition process of CH3NO2, we consider bimolecular reactions also to be of great importance, and worthy of further investigation. Moreover, our calculations show that NO2 can be oxidized by CH3NO2 to NO3 radical, which confirms the conclusion reached formerly by Irikura and Johnson [(2006) J Phys Chem A 110:13974-13978] that NO3 radical can be formed during the decomposition of nitramine explosives.

Methanol decomposition reactions over a boron-doped graphene supported Ru-Pt catalyst.

PubMed

Damte, Jemal Yimer; Lyu, Shang-Lin; Leggesse, Ermias Girma; Jiang, Jyh Chiang

2018-04-04

The decomposition of methanol is currently attracting research attention due to the potential widespread applications of its end products. In this work, density functional theory (DFT) calculations have been performed to investigate the adsorption and decomposition of methanol on a Ru-Pt/boron doped graphene surface. We find that the most favorable reaction pathway is methanol (CH3OH) decomposition through O-H bond breaking to form methoxide (CH3O) as the initial step, followed by further dehydrogenation steps which generate formaldehyde (CH2O), formyl (CHO), and carbon monoxide (CO). The calculations illustrate that CH3OH and CO groups prefer to adsorb at the Ru-top sites, while CH2OH, CH3O, CH2O, CHO, and H2 groups favor the Ru-Pt bridge sites, indicating the preference of Ru atoms to adsorb the active intermediates or species having lone-pair electrons. Based on the results, it is found that the energy barrier for CH3OH decomposition through the initial O-H bond breaking is less than its desorption energy of 0.95 eV, showing that CH3OH prefers to undergo decomposition to CH3O rather than direct desorption. The study provides in-depth theoretical insights into the potentially enhanced catalytic activity of Ru-Pt/boron doped graphene surfaces for methanol decomposition reactions, thereby contributing to the understanding and designing of an efficient catalyst under optimum conditions.

Force Analysis and Energy Operation of Chaotic System of Permanent-Magnet Synchronous Motor

NASA Astrophysics Data System (ADS)

Qi, Guoyuan; Hu, Jianbing

2017-12-01

The disadvantage of a nondimensionalized model of a permanent-magnet synchronous Motor (PMSM) is identified. The original PMSM model is transformed into a Kolmogorov system to aid dynamic force analysis. The vector field of the PMSM is analogous to the force field including four types of torque — inertial, internal, dissipative, and generalized external. Using the feedback thought, the error torque between external torque and dissipative torque is identified. The pitchfork bifurcation of the PMSM is performed. Four forms of energy are identified for the system — kinetic, potential, dissipative, and supplied. The physical interpretations of the decomposition of force and energy exchange are given. Casimir energy is stored energy, and its rate of change is the error power between the dissipative energy and the energy supplied to the motor. Error torque and error power influence the different types of dynamic modes. The Hamiltonian energy and Casimir energy are compared to find the function of each in producing the dynamic modes. A supremum bound for the chaotic attractor is proposed using the error power and Lagrange multiplier.

Breast composition measurement with a cadmium-zinc-telluride based spectral computed tomography system

PubMed Central

Ding, Huanjun; Ducote, Justin L.; Molloi, Sabee

2012-01-01

Purpose: To investigate the feasibility of breast tissue composition in terms of water, lipid, and protein with a cadmium-zinc-telluride (CZT) based computed tomography (CT) system to help better characterize suspicious lesions. Methods: Simulations and experimental studies were performed using a spectral CT system equipped with a CZT-based photon-counting detector with energy resolution. Simulations of the figure-of-merit (FOM), the signal-to-noise ratio (SNR) of the dual energy image with respect to the square root of mean glandular dose (MGD), were performed to find the optimal configuration of the experimental acquisition parameters. A calibration phantom 3.175 cm in diameter was constructed from polyoxymethylene plastic with cylindrical holes that were filled with water and oil. Similarly, sized samples of pure adipose and pure lean bovine tissues were used for the three-material decomposition. Tissue composition results computed from the images were compared to the chemical analysis data of the tissue samples. Results: The beam energy was selected to be 100 kVp with a splitting energy of 40 keV. The tissue samples were successfully decomposed into water, lipid, and protein contents. The RMS error of the volumetric percentage for the three-material decomposition, as compared to data from the chemical analysis, was estimated to be approximately 5.7%. Conclusions: The results of this study suggest that the CZT-based photon-counting detector may be employed in the CT system to quantify the water, lipid, and protein mass densities in tissue with a relatively good agreement. PMID:22380361

Hydrogen scrambling in ethane induced by intense laser fields: statistical analysis of coincidence events.

PubMed

Kanya, Reika; Kudou, Tatsuya; Schirmel, Nora; Miura, Shun; Weitzel, Karl-Michael; Hoshina, Kennosuke; Yamanouchi, Kaoru

2012-05-28

Two-body Coulomb explosion processes of ethane (CH(3)CH(3)) and its isotopomers (CD(3)CD(3) and CH(3)CD(3)) induced by an intense laser field (800 nm, 1.0 × 10(14) W/cm(2)) with three different pulse durations (40 fs, 80 fs, and 120 fs) are investigated by a coincidence momentum imaging method. On the basis of statistical treatment of the coincidence data, the contributions from false coincidence events are estimated and the relative yields of the decomposition pathways are determined with sufficiently small uncertainties. The branching ratios of the two body decomposition pathways of CH(3)CD(3) from which triatomic hydrogen molecular ions (H(3)(+), H(2)D(+), HD(2)(+), D(3)(+)) are ejected show that protons and deuterons within CH(3)CD(3) are scrambled almost statistically prior to the ejection of a triatomic hydrogen molecular ion. The branching ratios were estimated by statistical Rice-Ramsperger-Kassel-Marcus calculations by assuming a transition state with a hindered-rotation of a diatomic hydrogen moiety. The hydrogen scrambling dynamics followed by the two body decomposition processes are discussed also by using the anisotropies in the ejection directions of the fragment ions and the kinetic energy distribution of the two body decomposition pathways.

Synthesis, characterization and non-isothermal decomposition kinetic of a new galactochloralose based polymer.

PubMed

Kök, Gökhan; Ay, Kadir; Ay, Emriye; Doğan, Fatih; Kaya, Ismet

2014-01-30

A glycopolymer, poly(3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose) (PMIPTEG) was synthesized from the sugar-carrying methacrylate monomer, 3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose (MIPTEG) via conventional free radical polymerization with AIBN in 1,4-dioxane. The structures of glycomonomer and their polymers were confirmed by UV-vis, FT-IR, (1)H NMR, (13)C NMR, GPC, TG/DTG-DTA, DSC, and SEM techniques. SEM images showed that PMIPTEG had a straight-chain length structure. On the other hand, the thermal decomposition kinetics of polymer were investigated by means of thermogravimetric analysis in dynamic nitrogen atmosphere at different heating rates. The apparent activation energies for thermal decomposition of the PMIPTEG were calculated using the Kissinger, Kim-Park, Tang, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Friedman methods and were found to be 100.15, 104.40, 102.0, 102.2, 103.2 and 99.6 kJ/mol, respectively. The most likely process mechanism related to the thermal decomposition stage of PMIPTEG was determined to be a Dn deceleration type in terms of master plots results. Copyright © 2013 Elsevier Ltd. All rights reserved.

Differential Decomposition Among Pig, Rabbit, and Human Remains.

PubMed

Dautartas, Angela; Kenyhercz, Michael W; Vidoli, Giovanna M; Meadows Jantz, Lee; Mundorff, Amy; Steadman, Dawnie Wolfe

2018-03-30

While nonhuman animal remains are often utilized in forensic research to develop methods to estimate the postmortem interval, systematic studies that directly validate animals as proxies for human decomposition are lacking. The current project compared decomposition rates among pigs, rabbits, and humans at the University of Tennessee's Anthropology Research Facility across three seasonal trials that spanned nearly 2 years. The Total Body Score (TBS) method was applied to quantify decomposition changes and calculate the postmortem interval (PMI) in accumulated degree days (ADD). Decomposition trajectories were analyzed by comparing the estimated and actual ADD for each seasonal trial and by fuzzy cluster analysis. The cluster analysis demonstrated that the rabbits formed one group while pigs and humans, although more similar to each other than either to rabbits, still showed important differences in decomposition patterns. The decomposition trends show that neither nonhuman model captured the pattern, rate, and variability of human decomposition. © 2018 American Academy of Forensic Sciences.

Quantifying and characterizing dissolved carbon and nitrogen leaching from litter: a comparison of methods

USDA-ARS?s Scientific Manuscript database

Litter decomposition has a fundamental role in ecosystem functioning. It recycles energy, carbon and nutrients, supporting ecosystem productivity and soil organic matter formation. Litter decomposition occurs through leaching, fragmentation, and catabolism. Leaching is, arguably, the least studie...

Basis material decomposition method for material discrimination with a new spectrometric X-ray imaging detector

NASA Astrophysics Data System (ADS)

Brambilla, A.; Gorecki, A.; Potop, A.; Paulus, C.; Verger, L.

2017-08-01

Energy sensitive photon counting X-ray detectors provide energy dependent information which can be exploited for material identification. The attenuation of an X-ray beam as a function of energy depends on the effective atomic number Zeff and the density. However, the measured attenuation is degraded by the imperfections of the detector response such as charge sharing or pile-up. These imperfections lead to non-linearities that limit the benefits of energy resolved imaging. This work aims to implement a basis material decomposition method which overcomes these problems. Basis material decomposition is based on the fact that the attenuation of any material or complex object can be accurately reproduced by a combination of equivalent thicknesses of basis materials. Our method is based on a calibration phase to learn the response of the detector for different combinations of thicknesses of the basis materials. The decomposition algorithm finds the thicknesses of basis material whose spectrum is closest to the measurement, using a maximum likelihood criterion assuming a Poisson law distribution of photon counts for each energy bin. The method was used with a ME100 linear array spectrometric X-ray imager to decompose different plastic materials on a Polyethylene and Polyvinyl Chloride base. The resulting equivalent thicknesses were used to estimate the effective atomic number Zeff. The results are in good agreement with the theoretical Zeff, regardless of the plastic sample thickness. The linear behaviour of the equivalent lengths makes it possible to process overlapped materials. Moreover, the method was tested with a 3 materials base by adding gadolinium, whose K-edge is not taken into account by the other two materials. The proposed method has the advantage that it can be used with any number of energy channels, taking full advantage of the high energy resolution of the ME100 detector. Although in principle two channels are sufficient, experimental measurements show that the use of a high number of channels significantly improves the accuracy of decomposition by reducing noise and systematic bias.

WE-FG-207B-06: Plaque Composition Measurement with Dual Energy Computed Tomography

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

Wang, C; Ding, H; Malkasian, S

Purpose: To investigate the feasibility of characterizing arterial plaque composition in terms of water, lipid and protein or calcium using dual energy computed tomography. Characterization of plaque composition can potentially help distinguish vulnerable from stable plaques. Methods: Simulations studies were performed by the CT simulator based on ASTRA tomography toolbox. The beam energy for dual energy images was selected to be 80 kVp and 135 kVp. The radiation dose and energy spectrum for the CT simulator were carefully calibrated with respect to a 320-slice CT scanner. A digital chest phantom was constructed using Matlab for calibration and plaque measurement. Puremore » water, lipid, protein or calcium was used for calibration and a mixture of different volume percentages of these materials were used for validation purposes. Non-calcified plaque was simulated using water, lipid and protein with volumetric percentage range of 35%∼65%, 5%∼60% and 5%∼40%, respectively. Calcified plaque was simulated using water, lipid and calcium with volumetric percentage range of 50%∼80%, 8%∼45% and 3%∼13%, respectively. We employed iterative sinogram processing (ISP) to reduce the beam hardening effect in the simulation to improve the decomposition results. Results: The simulated known composition and dual energy decomposition results were in good agreement. Water, lipid and protein (calcium) mixtures were decomposed into water, lipid and protein (calcium) contents. The RMS errors of volumetric percentage for the water, lipid and protein (non-calcified plaque) decomposition, as compared to known values, were estimated to be approximately 5.74%, 2.54%, and 0.95% respectively. The RMS errors of volumetric percentage for the water, lipid and Calcium (calcified plaque) decomposition, as compared to known values, were estimated to be approximately 7.4%, 8.64%, and 0.08% respectively. Conclusion: The results of this study suggest that the dual energy decomposition can potentially be used to quantify the water, lipid, and protein or calcium composition of a plaque with relatively good accuracy. Grant funding from Toshiba Medical Systems and Philips Medical Systems.« less

Identification of channel geometries applying seismic attributes and spectral decomposition techniques, Temsah Field, Offshore East Nile Delta, Egypt

NASA Astrophysics Data System (ADS)

Othman, Adel A. A.; Fathy, M.; Negm, Adel

2018-06-01

The Temsah field is located in eastern part of the Nile delta to seaward. The main reservoirs of the area are Middle Pliocene mainly consist from siliciclastic which associated with a close deep marine environment. The Distribution pattern of the reservoir facies is limited scale indicating fast lateral and vertical changes which are not easy to resolve by applying of conventional seismic attribute. The target of the present study is to create geophysical workflows to a better image of the channel sand distribution in the study area. We apply both Average Absolute Amplitude and Energy attribute which are indicated on the distribution of the sand bodies in the study area but filled to fully described the channel geometry. So another tool, which offers more detailed geometry description is needed. The spectral decomposition analysis method is an alternative technique focused on processing Discrete Fourier Transform which can provide better results. Spectral decomposition have been done over the upper channel shows that the frequency in the eastern part of the channel is the same frequency in places where the wells are drilled, which confirm the connection of both the eastern and western parts of the upper channel. Results suggest that application of the spectral decomposition method leads to reliable inferences. Hence, using the spectral decomposition method alone or along with other attributes has a positive impact on reserves growth and increased production where the reserve in the study area increases to 75bcf.

Dual energy computed tomography for the head.

PubMed

Naruto, Norihito; Itoh, Toshihide; Noguchi, Kyo

2018-02-01

Dual energy CT (DECT) is a promising technology that provides better diagnostic accuracy in several brain diseases. DECT can generate various types of CT images from a single acquisition data set at high kV and low kV based on material decomposition algorithms. The two-material decomposition algorithm can separate bone/calcification from iodine accurately. The three-material decomposition algorithm can generate a virtual non-contrast image, which helps to identify conditions such as brain hemorrhage. A virtual monochromatic image has the potential to eliminate metal artifacts by reducing beam-hardening effects. DECT also enables exploration of advanced imaging to make diagnosis easier. One such novel application of DECT is the X-Map, which helps to visualize ischemic stroke in the brain without using iodine contrast medium.

Thermal Analysis of porous fin with uniform magnetic field using Adomian decomposition Sumudu transform method

NASA Astrophysics Data System (ADS)

Patel, Trushit; Meher, Ramakanta

2017-09-01

In this paper, we consider a Roseland approximation to radiate heat transfer, Darcy's model to simulate the flow in porous media and finite-length fin with insulated tip to study the thermal performance and to predict the temperature distribution in a vertical isothermal surface. The energy balance equations of the porous fin with several temperature dependent properties are solved using the Adomian Decomposition Sumudu Transform Method (ADSTM). The effects of various thermophysical parameters, such as the convection-conduction parameter, Surface-ambient radiation parameter, Rayleigh numbers and Hartman number are determined. The results obtained from the ADSTM are further compared with the fourth-fifth order Runge-Kutta-Fehlberg method and Least Square Method(LSM) (Hoshyar et al. 2016 ) to determine the accuracy of the solution.

Low-rank canonical-tensor decomposition of potential energy surfaces: application to grid-based diagrammatic vibrational Green's function theory

DOE PAGES

Rai, Prashant; Sargsyan, Khachik; Najm, Habib; ...

2017-03-07

Here, a new method is proposed for a fast evaluation of high-dimensional integrals of potential energy surfaces (PES) that arise in many areas of quantum dynamics. It decomposes a PES into a canonical low-rank tensor format, reducing its integral into a relatively short sum of products of low-dimensional integrals. The decomposition is achieved by the alternating least squares (ALS) algorithm, requiring only a small number of single-point energy evaluations. Therefore, it eradicates a force-constant evaluation as the hotspot of many quantum dynamics simulations and also possibly lifts the curse of dimensionality. This general method is applied to the anharmonic vibrationalmore » zero-point and transition energy calculations of molecules using the second-order diagrammatic vibrational many-body Green's function (XVH2) theory with a harmonic-approximation reference. In this application, high dimensional PES and Green's functions are both subjected to a low-rank decomposition. Evaluating the molecular integrals over a low-rank PES and Green's functions as sums of low-dimensional integrals using the Gauss–Hermite quadrature, this canonical-tensor-decomposition-based XVH2 (CT-XVH2) achieves an accuracy of 0.1 cm -1 or higher and nearly an order of magnitude speedup as compared with the original algorithm using force constants for water and formaldehyde.« less

Low-rank canonical-tensor decomposition of potential energy surfaces: application to grid-based diagrammatic vibrational Green's function theory

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

Rai, Prashant; Sargsyan, Khachik; Najm, Habib

Here, a new method is proposed for a fast evaluation of high-dimensional integrals of potential energy surfaces (PES) that arise in many areas of quantum dynamics. It decomposes a PES into a canonical low-rank tensor format, reducing its integral into a relatively short sum of products of low-dimensional integrals. The decomposition is achieved by the alternating least squares (ALS) algorithm, requiring only a small number of single-point energy evaluations. Therefore, it eradicates a force-constant evaluation as the hotspot of many quantum dynamics simulations and also possibly lifts the curse of dimensionality. This general method is applied to the anharmonic vibrationalmore » zero-point and transition energy calculations of molecules using the second-order diagrammatic vibrational many-body Green's function (XVH2) theory with a harmonic-approximation reference. In this application, high dimensional PES and Green's functions are both subjected to a low-rank decomposition. Evaluating the molecular integrals over a low-rank PES and Green's functions as sums of low-dimensional integrals using the Gauss–Hermite quadrature, this canonical-tensor-decomposition-based XVH2 (CT-XVH2) achieves an accuracy of 0.1 cm -1 or higher and nearly an order of magnitude speedup as compared with the original algorithm using force constants for water and formaldehyde.« less

A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

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

Raupach, Marc; Tonner, Ralf, E-mail: tonner@chemie.uni-marburg.de

The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the bonding energy between two fragments (e.g., the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic, Pauli repulsion, and orbital relaxation energies. This is complemented by consideration of dispersion interactions via a pairwise scheme. One major extension toward a previous implementation [Philipsen and Baerends, J. Phys. Chem. B 110, 12470 (2006)] lies in the separate discussion of electrostatic and Pauli and the additionmore » of a dispersion term. The pEDA presented here for an implementation based on atomic orbitals can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy, and k-space sampling. Four typical bonding scenarios for surface-adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H{sub 2} on M(001), M = Pd, Cu), and semiconducting (CO and C{sub 2}H{sub 2} on Si(001)) substrates. These examples cover diverse substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence that the pEDA will be a powerful tool for the analysis of surface-adsorbate bonding in the future, enabling the transfer of concepts like ionic and covalent bonding, donor-acceptor interaction, steric repulsion, and others to extended systems.« less

Azole energetic materials: Initial mechanisms for the energy release from electronical excited nitropyrazoles

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

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

2014-01-21

Decomposition of energetic material 3,4-dinitropyrazole (DNP) and two model molecules 4-nitropyrazole and 1-nitropyrazole is investigated both theoretically and experimentally. The initial decomposition mechanisms for these three nitropyrazoles are explored with complete active space self-consistent field (CASSCF) level. The NO molecule is observed as an initial decomposition product from all three materials subsequent to UV excitation. Observed NO products are rotationally cold (<50 K) for all three systems. The vibrational temperature of the NO product from DNP is (3850 ± 50) K, 1350 K hotter than that of the two model species. Potential energy surface calculations at the CASSCF(12,8)/6-31+G(d) level illustratemore » that conical intersections plays an essential role in the decomposition mechanism. Electronically excited S{sub 2} nitropyraozles can nonradiatively relax to lower electronic states through (S{sub 2}/S{sub 1}){sub CI} and (S{sub 1}/S{sub 0}){sub CI} conical intersection and undergo a nitro-nitrite isomerization to generate NO product either in the S{sub 1} state or S{sub 0} state. In model systems, NO is generated in the S{sub 1} state, while in the energetic material DNP, NO is produced on the ground state surface, as the S{sub 1} decomposition pathway is energetically unavailable. The theoretically predicted mechanism is consistent with the experimental results, as DNP decomposes in a lower electronic state than do the model systems and thus the vibrational energy in the NO product from DNP should be hotter than from the model systems. The observed rotational energy distributions for NO are consistent with the final structures of the respective transition states for each molecule.« less

Thermal Analysis Study of Antihypertensive Drugs Telmisartan and Cilazapril

PubMed Central

Saber, Refaat Ahmed; Attia, Ali Kamal; Salem, Waheed Mohamed

2014-01-01

Purpose: The aim of the present work is to study the thermal analysis of telmisartan and cilazapril. Methods: Thermogravimetry (TGA), derivative thermogravimetry (DTG) and differential thermal analysis (DTA) were used through the work to achieve the thermal analysis study of some antihypertensive drugs, telmisartan and cilazapril. Results: The results led to thermal stability data and also to the interpretation concerning the thermal decomposition. Thermogravimetry data allowed determination of the kinetic parameters such as, activation energy and frequency factor. Conclusion: The simplicity, speed and low operational costs of thermal analysis justify its application in the quality control of pharmaceutical compounds for medications. PMID:24754013

MO-FG-CAMPUS-IeP1-02: Dose Reduction in Contrast-Enhanced Digital Mammography Using a Photon-Counting Detector

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

Lee, S; Kang, S; Eom, J

Purpose: Photon-counting detectors (PCDs) allow multi-energy X-ray imaging without additional exposures and spectral overlap. This capability results in the improvement of accuracy of material decomposition for dual-energy X-ray imaging and the reduction of radiation dose. In this study, the PCD-based contrast-enhanced dual-energy mammography (CEDM) was compared with the conventional CDEM in terms of radiation dose, image quality and accuracy of material decomposition. Methods: A dual-energy model was designed by using Beer-Lambert’s law and rational inverse fitting function for decomposing materials from a polychromatic X-ray source. A cadmium zinc telluride (CZT)-based PCD, which has five energy thresholds, and iodine solutions includedmore » in a 3D half-cylindrical phantom, which composed of 50% glandular and 50% adipose tissues, were simulated by using a Monte Carlo simulation tool. The low- and high-energy images were obtained in accordance with the clinical exposure conditions for the conventional CDEM. Energy bins of 20–33 and 34–50 keV were defined from X-ray energy spectra simulated at 50 kVp with different dose levels for implementing the PCD-based CDEM. The dual-energy mammographic techniques were compared by means of absorbed dose, noise property and normalized root-mean-square error (NRMSE). Results: Comparing to the conventional CEDM, the iodine solutions were clearly decomposed for the PCD-based CEDM. Although the radiation dose for the PCD-based CDEM was lower than that for the conventional CEDM, the PCD-based CDEM improved the noise property and accuracy of decomposition images. Conclusion: This study demonstrates that the PCD-based CDEM allows the quantitative material decomposition, and reduces radiation dose in comparison with the conventional CDEM. Therefore, the PCD-based CDEM is able to provide useful information for detecting breast tumor and enhancing diagnostic accuracy in mammography.« less

Decomposition pathways of C2 oxygenates on Rh-modified tungsten carbide surfaces

DOE PAGES

Kelly, Thomas G.; Ren, Hui; Chen, Jingguang G.

2015-03-27

Ethanol decomposition on tungsten monocarbide (WC) and Rh-modified WC was investigated using ultrahigh vacuum (UHV) surface science experiments and density functional theory (DFT) calculations. DFT calculations indicated that the binding energies of ethanol and its decomposition intermediates on WC(0001) were modified by Rh, with Rh/WC(0001) showing similar values to those on Rh(111). Through temperature-programmed desorption (TPD) experiments on polycrystalline WC and Rh-modified WC, it was shown that the selectivity for ethanol decomposition was different on these surfaces. On WC, the C-O bond of ethanol was preferentially broken to produce ethylene; on Rh-modified WC, the C-C bond was broken to producemore » carbon monoxide and methane. In addition, high-resolution electron energy loss spectroscopy (HREELS) was used to determine likely surface intermediates. On Rh-modified WC, ethanol first formed ethoxy through O-H scission, then reacted through an aldehyde intermediate to form the C1 products.« less

Water/cortical bone decomposition: A new approach in dual energy CT imaging for bone marrow oedema detection. A feasibility study.

PubMed

Biondi, M; Vanzi, E; De Otto, G; Banci Buonamici, F; Belmonte, G M; Mazzoni, L N; Guasti, A; Carbone, S F; Mazzei, M A; La Penna, A; Foderà, E; Guerreri, D; Maiolino, A; Volterrani, L

2016-12-01

Many studies aimed at validating the application of Dual Energy Computed Tomography (DECT) in clinical practice where conventional CT is not exhaustive. An example is given by bone marrow oedema detection, in which DECT based on water/calcium (W/Ca) decomposition was applied. In this paper a new DECT approach, based on water/cortical bone (W/CB) decomposition, was investigated. Eight patients suffering from marrow oedema were scanned with MRI and DECT. Two-materials density decomposition was performed in ROIs corresponding to normal bone marrow and oedema. These regions were drawn on DECT images using MRI informations. Both W/Ca and W/CB were considered as material basis. Scatter plots of W/Ca and W/CB concentrations were made for each ROI in order to evaluate if oedema could be distinguished from normal bone marrow. Thresholds were defined on the scatter plots in order to produce DECT images where oedema regions were highlighted through color maps. The agreement between these images and MR was scored by two expert radiologists. For all the patients, the best scores were obtained using W/CB density decomposition. In all cases, DECT color map images based on W/CB decomposition showed better agreement with MR in bone marrow oedema identification with respect to W/Ca decomposition. This result encourages further studies in order to evaluate if DECT based on W/CB decomposition could be an alternative technique to MR, which would be important when short scanning duration is relevant, as in the case of aged or traumatic patients. Copyright © 2016 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

Energy recovery from solid waste. Volume 1: Summary report

NASA Technical Reports Server (NTRS)

1975-01-01

A systems analysis of energy recovery from solid waste which demonstrates the feasibility of several processes for converting solid waste to an energy form is presented. The social, legal, environmental, and political factors are considered and recommendations made in regard to legislation and policy. A technical and economic evaluation of available and developing energy-recovery processes is given with emphasis on thermal decomposition and biodegradation. A pyrolysis process is suggested. The use of prepared solid waste as a fuel supplemental to coal is considered to be the most economic process for recovery of energy from solid waste. Markets are discussed with suggestions for improving market conditions and for developing market stability. A decision procedure is given to aid a community in deciding on its options in dealing with solid waste.

Low to high temperature energy conversion system

NASA Technical Reports Server (NTRS)

Miller, C. G. (Inventor)

1977-01-01

A method for converting heat energy from low temperature heat sources to higher temperature was developed. It consists of a decomposition chamber in which ammonia is decomposed into hydrogen and nitrogen by absorbing heat of decomposition from a low temperature energy source. A recombination reaction then takes place which increases the temperature of a fluid significantly. The system is of use for the efficient operation of compact or low capital investment turbine driven electrical generators, or in other applications, to enable chemical reactions that have a critical lower temperature to be used. The system also recovers heat energy from low temperature heat sources, such as solar collectors or geothermal sources, and converts it to high temperatures.

[Pb(H2O)]2+ and [Pb(OH)]+: four-component density functional theory calculations, correlated scalar relativistic constrained-space orbital variation energy decompositions, and topological analysis.

PubMed

Gourlaouen, Christophe; Piquemal, Jean-Philip; Parisel, Olivier

2006-05-07

Within the scope of studying the molecular implications of the Pb(2+) cation in environmental and polluting processes, this paper reports Hartree-Fock and density functional theory (B3LYP) four-component relativistic calculations using an all-electron basis set applied to [Pb(H(2)O)](2+) and [Pb(OH)](+), two complexes expected to be found in the terrestrial atmosphere. It is shown that full-relativistic calculations validate the use of scalar relativistic approaches within the framework of density functional theory. [Pb(H(2)O)](2+) is found C(2v) at any level of calculations whereas [Pb(OH)](+) can be found bent or linear depending of the computational methodology used. When C(s) is found the barrier to inversion through the C(infinityv) structure is very low, and can be overcome at high enough temperature, making the molecule floppy. In order to get a better understanding of the bonding occurring between the Pb(2+) cation and the H(2)O and OH(-) ligands, natural bond orbital and atoms-in-molecule calculations have been performed. These approaches are supplemented by a topological analysis of the electron localization function. Finally, the description of these complexes is refined using constrained-space orbital variation complexation energy decompositions.

Performance of the AMOEBA Water Model in the Vicinity of QM Solutes: A Diagnosis Using Energy Decomposition Analysis.

PubMed

Mao, Yuezhi; Shao, Yihan; Dziedzic, Jacek; Skylaris, Chris-Kriton; Head-Gordon, Teresa; Head-Gordon, Martin

2017-05-09

The importance of incorporating solvent polarization effects into the modeling of solvation processes has been well-recognized, and therefore a new generation of hybrid quantum mechanics/molecular mechanics (QM/MM) approaches that accounts for this effect is desirable. We present a fully self-consistent, mutually polarizable QM/MM scheme using the AMOEBA force field, in which the total energy of the system is variationally minimized with respect to both the QM electronic density and the MM induced dipoles. This QM/AMOEBA model is implemented through the Q-Chem/LibEFP code interface and then applied to the evaluation of solute-solvent interaction energies for various systems ranging from the water dimer to neutral and ionic solutes (NH 3 , NH 4 + , CN - ) surrounded by increasing numbers of water molecules (up to 100). In order to analyze the resulting interaction energies, we also utilize an energy decomposition analysis (EDA) scheme which identifies contributions from permanent electrostatics, polarization, and van der Waals (vdW) interaction for the interaction between the QM solute and the solvent molecules described by AMOEBA. This facilitates a component-wise comparison against full QM calculations where the corresponding energy components are obtained via a modified version of the absolutely localized molecular orbitals (ALMO)-EDA. The results show that the present QM/AMOEBA model can yield reasonable solute-solvent interaction energies for neutral and cationic species, while further scrutiny reveals that this accuracy highly relies on the delicate balance between insufficiently favorable permanent electrostatics and softened vdW interaction. For anionic solutes where the charge penetration effect becomes more pronounced, the QM/MM interface turns out to be unbalanced. These results are consistent with and further elucidate our findings in a previous study using a slightly different QM/AMOEBA model ( Dziedzic et al. J. Chem. Phys. 2016 , 145 , 124106 ). The implications of these results for further refinement of this model are also discussed.

Proper Orthogonal Decomposition on Experimental Multi-phase Flow in a Pipe

NASA Astrophysics Data System (ADS)

Viggiano, Bianca; Tutkun, Murat; Cal, Raúl Bayoán

2016-11-01

Multi-phase flow in a 10 cm diameter pipe is analyzed using proper orthogonal decomposition. The data were obtained using X-ray computed tomography in the Well Flow Loop at the Institute for Energy Technology in Kjeller, Norway. The system consists of two sources and two detectors; one camera records the vertical beams and one camera records the horizontal beams. The X-ray system allows measurement of phase holdup, cross-sectional phase distributions and gas-liquid interface characteristics within the pipe. The mathematical framework in the context of multi-phase flows is developed. Phase fractions of a two-phase (gas-liquid) flow are analyzed and a reduced order description of the flow is generated. Experimental data deepens the complexity of the analysis with limited known quantities for reconstruction. Comparison between the reconstructed fields and the full data set allows observation of the important features. The mathematical description obtained from the decomposition will deepen the understanding of multi-phase flow characteristics and is applicable to fluidized beds, hydroelectric power and nuclear processes to name a few.

Speech rhythm analysis with decomposition of the amplitude envelope: characterizing rhythmic patterns within and across languages.

PubMed

Tilsen, Sam; Arvaniti, Amalia

2013-07-01

This study presents a method for analyzing speech rhythm using empirical mode decomposition of the speech amplitude envelope, which allows for extraction and quantification of syllabic- and supra-syllabic time-scale components of the envelope. The method of empirical mode decomposition of a vocalic energy amplitude envelope is illustrated in detail, and several types of rhythm metrics derived from this method are presented. Spontaneous speech extracted from the Buckeye Corpus is used to assess the effect of utterance length on metrics, and it is shown how metrics representing variability in the supra-syllabic time-scale components of the envelope can be used to identify stretches of speech with targeted rhythmic characteristics. Furthermore, the envelope-based metrics are used to characterize cross-linguistic differences in speech rhythm in the UC San Diego Speech Lab corpus of English, German, Greek, Italian, Korean, and Spanish speech elicited in read sentences, read passages, and spontaneous speech. The envelope-based metrics exhibit significant effects of language and elicitation method that argue for a nuanced view of cross-linguistic rhythm patterns.

Cerebrospinal fluid PCR analysis and biochemistry in bodies with severe decomposition.

PubMed

Palmiere, Cristian; Vanhaebost, Jessica; Ventura, Francesco; Bonsignore, Alessandro; Bonetti, Luca Reggiani

2015-02-01

The aim of this study was to assess whether Neisseria meningitidis, Listeria monocytogenes, Streptococcus pneumoniae and Haemophilus influenzae can be identified using the polymerase chain reaction technique in the cerebrospinal fluid of severely decomposed bodies with known, noninfectious causes of death or whether postmortem changes can lead to false positive results and thus erroneous diagnostic information. Biochemical investigations, postmortem bacteriology and real-time polymerase chain reaction analysis in cerebrospinal fluid were performed in a series of medico-legal autopsies that included noninfectious causes of death with decomposition, bacterial meningitis without decomposition, bacterial meningitis with decomposition, low respiratory tract infections with decomposition and abdominal infections with decomposition. In noninfectious causes of death with decomposition, postmortem investigations failed to reveal results consistent with generalized inflammation or bacterial infections at the time of death. Real-time polymerase chain reaction analysis in cerebrospinal fluid did not identify the studied bacteria in any of these cases. The results of this study highlight the usefulness of molecular approaches in bacteriology as well as the use of alternative biological samples in postmortem biochemistry in order to obtain suitable information even in corpses with severe decompositional changes. Copyright © 2014 Elsevier Ltd and Faculty of Forensic and Legal Medicine. All rights reserved.

System for thermal energy storage, space heating and cooling and power conversion

DOEpatents

Gruen, Dieter M.; Fields, Paul R.

1981-04-21

An integrated system for storing thermal energy, for space heating and cong and for power conversion is described which utilizes the reversible thermal decomposition characteristics of two hydrides having different decomposition pressures at the same temperature for energy storage and space conditioning and the expansion of high-pressure hydrogen for power conversion. The system consists of a plurality of reaction vessels, at least one containing each of the different hydrides, three loops of circulating heat transfer fluid which can be selectively coupled to the vessels for supplying the heat of decomposition from any appropriate source of thermal energy from the outside ambient environment or from the spaces to be cooled and for removing the heat of reaction to the outside ambient environment or to the spaces to be heated, and a hydrogen loop for directing the flow of hydrogen gas between the vessels. When used for power conversion, at least two vessels contain the same hydride and the hydrogen loop contains an expansion engine. The system is particularly suitable for the utilization of thermal energy supplied by solar collectors and concentrators, but may be used with any source of heat, including a source of low-grade heat.

Effect of sulfation on the surface activity of CaO for N2O decomposition

NASA Astrophysics Data System (ADS)

Wu, Lingnan; Hu, Xiaoying; Qin, Wu; Dong, Changqing; Yang, Yongping

2015-12-01

Limestone addition to circulating fluidized bed boilers for sulfur removal affects nitrous oxide (N2O) emission at the same time, but mechanism of how sulfation process influences the surface activity of CaO for N2O decomposition remains unclear. In this paper, we investigated the effect of sulfation on the surface properties and catalytic activity of CaO for N2O decomposition using density functional theory calculations. Sulfation of CaO (1 0 0) surface by the adsorption of a single gaseous SO2 or SO3 molecule forms stable local CaSO3 or CaSO4 on the CaO (1 0 0) surface with strong hybridization between the S atom of SOx and the surface O anion. The formed local CaSO3 increases the barrier energy of N2O decomposition from 0.989 eV (on the CaO (1 0 0) surface) to 1.340 eV, and further sulfation into local CaSO4 remarkably increases the barrier energy to 2.967 eV. Sulfation from CaSO3 into CaSO4 is therefore the crucial step for deactivating the surface activity for N2O decomposition. Completely sulfated CaSO4 (0 0 1) and (0 1 0) surfaces further validate the negligible catalytic ability of CaSO4 for N2O decomposition.

Analysis of electron beam induced deposition (EBID) of residual hydrocarbons in electron microscopy

NASA Astrophysics Data System (ADS)

Rykaczewski, Konrad; White, William B.; Fedorov, Andrei G.

2007-03-01

In this work we have developed a comprehensive dynamic model of electron beam induced deposition (EBID) of residual hydrocarbon coupling mass transport, electron transport and scattering, and species decomposition to predict the deposition of carbon nanopillars. The simulations predict the local species and electron density distributions, as well as the three-demensional morphology and the growth rate of the deposit. Since the process occurs in a high vacuum environment, surface diffusion is considered as the primary transport mode of surface-adsorbed hydrocarbon precursor. The governing surface transport equation (STE) of the adsorbed species is derived and solved numerically. The transport, scattering, and absorption of primary electron as well as secondary electron generation are treated using the Monte Carlo method. Low energy secondary electrons are the major contributors to hydrocarbon decomposition due to their energy range matching peak dissociation reaction cross section energies for precursor molecules. The deposit and substrate are treated as a continuous entity allowing the simulation of the growth of a realistically sized deposit rather than a large number of cells representing each individual atom as in previously published simulations [Mitsuishi et al., Ultramicroscopy 103, 17 (2005); Silvis-Cividjian, Ph.D. thesis, University of Delft, 2002]. Such formulation allows for simple coupling of the STE with the dynamic growth of the nanopillar. Three different growth regimes occurring in EBID are identified using scaling analysis, and simulations are used to describe the deposit morphology and precursor surface concentration specific for each growth regime.

Directional Dependence of Hydrogen Bonds: a Density-based Energy Decomposition Analysis and Its Implications on Force Field Development

PubMed Central

Lu, Zhenyu; Zhou, Nengjie; Wu, Qin; Zhang, Yingkai

2011-01-01

One well-known shortcoming of widely-used biomolecular force fields is the description of the directional dependence of hydrogen bonding (HB). Here we aim to better understand the origin of this difficulty and thus provide some guidance for further force field development. Our theoretical approaches center on a novel density-based energy decomposition analysis (DEDA) method [J. Chem. Phys., 131, 164112 (2009)], in which the frozen density energy is variationally determined through constrained search. This unique and most significant feature of DEDA enables us to find that the frozen density interaction term is the key factor in determining the HB orientation, while the sum of polarization and charge-transfer components shows very little HB directional dependence. This new insight suggests that the difficulty for current non-polarizable force fields to describe the HB directional dependence is not due to the lack of explicit polarization or charge-transfer terms. Using the DEDA results as reference, we further demonstrate that the main failure coming from the atomic point charge model can be overcome largely by introducing extra charge sites or higher order multipole moments. Among all the electrostatic models explored, the smeared charge distributed multipole model (up to quadrupole), which also takes account of charge penetration effects, gives the best agreement with the corresponding DEDA results. Meanwhile, our results indicate that the van der Waals interaction term needs to be further improved to better model directional hydrogen bonding. PMID:22267958

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

NASA Astrophysics Data System (ADS)

Sun, Hongyan; Vaghjiani, Ghanshyam L.

2015-05-01

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358-366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

Ab Initio Kinetics and Thermal Decomposition Mechanism of Mononitrobiuret and 1,5- Dinitrobiuret

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

Sun, Hongyan; Vaghjiani, Ghanshyam G.

2015-05-26

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was foundmore » that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358–366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.« less

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret.

PubMed

Sun, Hongyan; Vaghjiani, Ghanshyam L

2015-05-28

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was found that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH2 group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C2v symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice-Ramsperger-Kassel-Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO2 + H2O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358-366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.

The Effect of Body Mass on Outdoor Adult Human Decomposition.

PubMed

Roberts, Lindsey G; Spencer, Jessica R; Dabbs, Gretchen R

2017-09-01

Forensic taphonomy explores factors impacting human decomposition. This study investigated the effect of body mass on the rate and pattern of adult human decomposition. Nine males and three females aged 49-95 years ranging in mass from 73 to 159 kg who were donated to the Complex for Forensic Anthropology Research between December 2012 and September 2015 were included in this study. Kelvin accumulated degree days (KADD) were used to assess the thermal energy required for subjects to reach several total body score (TBS) thresholds: early decomposition (TBS ≥6.0), TBS ≥12.5, advanced decomposition (TBS ≥19.0), TBS ≥23.0, and skeletonization (TBS ≥27.0). Results indicate no significant correlation between body mass and KADD at any TBS threshold. Body mass accounted for up to 24.0% of variation in decomposition rate depending on stage, and minor differences in decomposition pattern were observed. Body mass likely has a minimal impact on postmortem interval estimation. © 2017 American Academy of Forensic Sciences.

Transport, anoxia and energy control on anaerobic respiration and methanogenesis in anoxic peat soils

NASA Astrophysics Data System (ADS)

Bonaiuti, Simona; Blodau, Christian; Knorr, Klaus-Holger

2017-04-01

In deep and permanently water saturated peat deposits, extremely low diffusive transport and concomitant build-up of metabolic end-products, i.e of dissolved inorganic carbon (DIC) and methane (CH4), have been found to slow-down anaerobic respiration and methanogenesis. Such accumulation of DIC and CH4 lowers the Gibbs free energy yield of terminal respiration and methanogenesis, which can inhibit the course of anaerobic metabolic processes. In particular, this affects terminal steps of the breakdown of organic carbon (C), such as methanogenesis, acetogenesis and fermentation processes, which occur near thermodynamic minimum energy thresholds. This effect is thus of critical importance for the long-term C sequestration, as the slow-down of decomposition ultimately regulates the long-term fate of C in deep peat deposits. The exact controls of this observed slow-down of organic matter mineralization are not yet fully understood. Moreover, altered patterns of water or gas transport due to predicted changes in climate may affect these controls in peat soils. Therefore, the aim of this study was to investigate how burial of peat leads to an inactivation of anaerobic decomposition and to investigate the effects of advective water transport and persistently anoxic conditions on anaerobic decomposition, temporal evolution of thermodynamic energy yields to methanogenesis and methanogenic pathways. To this end, we conducted a column experiment with homogenized, ombrotrophic peat over a period of 300 days at 20˚ C. We tested i) a control treatment under diffusive transport only, ii) an advective flow treatment with a flow of 10 mm d-1, and iv) an anoxic treatment to evaluate changes in decomposition in absence of oxygen in the unsaturated zone of the cores. A slow-down of anaerobic respiration and methanogenesis generally set in at larger depths after 150 days at CH4 concentrations of 0.6-0.9 mmol L-1 and DIC concentrations of 6-12 mmol L-1. This effect occurred at higher concentration levels and faster than previously observed. Advective water transport effectively extended the zone of methanogenesis down to 40 cm depth until inhibiting conditions were reached, although net turnover at greater depths was not affected. Strictly anoxic conditions in the unsaturated zone, where diffusive transport is high, had little effect on accelerating anaerobic decomposition. The slow-down of net production rates of CO2 and CH4 agreed well with the decline over time of Gibbs free energies available to methanogenesis, supporting a thermodynamic constraint on decomposition in deeper peat deposits. Keywords: Peatlands; Anaerobic decomposition; Methanogenesis; Production rates; Advection; Anoxia; Thermodynamic calculations.

Computation of forces arising from the polarizable continuum model within the domain-decomposition paradigm

NASA Astrophysics Data System (ADS)

Gatto, Paolo; Lipparini, Filippo; Stamm, Benjamin

2017-12-01

The domain-decomposition (dd) paradigm, originally introduced for the conductor-like screening model, has been recently extended to the dielectric Polarizable Continuum Model (PCM), resulting in the ddPCM method. We present here a complete derivation of the analytical derivatives of the ddPCM energy with respect to the positions of the solute's atoms and discuss their efficient implementation. As it is the case for the energy, we observe a quadratic scaling, which is discussed and demonstrated with numerical tests.

Design and Scheduling of Microgrids using Benders Decomposition

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

Nagarajan, Adarsh; Ayyanar, Raja

2016-11-21

The distribution feeder laterals in a distribution feeder with relatively high PV generation as compared to the load can be operated as microgrids to achieve reliability, power quality and economic benefits. However, renewable resources are intermittent and stochastic in nature. A novel approach for sizing and scheduling an energy storage system and microturbine for reliable operation of microgrids is proposed. The size and schedule of an energy storage system and microturbine are determined using Benders' decomposition, considering PV generation as a stochastic resource.

Investigation of thermodynamic parameters in the thermal decomposition of plastic waste-waste lube oil compounds.

PubMed

Kim, Yong Sang; Kim, Young Seok; Kim, Sung Hyun

2010-07-01

Thermal decomposition properties of plastic waste-waste lube oil compounds were investigated under nonisothermal conditions. Polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET) were selected as representative household plastic wastes. A plastic waste mixture (PWM) and waste lube oil (WLO) were mixed with mixing ratios of 33, 50, and 67 (w/w) % on a PWM weight basis, and thermogravimetric (TG) experiments were performed from 25 to 600 degrees C. The Flynn-Wall method and the Ozawa-Flynn-Wall method were used for analyses of thermodynamic parameters. In this study, activation energies of PWM/WLO compounds ranged from 73.4 to 229.6 kJ/mol between 0.2 and 0.8 of normalized mass conversions, and the 50% PWM/WLO compound had lower activation energies and enthalpies among the PWM/WLO samples at each mass conversion. At the point of maximum differential mass conversion, the analyzed activation energies, enthalpies, entropies, and Gibbs free energies indicated that mixing PWM and WLO has advantages in reducing energy to decrease the degree of disorder. However, no difference in overall energy that would require overcoming both thermal decomposition reactions and degree of disorder was observed among PWM/WLO compounds under these experimental conditions.

Study on Influencing Factors of Carbon Emissions from Energy Consumption of Shandong Province of China from 1995 to 2012

PubMed Central

Song, Jiekun; Song, Qing; Zhang, Dong; Lu, Youyou; Luan, Long

2014-01-01

Carbon emissions from energy consumption of Shandong province from 1995 to 2012 are calculated. Three zero-residual decomposition models (LMDI, MRCI and Shapley value models) are introduced for decomposing carbon emissions. Based on the results, Kendall coordination coefficient method is employed for testing their compatibility, and an optimal weighted combination decomposition model is constructed for improving the objectivity of decomposition. STIRPAT model is applied to evaluate the impact of each factor on carbon emissions. The results show that, using 1995 as the base year, the cumulative effects of population, per capita GDP, energy consumption intensity, and energy consumption structure of Shandong province in 2012 are positive, while the cumulative effect of industrial structure is negative. Per capita GDP is the largest driver of the increasing carbon emissions and has a great impact on carbon emissions; energy consumption intensity is a weak driver and has certain impact on carbon emissions; population plays a weak driving role, but it has the most significant impact on carbon emissions; energy consumption structure is a weak driver of the increasing carbon emissions and has a weak impact on carbon emissions; industrial structure has played a weak inhibitory role, and its impact on carbon emissions is great. PMID:24977216

Essays on the Determinants of Energy Related CO2 Emissions =

NASA Astrophysics Data System (ADS)

Moutinho, Victor Manuel Ferreira

Overall, amongst the most mentioned factors for Greenhouse Gases (GHG) growth are the economic growth and the energy demand growth. To assess the determinants GHG emissions, this thesis proposed and developed a new analysis which links the emissions intensity to its main driving factors. In the first essay, we used the 'complete decomposition' technique to examine CO2 emissions intensity and its components, considering 36 economic sectors and the 1996-2009 periods in Portugal. The industry (in particular 5 industrial sectors) is contributing largely to the effects of variation of CO2 emissions intensity. We concluded, among others, the emissions intensity reacts more significantly to shocks in the weight of fossil fuels in total energy consumption compared to shocks in other variables. In the second essay, we conducted an analysis for 16 industrial sectors (Group A) and for the group of the 5 most polluting manufacturing sectors (Group B) based on the convergence examination for emissions intensity and its main drivers, as well as on an econometric analysis. We concluded that there is sigma convergence for all the effects with exception to the fossil fuel intensity, while gamma convergence was verified for all the effects, with exception of CO2 emissions by fossil fuel and fossil fuel intensity in Group B. From the econometric approach we concluded that the considered variables have a significant importance in explaining CO2 emissions and CO2 emissions intensity. In the third essay, the Tourism Industry in Portugal over 1996-2009 period was examined, specifically two groups of subsectors that affect the impacts on CO2 emissions intensity. The generalized variance decomposition and the impulse response functions pointed to sectors that affect tourism more directly, i. e. a bidirectional causality between the intensity of emissions and energy intensity. The effect of intensity of emissions is positive on energy intensity, and the effect of energy intensity on emissions intensity is negative. The percentage of fossil fuels used reacts positively to the economic structure and to carbon intensity, i. e., the more the economic importance of the sector, the more it uses fossil fuels, and when it raises its carbon intensity, in the future the use of fossil fuel may rise. On the other hand, positive shocks on energy intensity tend to reduce the percentage of fossil fuels used. In fourth essay, we conducted an analysis to identify the effects that contribute to the intensity of GHG emissions (EI) in agriculture as well as their development. With that aim, we used the 'complete decomposition' technique in the 1995-2008 periods, for a set of European countries. It is shown that the use of Nitrogen per cultivated area is an important factor of emissions and in those countries where labour productivity increases (the inverse of average labour productivity in agriculture decreases), emissions intensity tends to decrease. These results imply that the way to reduce emissions in agriculture would be to provide better training of agricultural workers to increase their productivity, which would lead to a less need for energy and use of Nitrogen. The purpose of the last essay is to examine the long and short-run causality of the share of renewable sources on the environmental relation CO2 per KWh electricity generation- real GDP for 20 European countries over the 2001-2010 periods. It is important to analyze how the percentage of renewable energy used for electricity production affects the relationship between economic growth and emissions from this sector. The study of these relationships is important from the point of view of environmental and energy policy as it gives us information on the costs in terms of economic growth, on the application of restrictive levels of emissions and also on the effects of the policies concerning the use of renewable energy in the electricity sector (see for instance European Commission Directive 2001/77/EC, [4]). For that purpose, in this study we use Cointegration Analysis on the set of cross-country panel data between CO2 emissions from electricity generation (CO2 kWh), economic growth (GDP) and the share of renewable energy for 20 European countries. We estimated the long-run equilibrium to validate the EKC with a new approach specification. Additionally, we have implemented the Innovative Accounting Approach (IAA) that includes Forecast Error Variance Decomposition and Impulse Response Functions (IRFs), applied to those variables. This can allow us, for example, to know (i) how CO2 kWh responds to an impulse in GDP and (ii) how CO2 kWh responds to an impulse in the share of renewable sources. The contributions of this thesis to the energy-related CO2 emissions at sectorial level are threefold: First, it provides a new econometric decomposition approach for analysing and developing CO2 emissions in collaboration with science societies that can serve as a starting point for future research approaches. Second, it presents a hybrid energy-economy mathematic and econometric model which relates CO2 emissions in Portugal based on economic theory. Third, it contributes to explain the change of CO2 emissions in important economic sectors in Europe, in particular in Portugal, taking normative considerations into account more openly and explicitly, with political implications at energy-environment level within the European commitment. None

Focused-based multifractal analysis of the wake in a wind turbine array utilizing proper orthogonal decomposition

NASA Astrophysics Data System (ADS)

Kadum, Hawwa; Ali, Naseem; Cal, Raúl

2016-11-01

Hot-wire anemometry measurements have been performed on a 3 x 3 wind turbine array to study the multifractality of the turbulent kinetic energy dissipations. A multifractal spectrum and Hurst exponents are determined at nine locations downstream of the hub height, and bottom and top tips. Higher multifractality is found at 0.5D and 1D downstream of the bottom tip and hub height. The second order of the Hurst exponent and combination factor show an ability to predict the flow state in terms of its development. Snapshot proper orthogonal decomposition is used to identify the coherent and incoherent structures and to reconstruct the stochastic velocity using a specific number of the POD eigenfunctions. The accumulation of the turbulent kinetic energy in top tip location exhibits fast convergence compared to the bottom tip and hub height locations. The dissipation of the large and small scales are determined using the reconstructed stochastic velocities. The higher multifractality is shown in the dissipation of the large scale compared to small-scale dissipation showing consistency with the behavior of the original signals.

Geometric decompositions of collective motion

NASA Astrophysics Data System (ADS)

Mischiati, Matteo; Krishnaprasad, P. S.

2017-04-01

Collective motion in nature is a captivating phenomenon. Revealing the underlying mechanisms, which are of biological and theoretical interest, will require empirical data, modelling and analysis techniques. Here, we contribute a geometric viewpoint, yielding a novel method of analysing movement. Snapshots of collective motion are portrayed as tangent vectors on configuration space, with length determined by the total kinetic energy. Using the geometry of fibre bundles and connections, this portrait is split into orthogonal components each tangential to a lower dimensional manifold derived from configuration space. The resulting decomposition, when interleaved with classical shape space construction, is categorized into a family of kinematic modes-including rigid translations, rigid rotations, inertia tensor transformations, expansions and compressions. Snapshots of empirical data from natural collectives can be allocated to these modes and weighted by fractions of total kinetic energy. Such quantitative measures can provide insight into the variation of the driving goals of a collective, as illustrated by applying these methods to a publicly available dataset of pigeon flocking. The geometric framework may also be profitably employed in the control of artificial systems of interacting agents such as robots.

Geometric decompositions of collective motion

PubMed Central

Krishnaprasad, P. S.

2017-01-01

Collective motion in nature is a captivating phenomenon. Revealing the underlying mechanisms, which are of biological and theoretical interest, will require empirical data, modelling and analysis techniques. Here, we contribute a geometric viewpoint, yielding a novel method of analysing movement. Snapshots of collective motion are portrayed as tangent vectors on configuration space, with length determined by the total kinetic energy. Using the geometry of fibre bundles and connections, this portrait is split into orthogonal components each tangential to a lower dimensional manifold derived from configuration space. The resulting decomposition, when interleaved with classical shape space construction, is categorized into a family of kinematic modes—including rigid translations, rigid rotations, inertia tensor transformations, expansions and compressions. Snapshots of empirical data from natural collectives can be allocated to these modes and weighted by fractions of total kinetic energy. Such quantitative measures can provide insight into the variation of the driving goals of a collective, as illustrated by applying these methods to a publicly available dataset of pigeon flocking. The geometric framework may also be profitably employed in the control of artificial systems of interacting agents such as robots. PMID:28484319

Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.

PubMed

Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Wu, Joan; Chen, Shulin

2016-11-01

The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input. Copyright © 2016 Elsevier Ltd. All rights reserved.

Changes in Root Decomposition Rates Across Soil Depths

NASA Astrophysics Data System (ADS)

Hicks Pries, C.; Porras, R. C.; Castanha, C.; Torn, M. S.

2016-12-01

Over half of global soil organic carbon (SOC) is stored in subsurface soils (>30 cm). Turnover times of soil organic carbon (SOC) increases with depth as evidenced by radiocarbon ages of 1,000 to more than 10,000 years in many deep soil horizons but the reasons for this increase are unclear. Many factors that potentially control SOC decomposition change with depth such as increased protection of SOC in aggregates or organo-mineral complexes and increased spatial heterogeneity of SOC "hotspots" like roots, which limit the accessibility of SOC to microbes. Lower concentrations of organic matter at depth may inhibit microbial activity due to energy limitation, and the microbial community itself changes with depth. To investigate how SOC decomposition differs with depth, we inserted a 13C-labeled fine root substrate into three depths (15, 50, and 90 cm) in a coniferous forest Alfisol and measured the root carbon remaining in particulate (>2 mm), bulk (< 2mm), free light, and mineral soil fractions over 2.5 years. We also characterized how the microbial community and SOC changed with depth. Initial rates of decomposition were unaffected by soil depth—50% of root carbon was lost from all depths within the first year. However, after 2.5 years, decomposition rates were affected by soil depth with only 15% of the root carbon remaining at 15 cm while 35% remained at 90 cm. Microbial communities, based on phospholipid fatty acid analysis, changed with depth—fungal biomarkers decreased whereas actinomycetes biomarkers increased. However, the preferences of different microbial groups for the 13C-labeled root carbon were consistent with depth. In contrast, the amount of mineral-associated SOC did not change with depth. Thus, decreased decomposition rates in this deep soil are not due to mineral associations limiting SOC availability, but may instead be due to changes in microbial communities, particularly in the microbes needed to carry out the later stages of root decomposition.

Enhanced Thermal Decomposition Properties of CL-20 through Space-Confining in Three-Dimensional Hierarchically Ordered Porous Carbon.

PubMed

Chen, Jin; He, Simin; Huang, Bing; Wu, Peng; Qiao, Zhiqiang; Wang, Jun; Zhang, Liyuan; Yang, Guangcheng; Huang, Hui

2017-03-29

High energy and low signature properties are the future trend of solid propellant development. As a new and promising oxidizer, hexanitrohexaazaisowurtzitane (CL-20) is expected to replace the conventional oxidizer ammonium perchlorate to reach above goals. However, the high pressure exponent of CL-20 hinders its application in solid propellants so that the development of effective catalysts to improve the thermal decomposition properties of CL-20 still remains challenging. Here, 3D hierarchically ordered porous carbon (3D HOPC) is presented as a catalyst for the thermal decomposition of CL-20 via synthesizing a series of nanostructured CL-20/HOPC composites. In these nanocomposites, CL-20 is homogeneously space-confined into the 3D HOPC scaffold as nanocrystals 9.2-26.5 nm in diameter. The effect of the pore textural parameters and surface modification of 3D HOPC as well as CL-20 loading amount on the thermal decomposition of CL-20 is discussed. A significant improvement of the thermal decomposition properties of CL-20 is achieved with remarkable decrease in decomposition peak temperature (from 247.0 to 174.8 °C) and activation energy (from 165.5 to 115.3 kJ/mol). The exceptional performance of 3D HOPC could be attributed to its well-connected 3D hierarchically ordered porous structure, high surface area, and the confined CL-20 nanocrystals. This work clearly demonstrates that 3D HOPC is a superior catalyst for CL-20 thermal decomposition and opens new potential for further applications of CL-20 in solid propellants.

Let's Break it Down: A Study of Organic Decomposition Rates in Clay Soil

NASA Astrophysics Data System (ADS)

Weiss, E.

2016-12-01

In this experiment I will be testing if temperature affects the organic decomposition rates in clay soil. I will need to be able to clean and weigh each filter paper without disrupting my data damaging or brushing off additional paper material. From there I need to be able to analyze and interpret my data to factor anything else that may affect the decomposition rates in the soil. Soil decomposers include bacteria and fungi. They obtain energy from plant and animal detritus through aerobic decomposition, which is similar to how humans break down sugar. The formula is: C6H12O6 + O2 → CO2 + H2O + energy. Besides oxygen and sugar the organisms need nutrients such as water and sustainable temperatures. Decomposition is important to us because it helps regulate soil structure, moisture, temperature, and provides nutrients to soil organisms. This matters on a global scale since decomposers release a large amount of carbon when breaking down matter, which contributes to greenhouse gasses such as carbon dioxide and methane. These greenhouse gasses affect the earth's climate. People who care about decomposition are farmers and those in agriculture, as well as environmental scientists. Even national parks might care because decomposition may affect park safety, how the park looks, and the amount of plants and wildlife. Things that can affect decomposition are the decomposers in the soil, temperature, and water or moisture. My secondary research also showed that PH and chemical composition of the soil affect the rate of decomposition.Cold or freezing temperatures can help preserve organic material in soil because it freezes the soil and moisture, making it too dense for the organic decomposers to break down the organic matter. Soil also can be preserved by drying out and being stored at 4º Celsius (or 39º Fahrenheit) for 28 days. However, soil can degrade slowly in these conditions because it is not frozen and can be oxidized.

Thermal decomposition characteristics of microwave liquefied rape straw residues using thermogravimetric analysis

Treesearch

Xingyan Huang; Cornelis F. De Hoop; Jiulong Xie; Chung-Yun Hse; Jinqiu Qi; Yuzhu Chen; Feng Li

2017-01-01

The thermal decomposition characteristics of microwave liquefied rape straw residues with respect to liquefaction condition and pyrolysis conversion were investigated using a thermogravimetric (TG) analyzer at the heating rates of 5, 20, 50 °C min-1. The hemicellulose decomposition peak was absent at the derivative thermogravimetric analysis (DTG...

Interfacial contributions of H2O2 decomposition-induced reaction current on mesoporous Pt/TiO2 systems

NASA Astrophysics Data System (ADS)

Ray, Nathan J.; Styrov, Vladislav V.; Karpov, Eduard G.

2017-12-01

We report on conversion of energy released due to chemical reactions into current for the decomposition of aqueous hydrogen peroxide solution on single phases Pt and TiO2, in addition to Pt and TiO2 simultaneously. We observe that H2O2 decomposition-induced current on TiO2 drastically overshadows the current generated by H2O2 decomposition on Pt. Photo-effects avoided, H2O2 decomposition was found to yield a conversion efficiency of 10-3 electrons generated per H2O2 molecule. Further understanding of chemical reaction-induced current shows promise as a metric with which the surface reaction may be monitored and could be greatly extended into the field of analytical chemistry.

Alternative separation of exchange and correlation energies in multi-configuration range-separated density-functional theory.

PubMed

Stoyanova, Alexandrina; Teale, Andrew M; Toulouse, Julien; Helgaker, Trygve; Fromager, Emmanuel

2013-10-07

The alternative separation of exchange and correlation energies proposed by Toulouse et al. [Theor. Chem. Acc. 114, 305 (2005)] is explored in the context of multi-configuration range-separated density-functional theory. The new decomposition of the short-range exchange-correlation energy relies on the auxiliary long-range interacting wavefunction rather than the Kohn-Sham (KS) determinant. The advantage, relative to the traditional KS decomposition, is that the wavefunction part of the energy is now computed with the regular (fully interacting) Hamiltonian. One potential drawback is that, because of double counting, the wavefunction used to compute the energy cannot be obtained by minimizing the energy expression with respect to the wavefunction parameters. The problem is overcome by using short-range optimized effective potentials (OEPs). The resulting combination of OEP techniques with wavefunction theory has been investigated in this work, at the Hartree-Fock (HF) and multi-configuration self-consistent-field (MCSCF) levels. In the HF case, an analytical expression for the energy gradient has been derived and implemented. Calculations have been performed within the short-range local density approximation on H2, N2, Li2, and H2O. Significant improvements in binding energies are obtained with the new decomposition of the short-range energy. The importance of optimizing the short-range OEP at the MCSCF level when static correlation becomes significant has also been demonstrated for H2, using a finite-difference gradient. The implementation of the analytical gradient for MCSCF wavefunctions is currently in progress.

Thermal decomposition of 1,3,3-trinitroazetidine (TNAZ): A density functional theory and ab initio study

NASA Astrophysics Data System (ADS)

Veals, Jeffrey D.; Thompson, Donald L.

2014-04-01

Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO2 elimination by N-N and C-N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO2 group elimination or by a concerted H-atom and nitroalkyl NO2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO2 elimination by N-N bond fission, HONO elimination involving the nitramine NO2 group, HONO elimination involving a nitroalkyl NO2 group, and finally NO2 elimination by C-N bond fission.

Domain decomposition for aerodynamic and aeroacoustic analyses, and optimization

NASA Technical Reports Server (NTRS)

Baysal, Oktay

1995-01-01

The overarching theme was the domain decomposition, which intended to improve the numerical solution technique for the partial differential equations at hand; in the present study, those that governed either the fluid flow, or the aeroacoustic wave propagation, or the sensitivity analysis for a gradient-based optimization. The role of the domain decomposition extended beyond the original impetus of discretizing geometrical complex regions or writing modular software for distributed-hardware computers. It induced function-space decompositions and operator decompositions that offered the valuable property of near independence of operator evaluation tasks. The objectives have gravitated about the extensions and implementations of either the previously developed or concurrently being developed methodologies: (1) aerodynamic sensitivity analysis with domain decomposition (SADD); (2) computational aeroacoustics of cavities; and (3) dynamic, multibody computational fluid dynamics using unstructured meshes.

Decomposition of naphthalene by dc gliding arc gas discharge.

PubMed

Yu, Liang; Li, Xiaodong; Tu, Xin; Wang, Yu; Lu, Shengyong; Yan, Jianhua

2010-01-14

Gliding arc discharge has been proved to be effective in treatment of gas and liquid contaminants. In this study, physical characteristics of dc gliding arc discharge and its application to naphthalene destruction are investigated with different external resistances and carrier gases. The decomposition rate increases with increasing of oxygen concentration and decreases with external resistance. This value can be achieved up to 92.3% at the external resistance of 50 kOmega in the oxygen discharge, while the highest destruction energy efficiency reaches 3.6 g (kW h)(-1) with the external resistance of 93 kOmega. Possible reaction pathways and degradation mechanisms in the plasma with different gases are proposed by qualitative analysis of postdestructed products. In the air and oxygen gliding arc discharges, the naphthalene degradation is mainly governed by reactions with oxygen-derived radicals.

Feature extraction and identification in distributed optical-fiber vibration sensing system for oil pipeline safety monitoring

NASA Astrophysics Data System (ADS)

Wu, Huijuan; Qian, Ya; Zhang, Wei; Tang, Chenghao

2017-12-01

High sensitivity of a distributed optical-fiber vibration sensing (DOVS) system based on the phase-sensitivity optical time domain reflectometry (Φ-OTDR) technology also brings in high nuisance alarm rates (NARs) in real applications. In this paper, feature extraction methods of wavelet decomposition (WD) and wavelet packet decomposition (WPD) are comparatively studied for three typical field testing signals, and an artificial neural network (ANN) is built for the event identification. The comparison results prove that the WPD performs a little better than the WD for the DOVS signal analysis and identification in oil pipeline safety monitoring. The identification rate can be improved up to 94.4%, and the nuisance alarm rate can be effectively controlled as low as 5.6% for the identification network with the wavelet packet energy distribution features.

On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts

DOE PAGES

Li, Sha; Scaranto, Jessica; Mavrikakis, Manos

2016-08-03

Catalytic decomposition of formic acid (HCOOH) has attracted substantial attention since HCOOH is a major by-product in biomass reforming, a promising hydrogen carrier, and also a potential low temperature fuel cell feed. Despite the abundance of experimental studies for vapor-phase HCOOH decomposition on Cu catalysts, the reaction mechanism and its structure sensitivity is still under debate. In this work, self-consistent, periodic density functional theory calculations were performed on three model surfaces of copper—Cu(111), Cu(100) and Cu(211), and both the HCOO (formate)-mediated and COOH (carboxyl)-mediated pathways were investigated for HCOOH decomposition. The energetics of both pathways suggest that the HCOO-mediated routemore » is more favorable than the COOH-mediated route on all three surfaces, and that HCOOH decomposition proceeds through two consecutive dehydrogenation steps via the HCOO intermediate followed by the recombinative desorption of H 2. On all three surfaces, HCOO dehydrogenation is the likely rate determining step since it has the highest transition state energy and also the highest activation energy among the three catalytic steps in the HCOO pathway. The reaction is structure sensitive on Cu catalysts since the examined three Cu facets have dramatically different binding strengths for the key intermediate HCOO and varied barriers for the likely rate determining step—HCOO dehydrogenation. Cu(100) and Cu(211) bind HCOO much more strongly than Cu(111), and they are also characterized by potential energy surfaces that are lower in energy than that for the Cu(111) facet. Coadsorbed HCOO and H represents the most stable state along the reaction coordinate, indicating that, under reaction conditions, there might be a substantial surface coverage of the HCOO intermediate, especially at under-coordinated step, corner or defect sites. Therefore, under reaction conditions, HCOOH decomposition is predicted to occur most readily on the terrace sites of Cu nanoparticles. Finally, as a result, we hereby present an example of a fundamentally structure-sensitive reaction, which may present itself as structure-insensitive in typical varied particle-size experiments.« less

Diversity has stronger top-down than bottom-up effects on decomposition.

PubMed

Srivastava, Diane S; Cardinale, Bradley J; Downing, Amy L; Duffy, J Emmett; Jouseau, Claire; Sankaran, Mahesh; Wright, Justin P

2009-04-01

The flow of energy and nutrients between trophic levels is affected by both the trophic structure of food webs and the diversity of species within trophic levels. However, the combined effects of trophic structure and diversity on trophic transfer remain largely unknown. Here we ask whether changes in consumer diversity have the same effect as changes in resource diversity on rates of resource consumption. We address this question by focusing on consumer-resource dynamics for the ecologically important process of decomposition. This study compares the top-down effect of consumer (detritivore) diversity on the consumption of dead organic matter (decomposition) with the bottom-up effect of resource (detrital) diversity, based on a compilation of 90 observations reported in 28 studies. We did not detect effects of either detrital or consumer diversity on measures of detrital standing stock, and effects on consumer standing stock were equivocal. However, our meta-analysis indicates that reductions in detritivore diversity result in significant reductions in the rate of decomposition. Detrital diversity has both positive and negative effects on decomposition, with no overall trend. This difference between top-down and bottom-up effects of diversity is robust to different effect size metrics and could not be explained by differences in experimental systems or designs between detritivore and detrital manipulations. Our finding that resource diversity has no net effect on consumption in "brown" (detritus-consumer) food webs contrasts with previous findings from "green" (plant-herbivore) food webs and suggests that effects of plant diversity on consumption may fundamentally change after plant death.

Photoluminescence properties of Tb3Al5O12:Ce3+ garnet synthesized by the metal organic decomposition method

NASA Astrophysics Data System (ADS)

Onishi, Yuya; Nakamura, Toshihiro; Adachi, Sadao

2017-02-01

Tb3Al5O12:Ce3+ garnet (TAG:Ce3+) phosphor was synthesized by the metal organic decomposition (MOD) method and subsequent calcination at Tc = 800-1200°C for 1 h in air. The effects of Ce3+ concentration on the phosphor properties were investigated in detail using X-ray diffraction (XRD) analysis, photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and PL decay measurements. The maximum intensity in the Ce3+ yellow emission was observed at the Ce3+ concentration of ∼0.20%. PLE and PL decay measurements suggested an evidence of the energy transfer from Tb3+ to Ce3+. Calcination temperature dependence of the XRD and PL intensities yielded an energy of ∼1.5 eV both for the TAG formation in the MOD process and for the optical activation of Ce3+ in its lattice sites. Temperature dependences of the PL intensity for the TAG:Ce3+ yellow-emitting and K2SiF6:Mn4+ red-emitting phosphors were also examined for the future solid-state lighting applications at T = 20-500 K in 10-K steps. The data of TAG:Ce3+ were analyzed using a theoretical model with considering a reservoir level of Et ∼9 meV, yielding a quenching energy of Eq ∼0.35 eV, whereas the K2SiF6:Mn4+ red-emitting phosphor data yielded a value of Eq ∼1.0 eV. The schematic energy-level diagrams for Tb3+ and Ce3+ were proposed for the sake of a better understanding of these ions in the TAG host.

Oxidovanadium(IV) complexes involving dehydroacetic acid and β-diketones of bioinorganic and medicinal relevance: Their synthesis, characterization, thermal behavior and DFT aspects

NASA Astrophysics Data System (ADS)

Maurya, R. C.; Malik, B. A.; Mir, J. M.; Vishwakarma, P. K.

2015-03-01

Six new mixed-ligand complexes of oxidovanadium(IV) of the general composition [VO(dha)(L)(H2O)], where dhaH = dehydroacetic acid, LH = β-diketones, viz., acetoacetanilide (aaaH), o-acetoacetotoluidide (o-aatdH), o-acetoacetanisidide (o-aansH), acetylacetone (acacH), methyl acetoacetate (macacH) or ethyl acetoacetate (eacacH) have been synthesized by the reaction of VOSO4ṡ5H2O and the ligands given above in aqueous-ethanol medium. The resulting complexes have been characterized on the basis of elemental analyses, vanadium determination, molar conductance and magnetic measurements, mass spectrometry, thermogravimetric analysis, infrared and electron spin resonance spectral studies. The thermal decomposition processes of two representative complexes are discussed and the order of reaction (n) and the activation energy (Ea) for the particular decomposition steps have been calculated from thermogravimetric (TG) curve. Geometry optimizations were performed with the Gaussian 09 software package by using density functional theory (DFT) methods with Becke-3-Lee-Yang-Parr (B3LYP) hybrid exchange-correlation functional and the standard LANL2 MB basis set for dhaH and its complex [VO(dha)(acac)(H2O)]. Molecular surface electrostatic potentials (MSEP), vibrational frequency calculations, bond lengths, bond angles, dihedral angles, natural population analysis and calculations of molecular energies, HOMO and LUMO were made. No imaginary frequency was found in the optimized model compounds and hence ensures that the molecule is in the lowest point of the potential energy surface, that is, a energy minimum. Finally calculated results were applied to simulated Infrared spectra of the title compound which show good agreement with observed spectra. Based on experimental and theoretical data, suitable trans-octahedral structures have been proposed for these complexes.

MO-FG-204-03: Using Edge-Preserving Algorithm for Significantly Improved Image-Domain Material Decomposition in Dual Energy CT

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

Zhao, W; Niu, T; Xing, L

2015-06-15

Purpose: To significantly improve dual energy CT (DECT) imaging by establishing a new theoretical framework of image-domain material decomposition with incorporation of edge-preserving techniques. Methods: The proposed algorithm, HYPR-NLM, combines the edge-preserving non-local mean filter (NLM) with the HYPR-LR (Local HighlY constrained backPRojection Reconstruction) framework. Image denoising using HYPR-LR framework depends on the noise level of the composite image which is the average of the different energy images. For DECT, the composite image is the average of high- and low-energy images. To further reduce noise, one may want to increase the window size of the filter of the HYPR-LR, leadingmore » resolution degradation. By incorporating the NLM filtering and the HYPR-LR framework, HYPR-NLM reduces the boost material decomposition noise using energy information redundancies as well as the non-local mean. We demonstrate the noise reduction and resolution preservation of the algorithm with both iodine concentration numerical phantom and clinical patient data by comparing the HYPR-NLM algorithm to the direct matrix inversion, HYPR-LR and iterative image-domain material decomposition (Iter-DECT). Results: The results show iterative material decomposition method reduces noise to the lowest level and provides improved DECT images. HYPR-NLM significantly reduces noise while preserving the accuracy of quantitative measurement and resolution. For the iodine concentration numerical phantom, the averaged noise levels are about 2.0, 0.7, 0.2 and 0.4 for direct inversion, HYPR-LR, Iter- DECT and HYPR-NLM, respectively. For the patient data, the noise levels of the water images are about 0.36, 0.16, 0.12 and 0.13 for direct inversion, HYPR-LR, Iter-DECT and HYPR-NLM, respectively. Difference images of both HYPR-LR and Iter-DECT show edge effect, while no significant edge effect is shown for HYPR-NLM, suggesting spatial resolution is well preserved for HYPR-NLM. Conclusion: HYPR-NLM provides an effective way to reduce the generic magnified image noise of dual–energy material decomposition while preserving resolution. This work is supported in part by NIH grants 7R01HL111141 and 1R01-EB016777. This work is also supported by the Natural Science Foundation of China (NSFC Grant No. 81201091), Fundamental Research Funds for the Central Universities in China, and Fund Project for Excellent Abroad Scholar Personnel in Science and Technology.« less

Analysis and Prediction of Sea Ice Evolution using Koopman Mode Decomposition Techniques

DTIC Science & Technology

2018-04-30

Title: Analysis and Prediction of Sea Ice Evolution using Koopman Mode Decomposition Techniques Subject: Monthly Progress Report Period of...Resources: N/A TOTAL: $18,687 2 TECHNICAL STATUS REPORT Abstract The program goal is analysis of sea ice dynamical behavior using Koopman Mode Decompo...sition (KMD) techniques. The work in the program’s first month consisted of improvements to data processing code, inclusion of additional arctic sea ice

Analysis of cured carbon-phenolic decomposition products to investigate the thermal decomposition of nozzle materials

NASA Technical Reports Server (NTRS)

Thompson, James M.; Daniel, Janice D.

1989-01-01

The development of a mass spectrometer/thermal analyzer/computer (MS/TA/Computer) system capable of providing simultaneous thermogravimetry (TG), differential thermal analysis (DTA), derivative thermogravimetry (DTG) and evolved gas detection and analysis (EGD and EGA) under both atmospheric and high pressure conditions is described. The combined system was used to study the thermal decomposition of the nozzle material that constitutes the throat of the solid rocket boosters (SRB).

Synthesis and Electrocatalytic Activity of Ammonium Nickel Phosphate, [NH4]NiPO4·6H2O, and β-Nickel Pyrophosphate, β-Ni2P2O7: Catalysts for Electrocatalytic Decomposition of Urea.

PubMed

Meguerdichian, Andrew G; Jafari, Tahereh; Shakil, Md R; Miao, Ran; Achola, Laura A; Macharia, John; Shirazi-Amin, Alireza; Suib, Steven L

2018-02-19

Electrocatalytic decomposition of urea for the production of hydrogen, H 2, for clean energy applications, such as in fuel cells, has several potential advantages such as reducing carbon emissions in the energy sector and environmental applications to remove urea from animal and human waste facilities. The study and development of new catalyst materials containing nickel metal, the active site for urea decomposition, is a critical aspect of research in inorganic and materials chemistry. We report the synthesis and application of [NH 4 ]NiPO 4 ·6H 2 O and β-Ni 2 P 2 O 7 using in situ prepared [NH 4 ] 2 HPO 4 . The [NH 4 ]NiPO 4 ·6H 2 O is calcined at varying temperatures and tested for electrocatalytic decomposition of urea. Our results indicate that [NH 4 ]NiPO 4 ·6H 2 O calcined at 300 °C with an amorphous crystal structure and, for the first time applied for urea electrocatalytic decomposition, had the greatest reported electroactive surface area (ESA) of 142 cm 2 /mg and an onset potential of 0.33 V (SCE) and was stable over a 24-h test period.

Rate of hexabromocyclododecane decomposition and production of brominated polycyclic aromatic hydrocarbons during combustion in a pilot-scale incinerator.

PubMed

Miyake, Yuichi; Tokumura, Masahiro; Wang, Qi; Amagai, Takashi; Horii, Yuichi

2017-11-01

Here, we examined the incineration of extruded polystyrene containing hexabromocyclododecane (HBCD) in a pilot-scale incinerator under various combustion temperatures (800-950°C) and flue gas residence times (2-8sec). Rates of HBCD decomposition ranged from 99.996% (800°C, 2sec) to 99.9999% (950°C, 8sec); the decomposition of HBCD, except during the initial stage of combustion (flue gas residence time<2sec), followed a pseudo-first-order kinetics model. An Arrhenius plot revealed that the activation energy and frequency factor of the decomposition of HBCD by combustion were 14.2kJ/mol and 1.69sec -1 , respectively. During combustion, 11 brominated polycyclic aromatic hydrocarbons (BrPAHs) were detected as unintentional by-products. Of the 11 BrPAHs detected, 2-bromoanthracene and 1-bromopyrene were detected at the highest concentrations. The mutagenic and carcinogenic BrPAHs 1,5-dibromoanthracene and 1-bromopyrene were most frequently detected in the flue gases analyzed. The total concentration of BrPAHs exponentially increased (range, 87.8-2,040,000ng/m 3 ) with increasing flue gas residence time. Results from a qualitative analysis using gas chromatography/high-resolution mass spectrometry suggest that bromofluorene and bromopyrene (or fluoranthene) congeners were also produced during the combustion. Copyright © 2017. Published by Elsevier B.V.

Synthesis and characterization of nickel and zinc ferrite nanocatalysts for decomposition of CO2 greenhouse effect gas.

PubMed

Lin, Kuen-Song; Adhikari, Abhijit Krishna; Wang, Chi-Yu; Hsu, Pei-Ju; Chan, Ho-Yang

2013-04-01

The decomposition of CO2 over oxygen deficient nickel ferrite nanoparticles (NFNs) and zinc ferrite nanoparticles (ZFNs) at 573 K was studied. The oxidation states with fine structure of Fe/Ni or Fe/Zn species were also measured in NFNs and ZFNs catalysts, respectively. Oxygen deficiency of catalysts was obtained by reduction in hydrogen. Decomposition of CO2 into carbon and oxygen has been carried out within few minutes when it comes into contact with oxygen deficient catalysts through incorporation of oxygen into ferrite nanoparticles. Oxygen and carbon rather than CO were produced in the decomposition process. The complete decomposition of CO2 was possible because of higher degree of oxygen deficiency andsurface-to-volume ratio of the catalysts. The pre-edge XANES spectra of Fe species in both catalysts exhibit an absorbance feature at 7114 eV for the 1s to 3d transition which is forbidden by the selection rule in case of perfect octahedral symmetry. The EXAFS data showed that the NFNs had two central Fe atoms coordinated by primarily Fe-O and Fe-Fe with bond distances of 1.871 and 3.051 angstroms, respectively. In case of ZFNs these values are 1.889 and 3.062 A, respectively. Methane gas was produced during the reactivation of NFNs by flowing hydrogen gas. Decomposition of CO2, moreover, recovery of valuable methane using heat energy of offgas produced from power generation plant or steel industry is an appealing alternative for energy recovery.

Assessment of a new method for the analysis of decomposition gases of polymers by a combining thermogravimetric solid-phase extraction and thermal desorption gas chromatography mass spectrometry.

PubMed

Duemichen, E; Braun, U; Senz, R; Fabian, G; Sturm, H

2014-08-08

For analysis of the gaseous thermal decomposition products of polymers, the common techniques are thermogravimetry, combined with Fourier transformed infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS). These methods offer a simple approach to the decomposition mechanism, especially for small decomposition molecules. Complex spectra of gaseous mixtures are very often hard to identify because of overlapping signals. In this paper a new method is described to adsorb the decomposition products during controlled conditions in TGA on solid-phase extraction (SPE) material: twisters. Subsequently the twisters were analysed with thermal desorption gas chromatography mass spectrometry (TDS-GC-MS), which allows the decomposition products to be separated and identified using an MS library. The thermoplastics polyamide 66 (PA 66) and polybutylene terephthalate (PBT) were used as example polymers. The influence of the sample mass and of the purge gas flow during the decomposition process was investigated in TGA. The advantages and limitations of the method were presented in comparison to the common analysis techniques, TGA-FTIR and TGA-MS. Copyright © 2014 Elsevier B.V. All rights reserved.

Heterogeneous decomposition of silane in a fixed bed reactor

NASA Technical Reports Server (NTRS)

Iya, S. K.; Flagella, R. N.; Dipaolo, F. S.

1982-01-01

Heterogeneous decomposition of silane in a fluidized bed offers an attractive route for the low-cost production of silicon for photovoltaic application. To obtain design data for a fluid bed silane pyrolysis reactor, deposition experiments were conducted in a small-scale fixed bed apparatus. Data on the decomposition mode, plating rate, and deposition morphology were obtained in the temperature range 600-900 C. Conditions favorable for heterogeneous decomposition with good deposition morphology were identified. The kinetic rate data showed the reaction to be first order with an activation energy of 38.8 kcal/mol, which agrees well with work done by others. The results are promising for the development of an economically attractive fluid bed process.

Experimental and modeling study on decomposition kinetics of methane hydrates in different media.

PubMed

Liang, Minyan; Chen, Guangjin; Sun, Changyu; Yan, Lijun; Liu, Jiang; Ma, Qinglan

2005-10-13

The decomposition kinetic behaviors of methane hydrates formed in 5 cm3 porous wet activated carbon were studied experimentally in a closed system in the temperature range of 275.8-264.4 K. The decomposition rates of methane hydrates formed from 5 cm3 of pure free water and an aqueous solution of 650 g x m(-3) sodium dodecyl sulfate (SDS) were also measured for comparison. The decomposition rates of methane hydrates in seven different cases were compared. The results showed that the methane hydrates dissociate more rapidly in porous activated carbon than in free systems. A mathematical model was developed for describing the decomposition kinetic behavior of methane hydrates below ice point based on an ice-shielding mechanism in which a porous ice layer was assumed to be formed during the decomposition of hydrate, and the diffusion of methane molecules through it was assumed to be one of the control steps. The parameters of the model were determined by correlating the decomposition rate data, and the activation energies were further determined with respect to three different media. The model was found to well describe the decomposition kinetic behavior of methane hydrate in different media.

Unconditionally energy stable time stepping scheme for Cahn–Morral equation: Application to multi-component spinodal decomposition and optimal space tiling

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

Tavakoli, Rouhollah, E-mail: rtavakoli@sharif.ir

An unconditionally energy stable time stepping scheme is introduced to solve Cahn–Morral-like equations in the present study. It is constructed based on the combination of David Eyre's time stepping scheme and Schur complement approach. Although the presented method is general and independent of the choice of homogeneous free energy density function term, logarithmic and polynomial energy functions are specifically considered in this paper. The method is applied to study the spinodal decomposition in multi-component systems and optimal space tiling problems. A penalization strategy is developed, in the case of later problem, to avoid trivial solutions. Extensive numerical experiments demonstrate themore » success and performance of the presented method. According to the numerical results, the method is convergent and energy stable, independent of the choice of time stepsize. Its MATLAB implementation is included in the appendix for the numerical evaluation of algorithm and reproduction of the presented results. -- Highlights: •Extension of Eyre's convex–concave splitting scheme to multiphase systems. •Efficient solution of spinodal decomposition in multi-component systems. •Efficient solution of least perimeter periodic space partitioning problem. •Developing a penalization strategy to avoid trivial solutions. •Presentation of MATLAB implementation of the introduced algorithm.« less

Ab initio kinetics and thermal decomposition mechanism of mononitrobiuret and 1,5-dinitrobiuret

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

Sun, Hongyan, E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil; Vaghjiani, Ghanshyam L., E-mail: hongyan.sun1@gmail.com, E-mail: ghanshyam.vaghjiani@us.af.mil

2015-05-28

Mononitrobiuret (MNB) and 1,5-dinitrobiuret (DNB) are tetrazole-free, nitrogen-rich, energetic compounds. For the first time, a comprehensive ab initio kinetics study on the thermal decomposition mechanisms of MNB and DNB is reported here. In particular, the intramolecular interactions of amine H-atom with electronegative nitro O-atom and carbonyl O-atom have been analyzed for biuret, MNB, and DNB at the M06-2X/aug-cc-pVTZ level of theory. The results show that the MNB and DNB molecules are stabilized through six-member-ring moieties via intramolecular H-bonding with interatomic distances between 1.8 and 2.0 Å, due to electrostatic as well as polarization and dispersion interactions. Furthermore, it was foundmore » that the stable molecules in the solid state have the smallest dipole moment amongst all the conformers in the nitrobiuret series of compounds, thus revealing a simple way for evaluating reactivity of fuel conformers. The potential energy surface for thermal decomposition of MNB was characterized by spin restricted coupled cluster theory at the RCCSD(T)/cc-pV∞ Z//M06-2X/aug-cc-pVTZ level. It was found that the thermal decomposition of MNB is initiated by the elimination of HNCO and HNN(O)OH intermediates. Intramolecular transfer of a H-atom, respectively, from the terminal NH{sub 2} group to the adjacent carbonyl O-atom via a six-member-ring transition state eliminates HNCO with an energy barrier of 35 kcal/mol and from the central NH group to the adjacent nitro O-atom eliminates HNN(O)OH with an energy barrier of 34 kcal/mol. Elimination of HNN(O)OH is also the primary process involved in the thermal decomposition of DNB, which processes C{sub 2v} symmetry. The rate coefficients for the primary decomposition channels for MNB and DNB were quantified as functions of temperature and pressure. In addition, the thermal decomposition of HNN(O)OH was analyzed via Rice–Ramsperger–Kassel–Marcus/multi-well master equation simulations, the results of which reveal the formation of (NO{sub 2} + H{sub 2}O) to be the major decomposition path. Furthermore, we provide fundamental interpretations for the experimental results of Klapötke et al. [Combust. Flame 139, 358–366 (2004)] regarding the thermal stability of MNB and DNB, and their decomposition products. Notably, a fundamental understanding of fuel stability, decomposition mechanism, and key reactions leading to ignition is essential in the design and manipulation of molecular systems for the development of new energetic materials for advanced propulsion applications.« less

Combined iterative reconstruction and image-domain decomposition for dual energy CT using total-variation regularization

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

Dong, Xue; Niu, Tianye; Zhu, Lei, E-mail: leizhu@gatech.edu

2014-05-15

Purpose: Dual-energy CT (DECT) is being increasingly used for its capability of material decomposition and energy-selective imaging. A generic problem of DECT, however, is that the decomposition process is unstable in the sense that the relative magnitude of decomposed signals is reduced due to signal cancellation while the image noise is accumulating from the two CT images of independent scans. Direct image decomposition, therefore, leads to severe degradation of signal-to-noise ratio on the resultant images. Existing noise suppression techniques are typically implemented in DECT with the procedures of reconstruction and decomposition performed independently, which do not explore the statistical propertiesmore » of decomposed images during the reconstruction for noise reduction. In this work, the authors propose an iterative approach that combines the reconstruction and the signal decomposition procedures to minimize the DECT image noise without noticeable loss of resolution. Methods: The proposed algorithm is formulated as an optimization problem, which balances the data fidelity and total variation of decomposed images in one framework, and the decomposition step is carried out iteratively together with reconstruction. The noise in the CT images from the proposed algorithm becomes well correlated even though the noise of the raw projections is independent on the two CT scans. Due to this feature, the proposed algorithm avoids noise accumulation during the decomposition process. The authors evaluate the method performance on noise suppression and spatial resolution using phantom studies and compare the algorithm with conventional denoising approaches as well as combined iterative reconstruction methods with different forms of regularization. Results: On the Catphan©600 phantom, the proposed method outperforms the existing denoising methods on preserving spatial resolution at the same level of noise suppression, i.e., a reduction of noise standard deviation by one order of magnitude. This improvement is mainly attributed to the high noise correlation in the CT images reconstructed by the proposed algorithm. Iterative reconstruction using different regularization, including quadratic orq-generalized Gaussian Markov random field regularization, achieves similar noise suppression from high noise correlation. However, the proposed TV regularization obtains a better edge preserving performance. Studies of electron density measurement also show that our method reduces the average estimation error from 9.5% to 7.1%. On the anthropomorphic head phantom, the proposed method suppresses the noise standard deviation of the decomposed images by a factor of ∼14 without blurring the fine structures in the sinus area. Conclusions: The authors propose a practical method for DECT imaging reconstruction, which combines the image reconstruction and material decomposition into one optimization framework. Compared to the existing approaches, our method achieves a superior performance on DECT imaging with respect to decomposition accuracy, noise reduction, and spatial resolution.« less

Alumina nanowire growth by water decomposition and the peritectic reaction of decagonal Al{sub 65}Cu{sub 15}Co{sub 20} quasicrystals

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

Téllez-Vázquez, J.O., E-mail: oswald.tellez@gmail.com; Patiño-Carachure, C., E-mail: cpatino@pampano.unacar.mx; Rosas, G., E-mail: grtrejo@yahoo07.com.mx

2016-02-15

In this paper, the results of the Al{sub 2}O{sub 3} nanowires' growth through a chemical reaction between Al and water vapor at 1050 °C are presented. Our approach is based on two primary considerations. First, at room temperature, the Al{sub 65}Cu{sub 15}Co{sub 20} alloy is affected by the following mechanism: 2Al (s) + 3H{sub 2}O (g) → Al{sub 2}O{sub 3} (s) + H{sub 2} (g). In this reaction, the released hydrogen induces cleavage fracture of the material to form small particles. Second, the Al{sub 65}Cu{sub 15}Co{sub 20} quasicrystalline phase is transformed on heating to liquid + Al (Cu, Co) cubicmore » phase through a peritectic reaction at 1050 °C. The Al-rich liquid then reacts with water vapor, forming Al{sub 2}O{sub 3} nanowires. X-ray diffraction (XRD) analysis shows that the formed nanowires have a hexagonal structure, and infrared analysis further confirms the presence of α-Al{sub 2}O{sub 3} phase in the final products. Transmission electron microscopy observations show that nanoparticles are present at the end of nanowires, suggesting the VLS growth mechanism. Elemental analysis by energy dispersive spectroscopy (EDS) indicates that the particles at the tip of the nanowires are mainly formed by Co and Cu alloying elements and small amounts of Al. Electron microscopy observations showed nanowires with diameters ranging from 20 to 70 nm; the average diameter was 37 nm and the nanowire lengths were up to several micrometers. - Highlights: • Hexagonal alumina nanowires are grown at 1050 °C through the VLS process. • Alumina nanowires are obtained by the decomposition of decagonal quasicrystalline phase. • The decagonal phase decomposition follows a peritectic reaction at 1030 °C. • Nanoparticles are obtained by hydrogen embrittlement mechanism. • The nanoparticles catalyze the water decomposition to form wires.« less

Photoelectron Spectroscopy of Nitrogen Containing Molecules of Biological and Industrial Interest

NASA Astrophysics Data System (ADS)

Pinto, Rui Montenegro Val-do-Rio

The work presented herein is based on the gas-phase spectroscopic characterization of several molecules of high nitrogen content which are relevant to organic synthesis, industry and fundamental research on molecular physics. It is mainly an experimental enterprise on selected organic azides and tetrazoles, with heavy support on theoretical results from readily available computational methods. Part of the work relies on the design and construction of scientific apparatus, which substantially improve the existing equipment and extend the limits of the experiment. The electronic structure and gas-phase thermal decomposition of methyl 2-azidopropionate (M2AP, N3CH3CHCO2CH 3), benzyl azide (BA, C6H5CH2N 3), 2-, 3- and 4- methyl benzyl azide (2-, 3- and 4-MBA, CH3C 6H4CH2N3), 5-aminotetrazole (5ATZ, NH2CN4H), and 5-methyltetrazole (5MTZ, CH3CN 4H) are investigated through photoelectron spectroscopy, using either He(I) (21.22 eV) or synchrotron radiation in the Xray range. Relevant information obtained from mass spectrometry and matrix-isolation infrared spectroscopy is used to complement characterization of the samples. Regarding each molecules' thermal decomposition, pathways are proposed which account for the observed end products. Conformational analysis is performed, and the special case of annular tautomerism is addressed in the tetrazole compounds. High-temperature pyrolysis work is performed in collaboration with the University of Southampton, and XPS analysis using synchrotron radiation is performed at Elettra, the multidisciplinary synchrotron light laboratory in Trieste, Italy. Experimental findings are rationalized using different computational methods, based on post-Hartree-Fock approaches: many-body perturbation theory (MPn), configuration interaction (CI) and Green's function methods (OVGF, P3), as well as density functional theory (DFT), are used extensively to obtain optimized molecular geometries, ionization energies, orbital contours, relative energies, vibrational frequencies, and to assess possible pathways for thermal or electron impact fragmentation. Composite methods (G n and CBS) are used to estimate to kcal mol-1 accuracy the energy balance between reactants, transition structures and products in the overall decomposition process of the specified molecules.

SPHARA--a generalized spatial Fourier analysis for multi-sensor systems with non-uniformly arranged sensors: application to EEG.

PubMed

Graichen, Uwe; Eichardt, Roland; Fiedler, Patrique; Strohmeier, Daniel; Zanow, Frank; Haueisen, Jens

2015-01-01

Important requirements for the analysis of multichannel EEG data are efficient techniques for signal enhancement, signal decomposition, feature extraction, and dimensionality reduction. We propose a new approach for spatial harmonic analysis (SPHARA) that extends the classical spatial Fourier analysis to EEG sensors positioned non-uniformly on the surface of the head. The proposed method is based on the eigenanalysis of the discrete Laplace-Beltrami operator defined on a triangular mesh. We present several ways to discretize the continuous Laplace-Beltrami operator and compare the properties of the resulting basis functions computed using these discretization methods. We apply SPHARA to somatosensory evoked potential data from eleven volunteers and demonstrate the ability of the method for spatial data decomposition, dimensionality reduction and noise suppression. When employing SPHARA for dimensionality reduction, a significantly more compact representation can be achieved using the FEM approach, compared to the other discretization methods. Using FEM, to recover 95% and 99% of the total energy of the EEG data, on average only 35% and 58% of the coefficients are necessary. The capability of SPHARA for noise suppression is shown using artificial data. We conclude that SPHARA can be used for spatial harmonic analysis of multi-sensor data at arbitrary positions and can be utilized in a variety of other applications.

Global sensitivity analysis for fuzzy inputs based on the decomposition of fuzzy output entropy

NASA Astrophysics Data System (ADS)

Shi, Yan; Lu, Zhenzhou; Zhou, Yicheng

2018-06-01

To analyse the component of fuzzy output entropy, a decomposition method of fuzzy output entropy is first presented. After the decomposition of fuzzy output entropy, the total fuzzy output entropy can be expressed as the sum of the component fuzzy entropy contributed by fuzzy inputs. Based on the decomposition of fuzzy output entropy, a new global sensitivity analysis model is established for measuring the effects of uncertainties of fuzzy inputs on the output. The global sensitivity analysis model can not only tell the importance of fuzzy inputs but also simultaneously reflect the structural composition of the response function to a certain degree. Several examples illustrate the validity of the proposed global sensitivity analysis, which is a significant reference in engineering design and optimization of structural systems.

Image-based spectral distortion correction for photon-counting x-ray detectors

PubMed Central

Ding, Huanjun; Molloi, Sabee

2012-01-01

Purpose: To investigate the feasibility of using an image-based method to correct for distortions induced by various artifacts in the x-ray spectrum recorded with photon-counting detectors for their application in breast computed tomography (CT). Methods: The polyenergetic incident spectrum was simulated with the tungsten anode spectral model using the interpolating polynomials (TASMIP) code and carefully calibrated to match the x-ray tube in this study. Experiments were performed on a Cadmium-Zinc-Telluride (CZT) photon-counting detector with five energy thresholds. Energy bins were adjusted to evenly distribute the recorded counts above the noise floor. BR12 phantoms of various thicknesses were used for calibration. A nonlinear function was selected to fit the count correlation between the simulated and the measured spectra in the calibration process. To evaluate the proposed spectral distortion correction method, an empirical fitting derived from the calibration process was applied on the raw images recorded for polymethyl methacrylate (PMMA) phantoms of 8.7, 48.8, and 100.0 mm. Both the corrected counts and the effective attenuation coefficient were compared to the simulated values for each of the five energy bins. The feasibility of applying the proposed method to quantitative material decomposition was tested using a dual-energy imaging technique with a three-material phantom that consisted of water, lipid, and protein. The performance of the spectral distortion correction method was quantified using the relative root-mean-square (RMS) error with respect to the expected values from simulations or areal analysis of the decomposition phantom. Results: The implementation of the proposed method reduced the relative RMS error of the output counts in the five energy bins with respect to the simulated incident counts from 23.0%, 33.0%, and 54.0% to 1.2%, 1.8%, and 7.7% for 8.7, 48.8, and 100.0 mm PMMA phantoms, respectively. The accuracy of the effective attenuation coefficient of PMMA estimate was also improved with the proposed spectral distortion correction. Finally, the relative RMS error of water, lipid, and protein decompositions in dual-energy imaging was significantly reduced from 53.4% to 6.8% after correction was applied. Conclusions: The study demonstrated that dramatic distortions in the recorded raw image yielded from a photon-counting detector could be expected, which presents great challenges for applying the quantitative material decomposition method in spectral CT. The proposed semi-empirical correction method can effectively reduce these errors caused by various artifacts, including pulse pileup and charge sharing effects. Furthermore, rather than detector-specific simulation packages, the method requires a relatively simple calibration process and knowledge about the incident spectrum. Therefore, it may be used as a generalized procedure for the spectral distortion correction of different photon-counting detectors in clinical breast CT systems. PMID:22482608

Lipid oxidation. Part. 1. Effect of free carboxyl group on the decomposition of lipid hydroperoxide.

PubMed

Pokorný, J; Rzepa, J; Janícek, G

1976-01-01

Hydroperoxido butyl oleate was decomposed by heating in excess palmitic acid at 60-120 degrees C. The decomposition followed the kinetics of a first order reaction with formation of both monomeric and oligomeric secondary products. The proportions of oligomers slightly increased with increasing reaction temperature and decreased with increasing concentration of hydroperoxide. The activation energy was 70.4 kJ/mol +/- 4.7 kJ/mol. The decomposition of hydroperoxides proceeded partially by monomolecular cleavage, partially by formation of esters with palmitic acid.

A theoretical study of the molecular mechanism of the GAPDH Trypanosoma cruzi enzyme involving iodoacetate inhibitor

NASA Astrophysics Data System (ADS)

Carneiro, Agnaldo Silva; Lameira, Jerônimo; Alves, Cláudio Nahum

2011-10-01

The glyceraldehyde-3-phosphate dehydrogenase enzyme (GAPDH) is an important biological target for the development of new chemotherapeutic agents against Chagas disease. In this Letter, the inhibition mechanism of GAPDH involving iodoacetate (IAA) inhibitor was studied using the hybrid quantum mechanical/molecular mechanical (QM/MM) approach and molecular dynamic simulations. Analysis of the potential energy surface and potential of mean force show that the covalent attachment of IAA inhibitor to the active site of the enzyme occurs as a concerted process. In addition, the energy terms decomposition shows that NAD+ plays an important role in stabilization of the reagents and transition state.

Chemical bonding in silicon-carbene complexes.

PubMed

Liu, Z

2009-06-04

The bonding situations in the newly synthesized silicon-carbene complexes with formulas L:SiCl4, L:(Cl)Si-Si(Cl):L, and L:Si=Si:L (where L: is an N-heterocyclic carbene), are reported using density functional theory at the BP86/TZ2P level. The bonding analysis clearly shows that the bonding situation in the silicon-carbene complexes cannot be described in terms of donor-acceptor interactions depicted in the Dewar-Chatt-Duncanson model. The energy decomposition analysis (EDA) shows that the electrostatic attraction plays an important or even dominant role for the Si-C(carbene) binding interactions in the silicon-carbene complexes. That the molecular orbitals of the silicon-carbene complexes are lower in energy than the parent orbitals of carbenes indicates that these complexes are better described as stabilized carbene complexes.

Kinetic concepts of thermally stimulated reactions in solids

NASA Astrophysics Data System (ADS)

Vyazovkin, Sergey

Historical analysis suggests that the basic kinetic concepts of reactions in solids were inherited from homogeneous kinetics. These concepts rest upon the assumption of a single-step reaction that disagrees with the multiple-step nature of solid-state processes. The inadequate concepts inspire such unjustified anticipations of kinetic analysis as evaluating constant activation energy and/or deriving a single-step reaction mechanism for the overall process. A more adequate concept is that of the effective activation energy, which may vary with temperature and extent of conversion. The adequacy of this concept is illustrated by literature data as well as by experimental data on the thermal dehydration of calcium oxalate monohydrate and thermal decomposition of calcium carbonate, ammonium nitrate and 1,3,5,7- tetranitro-1,3,5,7-tetrazocine.

Use of Direct Dynamics Simulations to Determine Unimolecular Reaction Paths and Arrhenius Parameters for Large Molecules.

PubMed

Yang, Li; Sun, Rui; Hase, William L

2011-11-08

In a previous study (J. Chem. Phys.2008, 129, 094701) it was shown that for a large molecule, with a total energy much greater than its barrier for decomposition and whose vibrational modes are harmonic oscillators, the expressions for the classical Rice-Ramsperger-Kassel-Marcus (RRKM) (i.e., RRK) and classical transition-state theory (TST) rate constants become equivalent. Using this relationship, a molecule's unimolecular rate constants versus temperature may be determined from chemical dynamics simulations of microcanonical ensembles for the molecule at different total energies. The simulation identifies the molecule's unimolecular pathways and their Arrhenius parameters. In the work presented here, this approach is used to study the thermal decomposition of CH3-NH-CH═CH-CH3, an important constituent in the polymer of cross-linked epoxy resins. Direct dynamics simulations, at the MP2/6-31+G* level of theory, were used to investigate the decomposition of microcanonical ensembles for this molecule. The Arrhenius A and Ea parameters determined from the direct dynamics simulation are in very good agreement with the TST Arrhenius parameters for the MP2/6-31+G* potential energy surface. The simulation method applied here may be particularly useful for large molecules with a multitude of decomposition pathways and whose transition states may be difficult to determine and have structures that are not readily obvious.

High-energy coordination polymers (CPs) exhibiting good catalytic effect on the thermal decomposition of ammonium dinitramide

NASA Astrophysics Data System (ADS)

Li, Xin; Han, Jing; Zhang, Sheng; Zhai, Lianjie; Wang, Bozhou; Yang, Qi; Wei, Qing; Xie, Gang; Chen, Sanping; Gao, Shengli

2017-09-01

High-energy coordination polymers (CPs) not only exhibit good energetic performances but also have a good catalytic effect on the thermal decomposition of energetic materials. In this contribution, two high-energy CPs Cu2(DNBT)2(CH3OH)(H2O)3·3H2O (1) and [Cu3(DDT)2(H2O)2]n (2) (H2DNBT = 3,3‧-dinitro-5,5‧-bis(1H-1,2,4-triazole and H3DDT = 4,5-bis(1H-tetrazol-5-yl)-2H-1,2,3-triazole) were synthesized and structurally characterized. Furthermore, 1 was thermos-dehydrated to produce Cu2(DNBT)2(CH3OH)(H2O)3 (1a). The thermal decomposition kinetics of 1, 1a and 2 were studied by Kissinger's method and Ozawa's method. Thermal analyses and sensitivity tests show that all compounds exhibit high thermal stability and low sensitivity for external stimuli. Meanwhile, all compounds have large positive enthalpy of formation, which are calculated as being (1067.67 ± 2.62) kJ mol-1 (1), (1464.12 ± 3.12) kJ mol-1 (1a) and (3877.82 ± 2.75) kJ mol-1 (2), respectively. The catalytic effects of 1a and 2 on the thermal decomposition of ammonium dinitramide (ADN) were also investigated.

Scalable parallel elastic-plastic finite element analysis using a quasi-Newton method with a balancing domain decomposition preconditioner

NASA Astrophysics Data System (ADS)

Yusa, Yasunori; Okada, Hiroshi; Yamada, Tomonori; Yoshimura, Shinobu

2018-04-01

A domain decomposition method for large-scale elastic-plastic problems is proposed. The proposed method is based on a quasi-Newton method in conjunction with a balancing domain decomposition preconditioner. The use of a quasi-Newton method overcomes two problems associated with the conventional domain decomposition method based on the Newton-Raphson method: (1) avoidance of a double-loop iteration algorithm, which generally has large computational complexity, and (2) consideration of the local concentration of nonlinear deformation, which is observed in elastic-plastic problems with stress concentration. Moreover, the application of a balancing domain decomposition preconditioner ensures scalability. Using the conventional and proposed domain decomposition methods, several numerical tests, including weak scaling tests, were performed. The convergence performance of the proposed method is comparable to that of the conventional method. In particular, in elastic-plastic analysis, the proposed method exhibits better convergence performance than the conventional method.

Application of microscopy technology in thermo-catalytic methane decomposition to hydrogen

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

Mei, Irene Lock Sow, E-mail: irene.sowmei@gmail.com; Lock, S. S. M., E-mail: serenelock168@gmail.com; Abdullah, Bawadi, E-mail: bawadi-abdullah@petronas.com.my

2015-07-22

Hydrogen production from the direct thermo-catalytic decomposition of methane is a promising alternative for clean fuel production because it produces pure hydrogen without any CO{sub x} emissions. However, thermal decomposition of methane can hardly be of any practical and empirical interest in the industry unless highly efficient and effective catalysts, in terms of both specific activity and operational lifetime have been developed. In this work, bimetallic Ni-Pd on gamma alumina support have been developed for methane cracking process by using co-precipitation and incipient wetness impregnation method. The calcined catalysts were characterized to determine their morphologies and physico-chemical properties by usingmore » Brunauer-Emmett-Teller method, Field Emission Scanning Electron Microscopy, Energy-dispersive X-ray spectroscopy and Thermogravimetric Analysis. The results suggested that that the catalyst which is prepared by the co-precipitation method exhibits homogeneous morphology, higher surface area, have uniform nickel and palladium dispersion and higher thermal stability as compared to the catalyst which is prepared by wet impregnation method. This characteristics are significant to avoid deactivation of the catalysts due to sintering and carbon deposition during methane cracking process.« less

Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO 3, U 2O 7, and UO 4

DOE PAGES

Guo, Xiaofeng; Wu, Di; Xu, Hongwu; ...

2016-09-01

The thermal decomposition of studtite (UO 2)O 2(H 2O) 2·2H 2O results in a series of intermediate X-ray amorphous materials with general composition UO 3+x (x = 0, 0.5, 1). As an extension of a structural study on U 2O 7, this work provides detailed calorimetric data on these amorphous oxygen-rich materials since their energetics and thermal stability are unknown. These were characterized in situ by thermogravimetry, and mass spectrometry. Ex situ X-ray diffraction and infrared spectroscopy characterized their chemical bonding and local structures. This detailed characterization formed the basis for obtaining formation enthalpies by high temperature oxide melt solutionmore » calorimetry. The thermodynamic data demonstrate the metastability of the amorphous UO 3+x materials, and explain their irreversible and spontaneous reactions to generate oxygen and form metaschoepite. Thus, formation of studtite in the nuclear fuel cycle, followed by heat treatment, can produce metastable amorphous UO 3+x materials that pose the risk of significant O 2 gas. Quantitative knowledge of the energy landscape of amorphous UO 3+x was provided for stability analysis and assessment of conditions for decomposition.« less

Effect of anaerobic digestion on sequential pyrolysis kinetics of organic solid wastes using thermogravimetric analysis and distributed activation energy model.

PubMed

Li, Xiaowei; Mei, Qingqing; Dai, Xiaohu; Ding, Guoji

2017-03-01

Thermogravimetric analysis, Gaussian-fit-peak model (GFPM), and distributed activation energy model (DAEM) were firstly used to explore the effect of anaerobic digestion on sequential pyrolysis kinetic of four organic solid wastes (OSW). Results showed that the OSW weight loss mainly occurred in the second pyrolysis stage relating to organic matter decomposition. Compared with raw substrate, the weight loss of corresponding digestate was lower in the range of 180-550°C, but was higher in 550-900°C. GFPM analysis revealed that organic components volatized at peak temperatures of 188-263, 373-401 and 420-462°C had a faster degradation rate than those at 274-327°C during anaerobic digestion. DAEM analysis showed that anaerobic digestion had discrepant effects on activation energy for four OSW pyrolysis, possibly because of their different organic composition. It requires further investigation for the special organic matter, i.e., protein-like and carbohydrate-like groups, to confirm the assumption. Copyright © 2016 Elsevier Ltd. All rights reserved.

A density functional theory study of the decomposition mechanism of nitroglycerin.

PubMed

Pei, Liguan; Dong, Kehai; Tang, Yanhui; Zhang, Bo; Yu, Chang; Li, Wenzuo

2017-08-21

The detailed decomposition mechanism of nitroglycerin (NG) in the gas phase was studied by examining reaction pathways using density functional theory (DFT) and canonical variational transition state theory combined with a small-curvature tunneling correction (CVT/SCT). The mechanism of NG autocatalytic decomposition was investigated at the B3LYP/6-31G(d,p) level of theory. Five possible decomposition pathways involving NG were identified and the rate constants for the pathways at temperatures ranging from 200 to 1000 K were calculated using CVT/SCT. There was found to be a lower energy barrier to the β-H abstraction reaction than to the α-H abstraction reaction during the initial step in the autocatalytic decomposition of NG. The decomposition pathways for CHOCOCHONO 2 (a product obtained following the abstraction of three H atoms from NG by NO 2 ) include O-NO 2 cleavage or isomer production, meaning that the autocatalytic decomposition of NG has two reaction pathways, both of which are exothermic. The rate constants for these two reaction pathways are greater than the rate constants for the three pathways corresponding to unimolecular NG decomposition. The overall process of NG decomposition can be divided into two stages based on the NO 2 concentration, which affects the decomposition products and reactions. In the first stage, the reaction pathway corresponding to O-NO 2 cleavage is the main pathway, but the rates of the two autocatalytic decomposition pathways increase with increasing NO 2 concentration. However, when a threshold NO 2 concentration is reached, the NG decomposition process enters its second stage, with the two pathways for NG autocatalytic decomposition becoming the main and secondary reaction pathways.

Mitigation of Manhole Events Caused by Secondary Cable Failure

NASA Astrophysics Data System (ADS)

Zhang, Lili

"Manhole event" refers to a range of phenomena, such as smokers, fires and explosions which occur on underground electrical infrastructure, primarily in major cities. The most common cause of manhole events is decomposition of secondary cable initiated by an electric fault. The work presented in this thesis addresses various aspects related to the evolution and mitigation of the manhole events caused by secondary cable insulation failure. Manhole events develop as a result of thermal decomposition of organic materials present in the cable duct and manholes. Polymer characterization techniques are applied to intensively study the materials properties as related to manhole events, mainly the thermal decomposition behaviors of the polymers present in the cable duct. Though evolved gas analysis, the combustible gases have been quantitatively identified. Based on analysis and knowledge of field conditions, manhole events is divided into at least two classes, those in which exothermic chemical reactions dominate and those in which electrical energy dominates. The more common form of manhole event is driven by air flow down the duct. Numerical modeling of smolder propagation in the cable duct demonstrated that limiting air flow is effective in reducing the generation rate of combustible gas, in other words, limiting manhole events to relatively minor "smokers". Besides manhole events, another by-product of secondary cable insulation breakdown is stray voltage. The danger to personnel due to stray voltage is mostly caused by the 'step potential'. The amplitude of step potential as a result of various types of insulation defects is calculated using Finite Element Analysis (FEA) program.

Methanol decomposition bottoming cycle for IC engines

NASA Technical Reports Server (NTRS)

Purohit, G.; Houseman, J.

1979-01-01

This paper presents the concept of methanol decomposition using engine exhaust heat, and examines its potential for use in the operation of passenger cars, diesel trucks, and diesel-electric locomotives. Energy economy improvements of 10-20% are calculated over the representative driving cycles without a net loss in power. Some reductions in exhaust emissions are also projected.

Initial mechanisms for the decomposition of electronically excited energetic materials: 1,5′-BT, 5,5′-BT, and AzTT

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

Yuan, Bing; Yu, Zijun; Bernstein, Elliot R., E-mail: erb@lamar.Colostate.edu

2015-03-28

Decomposition of nitrogen-rich energetic materials 1,5′-BT, 5,5′-BT, and AzTT (1,5′-Bistetrazole, 5,5′-Bistetrazole, and 5-(5-azido-(1 or 4)H-1,2,4-triazol-3-yl)tetrazole, respectively), following electronic state excitation, is investigated both experimentally and theoretically. The N{sub 2} molecule is observed as an initial decomposition product from the three materials, subsequent to UV excitation, with a cold rotational temperature (<30 K). Initial decomposition mechanisms for these three electronically excited materials are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. Electronically excited S{sub 1} molecules can non-adiabatically relaxmore » to their ground electronic states through (S{sub 1}/S{sub 0}){sub CI} conical intersections. 1,5′-BT and 5,5′-BT materials have several (S{sub 1}/S{sub 0}){sub CI} conical intersections between S{sub 1} and S{sub 0} states, related to different tetrazole ring opening positions, all of which lead to N{sub 2} product formation. The N{sub 2} product for AzTT is formed primarily by N–N bond rupture of the –N{sub 3} group. The observed rotational energy distributions for the N{sub 2} products are consistent with the final structures of the respective transition states for each molecule on its S{sub 0} potential energy surface. The theoretically derived vibrational temperature of the N{sub 2} product is high, which is similar to that found for energetic salts and molecules studied previously.« less

The design and implementation of signal decomposition system of CL multi-wavelet transform based on DSP builder

NASA Astrophysics Data System (ADS)

Huang, Yan; Wang, Zhihui

2015-12-01

With the development of FPGA, DSP Builder is widely applied to design system-level algorithms. The algorithm of CL multi-wavelet is more advanced and effective than scalar wavelets in processing signal decomposition. Thus, a system of CL multi-wavelet based on DSP Builder is designed for the first time in this paper. The system mainly contains three parts: a pre-filtering subsystem, a one-level decomposition subsystem and a two-level decomposition subsystem. It can be converted into hardware language VHDL by the Signal Complier block that can be used in Quartus II. After analyzing the energy indicator, it shows that this system outperforms Daubenchies wavelet in signal decomposition. Furthermore, it has proved to be suitable for the implementation of signal fusion based on SoPC hardware, and it will become a solid foundation in this new field.

Catalytic effects of inorganic acids on the decomposition of ammonium nitrate.

PubMed

Sun, Jinhua; Sun, Zhanhui; Wang, Qingsong; Ding, Hui; Wang, Tong; Jiang, Chuansheng

2005-12-09

In order to evaluate the catalytic effects of inorganic acids on the decomposition of ammonium nitrate (AN), the heat releases of decomposition or reaction of pure AN and its mixtures with inorganic acids were analyzed by a heat flux calorimeter C80. Through the experiments, the different reaction mechanisms of AN and its mixtures were analyzed. The chemical reaction kinetic parameters such as reaction order, activation energy and frequency factor were calculated with the C80 experimental results for different samples. Based on these parameters and the thermal runaway models (Semenov and Frank-Kamenestkii model), the self-accelerating decomposition temperatures (SADTs) of AN and its mixtures were calculated and compared. The results show that the mixtures of AN with acid are more unsteady than pure AN. The AN decomposition reaction is catalyzed by acid. The calculated SADTs of AN mixtures with acid are much lower than that of pure AN.

Targeting human c-Myc promoter duplex DNA with actinomycin D by use of multi-way analysis of quantum-dot-mediated fluorescence resonance energy transfer.

PubMed

Gholami, Somayeh; Kompany-Zareh, Mohsen

2013-07-01

Actinomycin D (Act D), an oncogenic c-Myc promoter binder, interferes with the action of RNA polymerase. There is great demand for high-throughput technology able to monitor the activity of DNA-binding drugs. To this end, binding of 7-aminoactinomycin D (7AAD) to the duplex c-Myc promoter was investigated by use of 2D-photoluminescence emission (2D-PLE), and the resulting data were subjected to analysis by use of convenient and powerful multi-way approaches. Fluorescence measurements were performed by use of the quantum dot (QD)-conjugated c-Myc promoter. Intercalation of 7AAD within duplex base pairs resulted in efficient energy transfer from drug to QD via fluorescence resonance energy transfer (FRET). Multi-way analysis of the three-way data array obtained from titration experiments was performed by use of restricted Tucker3 and hard trilinear decomposition (HTD). These techniques enable analysis of high-dimensional and complex data from nanobiological systems which include several spectrally overlapped structures. It was almost impossible to obtain robust and meaningful information about the FRET process for such high overlap data by use of classical analysis. The soft approach had the important advantage over univariate classical methods of enabling us to investigate the source of variance in the fluorescence signal of the DNA-drug complex. It was established that hard trilinear decomposition analysis of FRET-measured data overcomes the problem of rank deficiency, enabling calculation of concentration profiles and pure spectra for all species, including non-fluorophores. The hard modeling approach was also used for determination of equilibrium constants for the hybridization and intercalation equilibria, using nonlinear fit data analysis. The intercalation constant 3.6 × 10(6) mol(-1) L and hybridization stability 1.0 × 10(8) mol(-1) L obtained were in good agreement with values reported in the literature. The analytical concentration of the QD-labeled DNA was determined by use of nonlinear fitting, without using external standard calibration samples. This study was a successful application of multi-way chemometric methods to investigation of nano-biotechnological systems where several overlapped species coexist in solution.

A model for finite-deformation nonlinear thermomechanical response of single crystal copper under shock conditions

NASA Astrophysics Data System (ADS)

Luscher, Darby J.; Bronkhorst, Curt A.; Alleman, Coleman N.; Addessio, Francis L.

2013-09-01

A physically consistent framework for combining pressure-volume-temperature equations of state with crystal plasticity models is developed for the application of modeling the response of single and polycrystals under shock conditions. The particular model is developed for copper, thus the approach focuses on crystals of cubic symmetry although many of the concepts in the approach are applicable to crystals of lower symmetry. We employ a multiplicative decomposition of the deformation gradient into isochoric elastic, thermoelastic dilation, and plastic parts leading to a definition of isochoric elastic Green-Lagrange strain. This finite deformation kinematic decomposition enables a decomposition of Helmholtz free-energy into terms reflecting dilatational thermoelasticity, strain energy due to long-range isochoric elastic deformation of the lattice and a term reflecting energy stored in short range elastic lattice deformation due to evolving defect structures. A model for the single crystal response of copper is implemented consistent with the framework into a three-dimensional Lagrangian finite element code. Simulations exhibit favorable agreement with single and bicrystal experimental data for shock pressures ranging from 3 to 110 GPa.

Crude oil price analysis and forecasting based on variational mode decomposition and independent component analysis

NASA Astrophysics Data System (ADS)

E, Jianwei; Bao, Yanling; Ye, Jimin

2017-10-01

As one of the most vital energy resources in the world, crude oil plays a significant role in international economic market. The fluctuation of crude oil price has attracted academic and commercial attention. There exist many methods in forecasting the trend of crude oil price. However, traditional models failed in predicting accurately. Based on this, a hybrid method will be proposed in this paper, which combines variational mode decomposition (VMD), independent component analysis (ICA) and autoregressive integrated moving average (ARIMA), called VMD-ICA-ARIMA. The purpose of this study is to analyze the influence factors of crude oil price and predict the future crude oil price. Major steps can be concluded as follows: Firstly, applying the VMD model on the original signal (crude oil price), the modes function can be decomposed adaptively. Secondly, independent components are separated by the ICA, and how the independent components affect the crude oil price is analyzed. Finally, forecasting the price of crude oil price by the ARIMA model, the forecasting trend demonstrates that crude oil price declines periodically. Comparing with benchmark ARIMA and EEMD-ICA-ARIMA, VMD-ICA-ARIMA can forecast the crude oil price more accurately.

Localized corrosion of 316L stainless steel in tritiated water containing aggressive radiolytic and decomposition products at different temperatures

NASA Astrophysics Data System (ADS)

Bellanger, G.

2008-02-01

Tritium is one of the more important radionuclides used in nuclear industry as plutonium and uranium. The tritium in tritiated water always causes difficulties in nuclear installations, including equipment corrosion. Moreover, with tritiated water there are, in addition, the radiolytic and decomposition products such as hydrogen peroxide formed during decay, chloride ions produced by degradation of organic seals and oils used for tightness and pumping, and acid pH produced by excitation of nitrogen in air by the β - particle. Highly concentrated tritiated water releases energy and its temperature is about 80 °C, moreover heating is necessary in the tritium processes. These conditions highly facilitate the corrosion of stainless steels by pitting and crevice attack. Corrosion tests were performed by electrochemical analysis methods and by visual inspection of the surface of stainless steel.

Pyrolytic and Kinetic Characteristics of the Thermal Decomposition of Perilla frutescens Polysaccharide

PubMed Central

Zhou, Quancheng; Sheng, Guihua

2012-01-01

The thermal decomposition of Perilla frutescens polysaccharide was examined by thermogravimetry, differential thermogravimetry, and differential thermal analysis. The results showed that the mass loss of the substance proceeded in three steps. The first stage can be attributed to the expulsion of the water from ambient temperature to 182°C. The second stage corresponded to devolatilization from 182°C to 439°C. The residue slowly degraded in the third stage. The weight loss in air is faster than that in nitrogen, because the oxygen in air accelerated the pyrolytic reaction speed reaction. The heating rate significantly affected the pyrolysis of the sample. Similar activation energies of the degradation process (210–211 kJ mol−1) were obtained by the FWO, KAS, and Popescu techniques. According to Popescu mechanism functions, the possible kinetic model was estimated to be Avrami–Erofeev 20 g(α) = [−ln(1–α)]4. PMID:23300715

Elucidation of high sensitivity of δ-HMX: New insight from first principles simulations

NASA Astrophysics Data System (ADS)

Kuklja, Maija M.; Tsyshevsky, Roman V.; Sharia, Onise

2017-01-01

Understanding of a significant difference in sensitivities of β and δ phases of cyclotetramethylene-tetranitramine (HMX) has been long one of the challenges in the field of high energy density materials. Despite many experimental and theoretical efforts to explain the high sensitivity of the δ phase, convincing reasons behind the HMX behavior remained unclear. We established that the presence of a polar surface in δ-HMX has fundamental implications for stability and overall chemical behavior of the material. A comparative quantum-chemical analysis of decomposition mechanisms in polar δ-HMX and nonpolar β-HMX discovered a considerable difference in dominating dissociation reactions, activation barriers, and reaction rates. The polarization-induced charge transfer offered a logical explanation for different sensitivity of β-HMX and δ-HMX polymorphs to detonation initiation. Our conclusions also removed long-standing contradictions and explained a large range of experimental data on thermal decomposition of HMX.

Kinetics of gas phase formic acid decomposition on platinum single crystal and polycrystalline surfaces

NASA Astrophysics Data System (ADS)

Detwiler, Michael D.; Milligan, Cory A.; Zemlyanov, Dmitry Y.; Delgass, W. Nicholas; Ribeiro, Fabio H.

2016-06-01

Formic acid dehydrogenation turnover rates (TORs) were measured on Pt(111), Pt(100), and polycrystalline Pt foil surfaces at a total pressure of 800 Torr between 413 and 513 K in a batch reactor connected to an ultra-high vacuum (UHV) system. The TORs, apparent activation energies, and reaction orders are not sensitive to the structure of the Pt surface, within the precision of the measurements. CO introduced into the batch reactor depressed the formic acid dehydrogenation TOR and increased the reaction's apparent activation energies on Pt(111) and Pt(100), consistent with behavior predicted by the Temkin equation. Two reaction mechanisms were explored which explain the formic acid decomposition mechanism on Pt, both of which include dissociative adsorption of formic acid, rate limiting formate decomposition, and quasi-equilibrated hydrogen recombination and CO adsorption. No evidence was found that catalytic supports used in previous studies altered the reaction kinetics or mechanism.

Exploring resistance mechanisms of HCV NS3/4A protease mutations to MK5172: insight from molecular dynamics simulations and free energy calculations.

PubMed

Guan, Yan; Sun, Huiyong; Pan, Peichen; Li, Youyong; Li, Dan; Hou, Tingjun

2015-09-01

Mutations at a number of key positions (Ala156, Asp168 and Arg155) of the HCV NS3/4A protease can induce medium to high resistance to MK5172. The emergence of the resistant mutations seriously compromises the antiviral therapy efficacy to hepatitis C. In this study, molecular dynamics (MD) simulations, free energy calculations and free energy decomposition were used to explore the interaction profiles of MK5172 with the wild-type (WT) and four mutated (R155K, D168A, D168V and A156T) HCV NS3/4A proteases. The binding free energies predicted by Molecular Mechanics/Generalized Born Solvent Area (MM/GBSA) are consistent with the trend of the experimental drug resistance data. The free energy decomposition analysis shows that the resistant mutants may change the protein-MK5172 interaction profiles, resulting in the unbalanced energetic distribution amongst the catalytic triad, the strand 135-139 and the strand 154-160. Moreover, umbrella sampling (US) simulations were employed to elucidate the unbinding processes of MK5172 from the active pockets of the WT HCV NS3/4A protease and the four mutants. The US simulations demonstrate that the dissociation pathways of MK5172 escaping from the binding pockets of the WT and mutants are quite different, and it is quite possible that MK5172 will be harder to get access to the correct binding sites of the mutated proteases, thereafter leading to drug resistance.

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

Yuan, Bing; Bernstein, Elliot R., E-mail: erb@Colostate.edu

Unimolecular decomposition of nitrogen-rich energetic salt molecules bis(ammonium)5,5′-bistetrazolate (NH{sub 4}){sub 2}BT and bis(triaminoguanidinium) 5,5′-azotetrazolate TAGzT, has been explored via 283 nm laser excitation. The N{sub 2} molecule, with a cold rotational temperature (<30 K), is observed as an initial decomposition product, subsequent to UV excitation. Initial decomposition mechanisms for the two electronically excited salt molecules are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) ((NH{sub 4}){sub 2}BT) and ONIOM (CASSCF/6-31G(d):UFF) (TAGzT) levels illustrate that conical intersections play an essential role in the decomposition mechanism as they provide non-adiabatic, ultrafast radiationless internalmore » conversion between upper and lower electronic states. The tetrazole ring opens on the S{sub 1} excited state surface and, through conical intersections (S{sub 1}/S{sub 0}){sub CI}, N{sub 2} product is formed on the ground state potential energy surface without rotational excitation. The tetrazole rings open at the N2—N3 ring bond with the lowest energy barrier: the C—N ring bond opening has a higher energy barrier than that for any of the N—N ring bonds: this is consistent with findings for other nitrogen-rich neutral organic energetic materials. TAGzT can produce N{sub 2} either by the opening of tetrazole ring or from the N=N group linking its two tetrazole rings. Nonetheless, opening of a tetrazole ring has a much lower energy barrier. Vibrational temperatures of N{sub 2} products are hot based on theoretical predictions. Energy barriers for opening of the tetrazole ring for all the nitrogen-rich energetic materials studied thus far, including both neutral organic molecules and salts, are in the range from 0.31 to 2.71 eV. Energy of the final molecular structure of these systems with dissociated N{sub 2} product is in the range from −1.86 to 3.11 eV. The main difference between energetic salts and neutral nitrogen-rich energetic material is that energetic salts usually have lower excitation energy.« less

Transportation Network Analysis and Decomposition Methods

DOT National Transportation Integrated Search

1978-03-01

The report outlines research in transportation network analysis using decomposition techniques as a basis for problem solutions. Two transportation network problems were considered in detail: a freight network flow problem and a scheduling problem fo...

Application of vacuum stability test to determine thermal decomposition kinetics of nitramines bonded by polyurethane matrix

NASA Astrophysics Data System (ADS)

Elbeih, Ahmed; Abd-Elghany, Mohamed; Elshenawy, Tamer

2017-03-01

Vacuum stability test (VST) is mainly used to study compatibility and stability of energetic materials. In this work, VST has been investigated to study thermal decomposition kinetics of four cyclic nitramines, 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-HNIW, CL-20), bonded by polyurethane matrix based on hydroxyl terminated polybutadiene (HTPB). Model fitting and model free (isoconversional) methods have been applied to determine the decomposition kinetics from VST results. For comparison, the decomposition kinetics were determined isothermally by ignition delay technique and non-isothermally by Advanced Kinetics and Technology Solution (AKTS) software. The activation energies for thermolysis obtained by isoconversional method based on VST technique of RDX/HTPB, HMX/HTPB, BCHMX/HTPB and CL20/HTPB were 157.1, 203.1, 190.0 and 176.8 kJ mol-1 respectively. Model fitting method proved that the mechanism of thermal decomposition of BCHMX/HTPB is controlled by the nucleation model while all the other studied PBXs are controlled by the diffusion models. A linear relationship between the ignition temperatures and the activation energies was observed. BCHMX/HTPB is interesting new PBX in the research stage.

Electrochemical and Infrared Absorption Spectroscopy Detection of SF₆ Decomposition Products.

PubMed

Dong, Ming; Zhang, Chongxing; Ren, Ming; Albarracín, Ricardo; Ye, Rixin

2017-11-15

Sulfur hexafluoride (SF₆) gas-insulated electrical equipment is widely used in high-voltage (HV) and extra-high-voltage (EHV) power systems. Partial discharge (PD) and local heating can occur in the electrical equipment because of insulation faults, which results in SF₆ decomposition and ultimately generates several types of decomposition products. These SF₆ decomposition products can be qualitatively and quantitatively detected with relevant detection methods, and such detection contributes to diagnosing the internal faults and evaluating the security risks of the equipment. At present, multiple detection methods exist for analyzing the SF₆ decomposition products, and electrochemical sensing (ES) and infrared (IR) spectroscopy are well suited for application in online detection. In this study, the combination of ES with IR spectroscopy is used to detect SF₆ gas decomposition. First, the characteristics of these two detection methods are studied, and the data analysis matrix is established. Then, a qualitative and quantitative analysis ES-IR model is established by adopting a two-step approach. A SF₆ decomposition detector is designed and manufactured by combining an electrochemical sensor and IR spectroscopy technology. The detector is used to detect SF₆ gas decomposition and is verified to reliably and accurately detect the gas components and concentrations.

One Step Synthesis of NiO Nanoparticles via Solid-State Thermal Decomposition at Low-Temperature of Novel Aqua(2,9-dimethyl-1,10-phenanthroline)NiCl2 Complex

PubMed Central

Barakat, Assem; Al-Noaimi, Mousa; Suleiman, Mohammed; Aldwayyan, Abdullah S.; Hammouti, Belkheir; Ben Hadda, Taibi; Haddad, Salim F.; Boshaala, Ahmed; Warad, Ismail

2013-01-01

[NiCl2(C14H12N2)(H2O)] complex has been synthesized from nickel chloride hexahydrate (NiCl2·6H2O) and 2,9-dimethyl-1,10-phenanthroline (dmphen) as N,N-bidentate ligand. The synthesized complex was characterized by elemental analysis, infrared (IR) spectroscopy, ultraviolet-visible (UV-vis) spectroscopy and differential thermal/thermogravimetric analysis (TG/DTA). The complex was further confirmed by single crystal X-ray diffraction (XRD) as triclinic with space group P-1. The desired complex, subjected to thermal decomposition at low temperature of 400 ºC in an open atmosphere, revealed a novel and facile synthesis of pure NiO nanoparticles with uniform spherical particle; the structure of the NiO nanoparticles product was elucidated on the basis of Fourier transform infrared (FT-IR), UV-vis spectroscopy, TG/DTA, XRD, scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDXS) and transmission electron microscopy (TEM). PMID:24351867

Energy in first order 2 +1 gravity

NASA Astrophysics Data System (ADS)

Corichi, Alejandro; Rubalcava-García, Iraís

2015-08-01

We consider Λ =0 three-dimensional gravity with asymptotically flat boundary conditions. This system was studied by Ashtekar and Varadarajan within the second-order formalism—with metric variables—who showed that the Regge-Teitelboim formalism yields a consistent Hamiltonian description where, surprisingly, the energy is bounded from below and from above. The energy of the spacetime is, however, determined up to an arbitrary constant. The natural choice was to fix that freedom such that Minkowski spacetime has zero energy. More recently, Marolf and Patiño started from the Einstein-Hilbert action supplemented with the Gibbons-Hawking term and showed that, in the (2 +1 ) decomposition of the theory, the energy is shifted from the Ashtekar-Varadarajan analysis in such a way that Minkowski spacetime possesses a negative energy. In this contribution we consider the first-order formalism, where the fundamental variables are a s o (2 ,1 ) connection waIJ and a triad eaI . We consider two actions. A natural extension to 3 dimensions of the consistent action in 4 D Palatini gravity is shown to be finite and differentiable. For this action, the (2 +1 ) decomposition (that we perform using two methods) yields a Hamiltonian boundary term that corresponds to energy. It assigns zero energy to Minkowski spacetime. We then put forward a totally gauge invariant action and show that it is also well defined and differentiable. Interestingly, it turns out to be related, on shell, to the 3D Palatini action by an additive constant in such a way that its associated energy is given by the Marolf-Patiño expression. Thus, we conclude that, from the perspective of the first-order formalism, Minkowski spacetime can consistently have either zero, or a negative energy equal to -1 /4 G , depending on the choice of consistent action employed as starting point.

On the combinatorics of sparsification.

PubMed

Huang, Fenix Wd; Reidys, Christian M

2012-10-22

We study the sparsification of dynamic programming based on folding algorithms of RNA structures. Sparsification is a method that improves significantly the computation of minimum free energy (mfe) RNA structures. We provide a quantitative analysis of the sparsification of a particular decomposition rule, Λ∗. This rule splits an interval of RNA secondary and pseudoknot structures of fixed topological genus. Key for quantifying sparsifications is the size of the so called candidate sets. Here we assume mfe-structures to be specifically distributed (see Assumption 1) within arbitrary and irreducible RNA secondary and pseudoknot structures of fixed topological genus. We then present a combinatorial framework which allows by means of probabilities of irreducible sub-structures to obtain the expectation of the Λ∗-candidate set w.r.t. a uniformly random input sequence. We compute these expectations for arc-based energy models via energy-filtered generating functions (GF) in case of RNA secondary structures as well as RNA pseudoknot structures. Furthermore, for RNA secondary structures we also analyze a simplified loop-based energy model. Our combinatorial analysis is then compared to the expected number of Λ∗-candidates obtained from the folding mfe-structures. In case of the mfe-folding of RNA secondary structures with a simplified loop-based energy model our results imply that sparsification provides a significant, constant improvement of 91% (theory) to be compared to an 96% (experimental, simplified arc-based model) reduction. However, we do not observe a linear factor improvement. Finally, in case of the "full" loop-energy model we can report a reduction of 98% (experiment). Sparsification was initially attributed a linear factor improvement. This conclusion was based on the so called polymer-zeta property, which stems from interpreting polymer chains as self-avoiding walks. Subsequent findings however reveal that the O(n) improvement is not correct. The combinatorial analysis presented here shows that, assuming a specific distribution (see Assumption 1), of mfe-structures within irreducible and arbitrary structures, the expected number of Λ∗-candidates is Θ(n2). However, the constant reduction is quite significant, being in the range of 96%. We furthermore show an analogous result for the sparsification of the Λ∗-decomposition rule for RNA pseudoknotted structures of genus one. Finally we observe that the effect of sparsification is sensitive to the employed energy model.

Kinetic measurement and prediction of the hydrogen outgassing from the polycrystalline LiH/Li 2O/LiOH system

NASA Astrophysics Data System (ADS)

Dinh, L. N.; Grant, D. M.; Schildbach, M. A.; Smith, R. A.; Siekhaus, W. J.; Balazs, B.; Leckey, J. H.; Kirkpatrick, J. R.; McLean, W.

2005-12-01

Due to the exothermic reaction of lithium hydride (LiH) salt with water during transportation and handling, there is always a thin film of lithium hydroxide (LiOH) present on the LiH surface. In dry or vacuum storage, this thin LiOH film slowly decomposes. The technique of temperature-programmed reaction/decomposition (TPR) was employed in combination with the isoconversion method of thermal analysis to determine the outgassing kinetics of H 2O from pure LiOH and H 2 and H 2O from this thin LiOH film. H 2 production via the reaction of LiH with LiOH, forming a lithium oxide (Li 2O) interlayer, is thermodynamically favored, with the rate of further reaction limited by diffusion through the Li 2O and the stability of the decomposing LiOH. Lithium hydroxide at the LiOH/vacuum interface also decomposes easily to Li 2O, releasing H 2O which subsequently reacts with LiH in a closed system to form H 2. At the onset of dry decomposition, where H 2 is the predominant product, the activation energy for outgassing from a thin LiOH film is lower than that for bulk LiOH. However, as the reactions at the LiH/Li 2O/LiOH and at the LiOH/vacuum interfaces proceed, the overall activation energy barrier for the outgassing approaches that of bulk LiOH decomposition. The kinetics developed here predict a hydrogen evolution profile in good agreement with hydrogen release observed during long term isothermal storage.

Calibration methods influence quantitative material decomposition in photon-counting spectral CT

NASA Astrophysics Data System (ADS)

Curtis, Tyler E.; Roeder, Ryan K.

2017-03-01

Photon-counting detectors and nanoparticle contrast agents can potentially enable molecular imaging and material decomposition in computed tomography (CT). Material decomposition has been investigated using both simulated and acquired data sets. However, the effect of calibration methods on material decomposition has not been systematically investigated. Therefore, the objective of this study was to investigate the influence of the range and number of contrast agent concentrations within a modular calibration phantom on quantitative material decomposition. A commerciallyavailable photon-counting spectral micro-CT (MARS Bioimaging) was used to acquire images with five energy bins selected to normalize photon counts and leverage the contrast agent k-edge. Material basis matrix values were determined using multiple linear regression models and material decomposition was performed using a maximum a posteriori estimator. The accuracy of quantitative material decomposition was evaluated by the root mean squared error (RMSE), specificity, sensitivity, and area under the curve (AUC). An increased maximum concentration (range) in the calibration significantly improved RMSE, specificity and AUC. The effects of an increased number of concentrations in the calibration were not statistically significant for the conditions in this study. The overall results demonstrated that the accuracy of quantitative material decomposition in spectral CT is significantly influenced by calibration methods, which must therefore be carefully considered for the intended diagnostic imaging application.

Thermal decomposition pathways of ethane

NASA Astrophysics Data System (ADS)

Gordon, Mark S.; Truong, Thanh N.; Pople, John A.

1986-10-01

The alternate thermal decomposition pathways for ethane in its ground state have been investigated, using ab initio electronic structure calculations. Single-point energies were obtained at the full MP4/6-311 G ∗∗ level, using 6-31 G ∗ geometries for reactant, products, and transition states. The thermodynamically favored products are ethylene and molecular hydrogen, but a very large barrier (130 kcal/mol) is found for the direct 1,2-elimination of hydrogen. When calculated barriers are taken into account, the lowest-energy process is the homolytic cleavage of the C-C bond to form two methyl radicals.

Electrochemical Energy Summit An International Summit in Support of Societal Energy Needs

DTIC Science & Technology

2015-03-31

40A/dm2, 80 deg.C. Raney Ni alloy coating had advantage for oxygen over- voltage. (100mV – 200mV saving against Ni metal) Thermal decomposition...100mV – 200mV saving against Ni base metal. Cathode: Thermal decomposition coating of mixed noble metal on Ni base metal showed low hydrogen over... thermal stability up to 210 ◦C, and exhibited a high proton conductivity (2.4×10−2 S cm−1 at 80 ◦C) and a low methanol permeability (3.3×10−7 cm2 s−1

Decomposition techniques

USGS Publications Warehouse

Chao, T.T.; Sanzolone, R.F.

1992-01-01

Sample decomposition is a fundamental and integral step in the procedure of geochemical analysis. It is often the limiting factor to sample throughput, especially with the recent application of the fast and modern multi-element measurement instrumentation. The complexity of geological materials makes it necessary to choose the sample decomposition technique that is compatible with the specific objective of the analysis. When selecting a decomposition technique, consideration should be given to the chemical and mineralogical characteristics of the sample, elements to be determined, precision and accuracy requirements, sample throughput, technical capability of personnel, and time constraints. This paper addresses these concerns and discusses the attributes and limitations of many techniques of sample decomposition along with examples of their application to geochemical analysis. The chemical properties of reagents as to their function as decomposition agents are also reviewed. The section on acid dissolution techniques addresses the various inorganic acids that are used individually or in combination in both open and closed systems. Fluxes used in sample fusion are discussed. The promising microwave-oven technology and the emerging field of automation are also examined. A section on applications highlights the use of decomposition techniques for the determination of Au, platinum group elements (PGEs), Hg, U, hydride-forming elements, rare earth elements (REEs), and multi-elements in geological materials. Partial dissolution techniques used for geochemical exploration which have been treated in detail elsewhere are not discussed here; nor are fire-assaying for noble metals and decomposition techniques for X-ray fluorescence or nuclear methods be discussed. ?? 1992.

Using Microwave Sample Decomposition in Undergraduate Analytical Chemistry

NASA Astrophysics Data System (ADS)

Griff Freeman, R.; McCurdy, David L.

1998-08-01

A shortcoming of many undergraduate classes in analytical chemistry is that students receive little exposure to sample preparation in chemical analysis. This paper reports the progress made in introducing microwave sample decomposition into several quantitative analysis experiments at Truman State University. Two experiments being performed in our current laboratory rotation include closed vessel microwave decomposition applied to the classical gravimetric determination of nickel and the determination of sodium in snack foods by flame atomic emission spectrometry. A third lab, using open-vessel microwave decomposition for the Kjeldahl nitrogen determination is now ready for student trial. Microwave decomposition reduces the time needed to complete these experiments and significantly increases the student awareness of the importance of sample preparation in quantitative chemical analyses, providing greater breadth and realism in the experiments.

Development of a novel hydroxyl ammonium nitrate based liquid propellant for air-independent propulsion

NASA Astrophysics Data System (ADS)

Fontaine, Joseph Henry

The focus of this dissertation is the development of an Unmanned Undersea Vehicle (UUV) liquid propellant employing Hydroxyl Ammonium Nitrate (HAN) as the oxidizer. Hydroxyl Ammonium Nitrate is a highly acidic aqueous based liquid oxidizer. Therefore, in order to achieve efficient combustion of a propellant using this oxidizer, the fuel must be highly water soluble and compatible with the oxidizer to prevent a premature ignition prior to being heated within the combustion chamber. An extensive search of the fuel to be used with this oxidizer was conducted. Propylene glycol was chosen as the fuel for this propellant, and the propellant given the name RF-402. The propellant development process will first evaluate the propellants thermal stability and kinetic parameters using a Differential Scanning Calorimeter (DSC). The purpose of the thermal stability analysis is to determine the temperature at which the propellant decomposition begins for the future safe handling of the propellant and the optimization of the combustion chamber. Additionally, the thermogram results will provide information regarding any undesirable endotherms prior to the decomposition and whether or not the decomposition process is a multi-step process. The Arrhenius type kinetic parameters will be determined using the ASTM method for thermally unstable materials. The activation energy and pre-exponential factor of the propellant will be determined by evaluating the decomposition peak temperature over a temperature scan rate ranging from 1°C per minute to 10°C per minute. The kinetic parameters of the propellant will be compared to those of 81 wt% HAN to determine if the HAN decomposition is controlling the overall decomposition of the propellant RF-402. The lifetime of individual droplets will be analyzed using both experimental and theoretical techniques. The theoretical technique will involve modeling the lifetime of an individual droplet in a combustion chamber like operating environment. The experimental technique will consist of subjecting droplets suspended from a fine gauge thermocouple to an instantaneous hot gas source and recording its temperature response while imaging it using a high power video microscope to determine the physical response of the droplet. This analysis will be the foundation for all future efforts in developing a propulsion system employing the use of RF-402.

Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition

NASA Astrophysics Data System (ADS)

Alavi, Saman; Ripmeester, J. A.

2010-04-01

Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

Nonequilibrium adiabatic molecular dynamics simulations of methane clathrate hydrate decomposition.

PubMed

Alavi, Saman; Ripmeester, J A

2010-04-14

Nonequilibrium, constant energy, constant volume (NVE) molecular dynamics simulations are used to study the decomposition of methane clathrate hydrate in contact with water. Under adiabatic conditions, the rate of methane clathrate decomposition is affected by heat and mass transfer arising from the breakup of the clathrate hydrate framework and release of the methane gas at the solid-liquid interface and diffusion of methane through water. We observe that temperature gradients are established between the clathrate and solution phases as a result of the endothermic clathrate decomposition process and this factor must be considered when modeling the decomposition process. Additionally we observe that clathrate decomposition does not occur gradually with breakup of individual cages, but rather in a concerted fashion with rows of structure I cages parallel to the interface decomposing simultaneously. Due to the concerted breakup of layers of the hydrate, large amounts of methane gas are released near the surface which can form bubbles that will greatly affect the rate of mass transfer near the surface of the clathrate phase. The effects of these phenomena on the rate of methane hydrate decomposition are determined and implications on hydrate dissociation in natural methane hydrate reservoirs are discussed.

Intelligent diagnosis of short hydraulic signal based on improved EEMD and SVM with few low-dimensional training samples

NASA Astrophysics Data System (ADS)

Zhang, Meijun; Tang, Jian; Zhang, Xiaoming; Zhang, Jiaojiao

2016-03-01

The high accurate classification ability of an intelligent diagnosis method often needs a large amount of training samples with high-dimensional eigenvectors, however the characteristics of the signal need to be extracted accurately. Although the existing EMD(empirical mode decomposition) and EEMD(ensemble empirical mode decomposition) are suitable for processing non-stationary and non-linear signals, but when a short signal, such as a hydraulic impact signal, is concerned, their decomposition accuracy become very poor. An improve EEMD is proposed specifically for short hydraulic impact signals. The improvements of this new EEMD are mainly reflected in four aspects, including self-adaptive de-noising based on EEMD, signal extension based on SVM(support vector machine), extreme center fitting based on cubic spline interpolation, and pseudo component exclusion based on cross-correlation analysis. After the energy eigenvector is extracted from the result of the improved EEMD, the fault pattern recognition based on SVM with small amount of low-dimensional training samples is studied. At last, the diagnosis ability of improved EEMD+SVM method is compared with the EEMD+SVM and EMD+SVM methods, and its diagnosis accuracy is distinctly higher than the other two methods no matter the dimension of the eigenvectors are low or high. The improved EEMD is very propitious for the decomposition of short signal, such as hydraulic impact signal, and its combination with SVM has high ability for the diagnosis of hydraulic impact faults.

Catalytically enhanced thermal decomposition of chemically grown silicon oxide layers on Si(001)

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

Leroy, F., E-mail: leroy@cinam.univ-mrs.fr; Passanante, T.; Cheynis, F.

2016-03-14

The thermal decomposition of Si dioxide layers formed by wet chemical treatment on Si(001) has been studied by low-energy electron microscopy. Independent nucleations of voids occur into the Si oxide layers that open by reaction at the void periphery. Depending on the voids, the reaction rates exhibit large differences via the occurrence of a nonlinear growth of the void radius. This non-steady state regime is attributed to the accumulation of defects and silicon hydroxyl species at the SiO{sub 2}/Si interface that enhances the silicon oxide decomposition at the void periphery.

Development Of Polarimetric Decomposition Techniques For Indian Forest Resource Assessment Using Radar Imaging Satellite (Risat-1) Images

NASA Astrophysics Data System (ADS)

Sridhar, J.

2015-12-01

The focus of this work is to examine polarimetric decomposition techniques primarily focussed on Pauli decomposition and Sphere Di-Plane Helix (SDH) decomposition for forest resource assessment. The data processing methods adopted are Pre-processing (Geometric correction and Radiometric calibration), Speckle Reduction, Image Decomposition and Image Classification. Initially to classify forest regions, unsupervised classification was applied to determine different unknown classes. It was observed K-means clustering method gave better results in comparison with ISO Data method.Using the algorithm developed for Radar Tools, the code for decomposition and classification techniques were applied in Interactive Data Language (IDL) and was applied to RISAT-1 image of Mysore-Mandya region of Karnataka, India. This region is chosen for studying forest vegetation and consists of agricultural lands, water and hilly regions. Polarimetric SAR data possess a high potential for classification of earth surface.After applying the decomposition techniques, classification was done by selecting region of interests andpost-classification the over-all accuracy was observed to be higher in the SDH decomposed image, as it operates on individual pixels on a coherent basis and utilises the complete intrinsic coherent nature of polarimetric SAR data. Thereby, making SDH decomposition particularly suited for analysis of high-resolution SAR data. The Pauli Decomposition represents all the polarimetric information in a single SAR image however interpretation of the resulting image is difficult. The SDH decomposition technique seems to produce better results and interpretation as compared to Pauli Decomposition however more quantification and further analysis are being done in this area of research. The comparison of Polarimetric decomposition techniques and evolutionary classification techniques will be the scope of this work.

Effects of anthropogenic heavy metal contamination on litter decomposition in streams - A meta-analysis.

PubMed

Ferreira, Verónica; Koricheva, Julia; Duarte, Sofia; Niyogi, Dev K; Guérold, François

2016-03-01

Many streams worldwide are affected by heavy metal contamination, mostly due to past and present mining activities. Here we present a meta-analysis of 38 studies (reporting 133 cases) published between 1978 and 2014 that reported the effects of heavy metal contamination on the decomposition of terrestrial litter in running waters. Overall, heavy metal contamination significantly inhibited litter decomposition. The effect was stronger for laboratory than for field studies, likely due to better control of confounding variables in the former, antagonistic interactions between metals and other environmental variables in the latter or differences in metal identity and concentration between studies. For laboratory studies, only copper + zinc mixtures significantly inhibited litter decomposition, while no significant effects were found for silver, aluminum, cadmium or zinc considered individually. For field studies, coal and metal mine drainage strongly inhibited litter decomposition, while drainage from motorways had no significant effects. The effect of coal mine drainage did not depend on drainage pH. Coal mine drainage negatively affected leaf litter decomposition independently of leaf litter identity; no significant effect was found for wood decomposition, but sample size was low. Considering metal mine drainage, arsenic mines had a stronger negative effect on leaf litter decomposition than gold or pyrite mines. Metal mine drainage significantly inhibited leaf litter decomposition driven by both microbes and invertebrates, independently of leaf litter identity; no significant effect was found for microbially driven decomposition, but sample size was low. Overall, mine drainage negatively affects leaf litter decomposition, likely through negative effects on invertebrates. Copyright © 2015 Elsevier Ltd. All rights reserved.

Density-functional theory computer simulations of CZTS0.25Se0.75 alloy phase diagrams

NASA Astrophysics Data System (ADS)

Chagarov, E.; Sardashti, K.; Haight, R.; Mitzi, D. B.; Kummel, A. C.

2016-08-01

Density-functional theory simulations of CZTS, CZTSe, and CZTS0.25Se0.75 photovoltaic compounds have been performed to investigate the stability of the CZTS0.25Se0.75 alloy vs. decomposition into CZTS, CZTSe, and other secondary compounds. The Gibbs energy for vibrational contributions was estimated by calculating phonon spectra and thermodynamic properties at finite temperatures. It was demonstrated that the CZTS0.25Se0.75 alloy is stabilized not by enthalpy of formation but primarily by the mixing contributions to the Gibbs energy. The Gibbs energy gains/losses for several decomposition reactions were calculated as a function of temperature with/without intermixing and vibration contributions to the Gibbs energy. A set of phase diagrams was built in the multidimensional space of chemical potentials at 300 K and 900 K temperatures to demonstrate alloy stability and boundary compounds at various chemical conditions. It demonstrated for CZTS0.25Se0.75 that the chemical potentials for stability differ between typical processing temperature (˜900 K) and operating temperature (300 K). This implies that as cooling progresses, the flux/concentration of S should be increased in MBE growth to maintain the CZTS0.25Se0.75 in a thermodynamically stable state to minimize phase decomposition.

Kinetic analysis of overlapping multistep thermal decomposition comprising exothermic and endothermic processes: thermolysis of ammonium dinitramide.

PubMed

Muravyev, Nikita V; Koga, Nobuyoshi; Meerov, Dmitry B; Pivkina, Alla N

2017-01-25

This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN occurs as a consecutive two step mass-loss process comprising the decomposition of ADN and subsequent evaporation/decomposition of in situ generated ammonium nitrate. These reaction steps provide exothermic and endothermic contributions, respectively, to the overall thermal effect. The overall reaction process was deconvoluted into two reaction steps using simultaneously recorded thermogravimetry and differential scanning calorimetry (TG-DSC) curves by considering the different physical meanings of the kinetic data derived from TG and DSC by P value analysis. The kinetic data thus separated into exothermic and endothermic reaction steps were kinetically characterized using kinetic computation methods including isoconversional method, combined kinetic analysis, and master plot method. The overall kinetic behavior was reproduced as the sum of the kinetic equations for each reaction step considering the contributions to the rate data derived from TG and DSC. During reproduction of the kinetic behavior, the kinetic parameters and contributions of each reaction step were optimized using kinetic deconvolution analysis. As a result, the thermal decomposition of ADN was successfully modeled as partially overlapping exothermic and endothermic reaction steps. The logic of the kinetic modeling was critically examined, and the practical usefulness of phenomenological modeling for the thermal decomposition of ADN was illustrated to demonstrate the validity of the methodology and its applicability to similar complex reaction processes.

Beyond Principal Component Analysis: A Trilinear Decomposition Model and Least Squares Estimation.

ERIC Educational Resources Information Center

Pham, Tuan Dinh; Mocks, Joachim

1992-01-01

Sufficient conditions are derived for the consistency and asymptotic normality of the least squares estimator of a trilinear decomposition model for multiway data analysis. The limiting covariance matrix is computed. (Author/SLD)

Automatic network coupling analysis for dynamical systems based on detailed kinetic models.

PubMed

Lebiedz, Dirk; Kammerer, Julia; Brandt-Pollmann, Ulrich

2005-10-01

We introduce a numerical complexity reduction method for the automatic identification and analysis of dynamic network decompositions in (bio)chemical kinetics based on error-controlled computation of a minimal model dimension represented by the number of (locally) active dynamical modes. Our algorithm exploits a generalized sensitivity analysis along state trajectories and subsequent singular value decomposition of sensitivity matrices for the identification of these dominant dynamical modes. It allows for a dynamic coupling analysis of (bio)chemical species in kinetic models that can be exploited for the piecewise computation of a minimal model on small time intervals and offers valuable functional insight into highly nonlinear reaction mechanisms and network dynamics. We present results for the identification of network decompositions in a simple oscillatory chemical reaction, time scale separation based model reduction in a Michaelis-Menten enzyme system and network decomposition of a detailed model for the oscillatory peroxidase-oxidase enzyme system.

Structural applications of metal foams considering material and geometrical uncertainty

NASA Astrophysics Data System (ADS)

Moradi, Mohammadreza

Metal foam is a relatively new and potentially revolutionary material that allows for components to be replaced with elements capable of large energy dissipation, or components to be stiffened with elements which will generate significant supplementary energy dissipation when buckling occurs. Metal foams provide a means to explore reconfiguring steel structures to mitigate cross-section buckling in many cases and dramatically increase energy dissipation in all cases. The microstructure of metal foams consists of solid and void phases. These voids have random shape and size. Therefore, randomness ,which is introduced into metal foams during the manufacturing processes, creating more uncertainty in the behavior of metal foams compared to solid steel. Therefore, studying uncertainty in the performance metrics of structures which have metal foams is more crucial than for conventional structures. Therefore, in this study, structural application of metal foams considering material and geometrical uncertainty is presented. This study applies the Sobol' decomposition of a function of many random variables to different problem in structural mechanics. First, the Sobol' decomposition itself is reviewed and extended to cover the case in which the input random variables have Gaussian distribution. Then two examples are given for a polynomial function of 3 random variables and the collapse load of a two story frame. In the structural example, the Sobol' decomposition is used to decompose the variance of the response, the collapse load, into contributions from the individual input variables. This decomposition reveals the relative importance of the individual member yield stresses in determining the collapse load of the frame. In applying the Sobol' decomposition to this structural problem the following issues are addressed: calculation of the components of the Sobol' decomposition by Monte Carlo simulation; the effect of input distribution on the Sobol' decomposition; convergence of estimates of the Sobol' decomposition with sample size using various sampling schemes; the possibility of model reduction guided by the results of the Sobol' decomposition. For the rest of the study the different structural applications of metal foam is investigated. In the first application, it is shown that metal foams have the potential to serve as hysteric dampers in the braces of braced building frames. Using metal foams in the structural braces decreases different dynamic responses such as roof drift, base shear and maximum moment in the columns. Optimum metal foam strengths are different for different earthquakes. In order to use metal foam in the structural braces, metal foams need to have stable cyclic response which might be achievable for metal foams with high relative density. The second application is to improve strength and ductility of a steel tube by filling it with steel foam. Steel tube beams and columns are able to provide significant strength for structures. They have an efficient shape with large second moment of inertia which leads to light elements with high bending strength. Steel foams with high strength to weight ratio are used to fill the steel tube to improves its mechanical behavior. The linear eigenvalue and plastic collapse finite element (FE) analysis are performed on steel foam filled tube under pure compression and three point bending simulation. It is shown that foam improves the maximum strength and the ability of energy absorption of the steel tubes significantly. Different configurations with different volume of steel foam and composite behavior are investigated. It is demonstrated that there are some optimum configurations with more efficient behavior. If composite action between steel foam and steel increases, the strength of the element will improve due to the change of the failure mode from local buckling to yielding. Moreover, the Sobol' decomposition is used to investigate uncertainty in the strength and ductility of the composite tube, including the sensitivity of the strength to input parameters such as the foam density, tube wall thickness, steel properties etc. Monte Carlo simulation is performed on aluminum foam filled tubes under three point bending conditions. The simulation method is nonlinear finite element analysis. Results show that the steel foam properties have a greater effect on ductility of the steel foam filled tube than its strength. Moreover, flexural strength is more sensitive to steel properties than to aluminum foam properties. Finally, the properties of hypothetical structural steel foam C-channels foamed are investigated via simulations. In thin-walled structural members, stability of the walls is the primary driver of structural limit states. Moreover, having a light weight is one of the main advantages of the thin-walled structural members. Therefore, thin-walled structural members made of steel foam exhibit improved strength while maintaining their low weight. Linear eigenvalue, finite strip method (FSM) and plastic collapse FE analysis is used to evaluate the strength and ductility of steel foam C-channels under uniform compression and bending. It is found that replacing steel walls of the C-channel with steel foam walls increases the local buckling resistance and decreases the global buckling resistance of the C-channel. By using the Sobol' decomposition, an optimum configuration for the variable density steel foam C-channel can be found. For high relative density, replacing solid steel of the lips and flange elements with steel foam increases the buckling strength. On the other hand, for low relative density replacing solid steel of the lips and flange elements with steel foam deceases the buckling strength. Moreover, it is shown that buckling strength of the steel foam C-channel is sensitive to the second order Sobol' indices. In summary, it is shown in this research that the metal foams have a great potential to improve different types of structural responses, and there are many promising application for metal foam in civil structures.

Nascent energy distribution of the Criegee intermediate CH2OO from direct dynamics calculations of primary ozonide dissociation.

PubMed

Pfeifle, Mark; Ma, Yong-Tao; Jasper, Ahren W; Harding, Lawrence B; Hase, William L; Klippenstein, Stephen J

2018-05-07

Ozonolysis produces chemically activated carbonyl oxides (Criegee intermediates, CIs) that are either stabilized or decompose directly. This branching has an important impact on atmospheric chemistry. Prior theoretical studies have employed statistical models for energy partitioning to the CI arising from dissociation of the initially formed primary ozonide (POZ). Here, we used direct dynamics simulations to explore this partitioning for decomposition of c-C 2 H 4 O 3 , the POZ in ethylene ozonolysis. A priori estimates for the overall stabilization probability were then obtained by coupling the direct dynamics results with master equation simulations. Trajectories were initiated at the concerted cycloreversion transition state, as well as the second transition state of a stepwise dissociation pathway, both leading to a CI (H 2 COO) and formaldehyde (H 2 CO). The resulting CI energy distributions were incorporated in master equation simulations of CI decomposition to obtain channel-specific stabilized CI (sCI) yields. Master equation simulations of POZ formation and decomposition, based on new high-level electronic structure calculations, were used to predict yields for the different POZ decomposition channels. A non-negligible contribution of stepwise POZ dissociation was found, and new mechanistic aspects of this pathway were elucidated. By combining the trajectory-based channel-specific sCI yields with the channel branching fractions, an overall sCI yield of (48 ± 5)% was obtained. Non-statistical energy release was shown to measurably affect sCI formation, with statistical models predicting significantly lower overall sCI yields (∼30%). Within the range of experimental literature values (35%-54%), our trajectory-based calculations favor those clustered at the upper end of the spectrum.

Nascent energy distribution of the Criegee intermediate CH2OO from direct dynamics calculations of primary ozonide dissociation

NASA Astrophysics Data System (ADS)

Pfeifle, Mark; Ma, Yong-Tao; Jasper, Ahren W.; Harding, Lawrence B.; Hase, William L.; Klippenstein, Stephen J.

2018-05-01

Ozonolysis produces chemically activated carbonyl oxides (Criegee intermediates, CIs) that are either stabilized or decompose directly. This branching has an important impact on atmospheric chemistry. Prior theoretical studies have employed statistical models for energy partitioning to the CI arising from dissociation of the initially formed primary ozonide (POZ). Here, we used direct dynamics simulations to explore this partitioning for decomposition of c-C2H4O3, the POZ in ethylene ozonolysis. A priori estimates for the overall stabilization probability were then obtained by coupling the direct dynamics results with master equation simulations. Trajectories were initiated at the concerted cycloreversion transition state, as well as the second transition state of a stepwise dissociation pathway, both leading to a CI (H2COO) and formaldehyde (H2CO). The resulting CI energy distributions were incorporated in master equation simulations of CI decomposition to obtain channel-specific stabilized CI (sCI) yields. Master equation simulations of POZ formation and decomposition, based on new high-level electronic structure calculations, were used to predict yields for the different POZ decomposition channels. A non-negligible contribution of stepwise POZ dissociation was found, and new mechanistic aspects of this pathway were elucidated. By combining the trajectory-based channel-specific sCI yields with the channel branching fractions, an overall sCI yield of (48 ± 5)% was obtained. Non-statistical energy release was shown to measurably affect sCI formation, with statistical models predicting significantly lower overall sCI yields (˜30%). Within the range of experimental literature values (35%-54%), our trajectory-based calculations favor those clustered at the upper end of the spectrum.

Material decomposition in an arbitrary number of dimensions using noise compensating projection

NASA Astrophysics Data System (ADS)

O'Donnell, Thomas; Halaweish, Ahmed; Cormode, David; Cheheltani, Rabee; Fayad, Zahi A.; Mani, Venkatesh

2017-03-01

Purpose: Multi-energy CT (e.g., dual energy or photon counting) facilitates the identification of certain compounds via data decomposition. However, the standard approach to decomposition (i.e., solving a system of linear equations) fails if - due to noise - a pixel's vector of HU values falls outside the boundary of values describing possible pure or mixed basis materials. Typically, this is addressed by either throwing away those pixels or projecting them onto the closest point on this boundary. However, when acquiring four (or more) energy volumes, the space bounded by three (or more) materials that may be found in the human body (either naturally or through injection) can be quite small. Noise may significantly limit the number of those pixels to be included within. Therefore, projection onto the boundary becomes an important option. But, projection in higher than 3 dimensional space is not possible with standard vector algebra: the cross-product is not defined. Methods: We describe a technique which employs Clifford Algebra to perform projection in an arbitrary number of dimensions. Clifford Algebra describes a manipulation of vectors that incorporates the concepts of addition, subtraction, multiplication, and division. Thereby, vectors may be operated on like scalars forming a true algebra. Results: We tested our approach on a phantom containing inserts of calcium, gadolinium, iodine, gold nanoparticles and mixtures of pairs thereof. Images were acquired on a prototype photon counting CT scanner under a range of threshold combinations. Comparison of the accuracy of different threshold combinations versus ground truth are presented. Conclusions: Material decomposition is possible with three or more materials and four or more energy thresholds using Clifford Algebra projection to mitigate noise.

Production of ammonia from plasma-catalytic decomposition of urea: Effects of carrier gas composition.

PubMed

Fan, Xing; Li, Jian; Qiu, Danqi; Zhu, Tianle

2018-04-01

Effects of carrier gas composition (N 2 /air) on NH 3 production, energy efficiency regarding NH 3 production and byproducts formation from plasma-catalytic decomposition of urea were systematically investigated using an Al 2 O 3 -packed dielectric barrier discharge (DBD) reactor at room temperature. Results show that the presence of O 2 in the carrier gas accelerates the conversion of urea but leads to less generation of NH 3 . The final yield of NH 3 in the gas phase decreased from 70.5%, 78.7%, 66.6% and 67.2% to 54.1%, 51.7%, 49.6% and 53.4% for applied voltages of 17, 19, 21 and 23kV, respectively when air was used as the carrier gas instead of N 2 . From the viewpoint of energy savings, however, air carrier gas is better than N 2 due to reduced energy consumption and increased energy efficiency for decomposition of a fixed amount of urea. Carrier gas composition has little influence on the major decomposition pathways of urea under the synergetic effects of plasma and Al 2 O 3 catalyst to give NH 3 and CO 2 as the main products. Compared to a small amount of N 2 O formed with N 2 as the carrier gas, however, more byproducts including N 2 O and NO 2 in the gas phase and NH 4 NO 3 in solid deposits were produced with air as the carrier gas, probably due to the unproductive consumption of NH 3 , the possible intermediate HNCO and even urea by the abundant active oxygen species and nitrogen oxides generated in air-DBD plasma. Copyright © 2017. Published by Elsevier B.V.

Physico-Geometrical Kinetics of Solid-State Reactions in an Undergraduate Thermal Analysis Laboratory

ERIC Educational Resources Information Center

Koga, Nobuyoshi; Goshi, Yuri; Yoshikawa, Masahiro; Tatsuoka, Tomoyuki

2014-01-01

An undergraduate kinetic experiment of the thermal decomposition of solids by microscopic observation and thermal analysis was developed by investigating a suitable reaction, applicable techniques of thermal analysis and microscopic observation, and a reliable kinetic calculation method. The thermal decomposition of sodium hydrogen carbonate is…

The Thermal Decomposition of Basic Copper(II) Sulfate.

ERIC Educational Resources Information Center

Tanaka, Haruhiko; Koga, Nobuyoshi

1990-01-01

Discussed is the preparation of synthetic brochantite from solution and a thermogravimetric-differential thermal analysis study of the thermal decomposition of this compound. Other analyses included are chemical analysis and IR spectroscopy. Experimental procedures and results are presented. (CW)

Thermal degradation of ternary blend films containing PVA/chitosan/vanillin

NASA Astrophysics Data System (ADS)

Kasai, Deepak; Chougale, Ravindra; Masti, Saraswati; Narasgoudar, Shivayogi

2018-05-01

The ternary chitosan/poly (vinyl alcohol)/vanillin blend films were prepared by solution casting method. The influence of equal weight percent of poly (vinyl alcohol) and vanillin on thermal stability of the chitosan blend films were investigated by using thermogravimetric analysis (TGA). The kinetic parameters such as enthalpy (ΔH*), entropy (ΔS*), and Gibbs free energy (ΔG*) in the first and second decomposition steps based on the thermogravimetric data were calculated. The thermal stabilities of the blend films were confirmed by thermodynamic parameters obtained in the activation energies, which indicated that increase in the equal weight percent of PVA/vanillin decreased the thermal stability of the chitosan film.

Performance optimization of the power user electric energy data acquire system based on MOEA/D evolutionary algorithm

NASA Astrophysics Data System (ADS)

Ding, Zhongan; Gao, Chen; Yan, Shengteng; Yang, Canrong

2017-10-01

The power user electric energy data acquire system (PUEEDAS) is an important part of smart grid. This paper builds a multi-objective optimization model for the performance of the PUEEADS from the point of view of the combination of the comprehensive benefits and cost. Meanwhile, the Chebyshev decomposition approach is used to decompose the multi-objective optimization problem. We design a MOEA/D evolutionary algorithm to solve the problem. By analyzing the Pareto optimal solution set of multi-objective optimization problem and comparing it with the monitoring value to grasp the direction of optimizing the performance of the PUEEDAS. Finally, an example is designed for specific analysis.

Electrochemical and Infrared Absorption Spectroscopy Detection of SF6 Decomposition Products

PubMed Central

Dong, Ming; Ren, Ming; Ye, Rixin

2017-01-01

Sulfur hexafluoride (SF6) gas-insulated electrical equipment is widely used in high-voltage (HV) and extra-high-voltage (EHV) power systems. Partial discharge (PD) and local heating can occur in the electrical equipment because of insulation faults, which results in SF6 decomposition and ultimately generates several types of decomposition products. These SF6 decomposition products can be qualitatively and quantitatively detected with relevant detection methods, and such detection contributes to diagnosing the internal faults and evaluating the security risks of the equipment. At present, multiple detection methods exist for analyzing the SF6 decomposition products, and electrochemical sensing (ES) and infrared (IR) spectroscopy are well suited for application in online detection. In this study, the combination of ES with IR spectroscopy is used to detect SF6 gas decomposition. First, the characteristics of these two detection methods are studied, and the data analysis matrix is established. Then, a qualitative and quantitative analysis ES-IR model is established by adopting a two-step approach. A SF6 decomposition detector is designed and manufactured by combining an electrochemical sensor and IR spectroscopy technology. The detector is used to detect SF6 gas decomposition and is verified to reliably and accurately detect the gas components and concentrations. PMID:29140268

Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

NASA Astrophysics Data System (ADS)

Faradzhev, N. S.; Perry, C. C.; Kusmierek, D. O.; Fairbrother, D. H.; Madey, T. E.

2004-11-01

The kinetics of decomposition and subsequent chemistry of adsorbed CF2Cl2, activated by low-energy electron irradiation, have been examined and compared with CCl4. These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF2Cl2 and CCl4 dissociation increase in an H2O (D2O) environment (2-3×), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H2O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2×10-15 cm2 for CF2Cl2 and 2.5±0.2×10-15 cm2 for CCl4. RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl- and F- anions in the halocarbon/water films and production of H3O+, CO2, and intermediate compounds COF2 (for CF2Cl2) and COCl2, C2Cl4 (for CCl4) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation.

Analysis methods for polarization state and energy transmission of rays propagating in optical systems

NASA Astrophysics Data System (ADS)

Liu, Chao; Liu, Qiangsheng; Cen, Zhaofeng; Li, Xiaotong

2010-11-01

Polarization state of only completely polarized light can be analyzed by some software, ZEMAX for example. Based on principles of geometrical optics, novel descriptions of the light with different polarization state are provided in this paper. Differential calculus is well used for saving the polarization state and amplitudes of sampling rays when ray tracing. The polarization state changes are analyzed in terms of several typical circumstances, such as Brewster incidence, total reflection. Natural light and partially polarized light are discussed as an important aspect. Further more, a computing method including composition and decomposition of sampling rays at each surface is also set up to analyze the energy transmission of the rays for optical systems. Adopting these analysis methods mentioned, not only the polarization state changes of the incident rays can be obtained, but also the energy distributions can be calculated. Since the energy distributions are obtained, the surface with the most energy loss will be found in the optical system. The energy value and polarization state of light reaching the image surface will also be available. These analysis methods are very helpful for designing or analyzing optical systems, such as analyzing the energy of stray light in high power optical systems, researching the influences of optical surfaces to rays' polarization state in polarization imaging systems and so on.

Vorticity filaments in two-dimensional turbulence: creation, stability and effect

NASA Astrophysics Data System (ADS)

Kevlahan, N. K.-R.; Farge, M.

1997-09-01

Vorticity filaments are characteristic structures of two-dimensional turbulence. The formation, persistence and effect of vorticity filaments are examined using a high-resolution direct numerical simulation (DNS) of the merging of two positive Gaussian vortices pushed together by a weaker negative vortex. Many intense spiral vorticity filaments are created during this interaction and it is shown using a wavelet packet decomposition that, as has been suggested, the coherent vortex stabilizes the filaments. This result is confirmed by a linear stability analysis at the edge of the vortex and by a calculation of the straining induced by the spiral structure of the filament in the vortex core. The time-averaged energy spectra for simulations using hyper-viscosity and Newtonian viscosity have slopes of [minus sign]3 and [minus sign]4 respectively. Apart from a much higher effective Reynolds number (which accounts for the difference in energy spectra), the hyper-viscous simulation has the same dynamics as the Newtonian viscosity simulation. A wavelet packet decomposition of the hyper-viscous simulation reveals that after the merger the energy spectra of the filamentary and coherent parts of the vorticity field have slopes of [minus sign]2 and [minus sign]6 respectively. An asymptotic analysis and DNS for weak external strain shows that a circular filament at a distance R from the vortex centre always reduces the deformation of a Lamb's (Gaussian) vortex in the region r[gt-or-equal, slanted]R. In the region r

Multimaterial Decomposition Algorithm for the Quantification of Liver Fat Content by Using Fast-Kilovolt-Peak Switching Dual-Energy CT: Experimental Validation.

PubMed

Hyodo, Tomoko; Hori, Masatoshi; Lamb, Peter; Sasaki, Kosuke; Wakayama, Tetsuya; Chiba, Yasutaka; Mochizuki, Teruhito; Murakami, Takamichi

2017-02-01

Purpose To assess the ability of fast-kilovolt-peak switching dual-energy computed tomography (CT) by using the multimaterial decomposition (MMD) algorithm to quantify liver fat. Materials and Methods Fifteen syringes that contained various proportions of swine liver obtained from an abattoir, lard in food products, and iron (saccharated ferric oxide) were prepared. Approval of this study by the animal care and use committee was not required. Solid cylindrical phantoms that consisted of a polyurethane epoxy resin 20 and 30 cm in diameter that held the syringes were scanned with dual- and single-energy 64-section multidetector CT. CT attenuation on single-energy CT images (in Hounsfield units) and MMD-derived fat volume fraction (FVF; dual-energy CT FVF) were obtained for each syringe, as were magnetic resonance (MR) spectroscopy measurements by using a 1.5-T imager (fat fraction [FF] of MR spectroscopy). Reference values of FVF (FVF ref ) were determined by using the Soxhlet method. Iron concentrations were determined by inductively coupled plasma optical emission spectroscopy and divided into three ranges (0 mg per 100 g, 48.1-55.9 mg per 100 g, and 92.6-103.0 mg per 100 g). Statistical analysis included Spearman rank correlation and analysis of covariance. Results Both dual-energy CT FVF (ρ = 0.97; P < .001) and CT attenuation on single-energy CT images (ρ = -0.97; P < .001) correlated significantly with FVF ref for phantoms without iron. Phantom size had a significant effect on dual-energy CT FVF after controlling for FVF ref (P < .001). The regression slopes for CT attenuation on single-energy CT images in 20- and 30-cm-diameter phantoms differed significantly (P = .015). In sections with higher iron concentrations, the linear coefficients of dual-energy CT FVF decreased and those of MR spectroscopy FF increased (P < .001). Conclusion Dual-energy CT FVF allows for direct quantification of fat content in units of volume percent. Dual-energy CT FVF was larger in 30-cm than in 20-cm phantoms, though the effect of object size on fat estimation was less than that of CT attenuation on single-energy CT images. In the presence of iron, dual-energy CT FVF led to underestimateion of FVF ref to a lesser degree than FF of MR spectroscopy led to overestimation of FVF ref . © RSNA, 2016 Online supplemental material is available for this article.

SPHARA - A Generalized Spatial Fourier Analysis for Multi-Sensor Systems with Non-Uniformly Arranged Sensors: Application to EEG

PubMed Central

Graichen, Uwe; Eichardt, Roland; Fiedler, Patrique; Strohmeier, Daniel; Zanow, Frank; Haueisen, Jens

2015-01-01

Important requirements for the analysis of multichannel EEG data are efficient techniques for signal enhancement, signal decomposition, feature extraction, and dimensionality reduction. We propose a new approach for spatial harmonic analysis (SPHARA) that extends the classical spatial Fourier analysis to EEG sensors positioned non-uniformly on the surface of the head. The proposed method is based on the eigenanalysis of the discrete Laplace-Beltrami operator defined on a triangular mesh. We present several ways to discretize the continuous Laplace-Beltrami operator and compare the properties of the resulting basis functions computed using these discretization methods. We apply SPHARA to somatosensory evoked potential data from eleven volunteers and demonstrate the ability of the method for spatial data decomposition, dimensionality reduction and noise suppression. When employing SPHARA for dimensionality reduction, a significantly more compact representation can be achieved using the FEM approach, compared to the other discretization methods. Using FEM, to recover 95% and 99% of the total energy of the EEG data, on average only 35% and 58% of the coefficients are necessary. The capability of SPHARA for noise suppression is shown using artificial data. We conclude that SPHARA can be used for spatial harmonic analysis of multi-sensor data at arbitrary positions and can be utilized in a variety of other applications. PMID:25885290

Transport and thermodynamics constrain belowground carbon turnover in a northern peatland

NASA Astrophysics Data System (ADS)

Beer, Julia; Blodau, Christian

2007-06-01

Rates of anaerobic respiration are of central importance for the long-term burial of carbon (C) in peatlands, which are a relevant sink in the global C cycle. To identify constraints on anaerobic peat decomposition, we determined detailed concentration depth profiles of decomposition end-products, i.e. methane (CH 4) and dissolved inorganic carbon (DIC), along with concentrations of relevant decomposition intermediates at an ombrotrophic Canadian peat bog. The magnitude of in situ net production rates of DIC and CH 4 was estimated by inverse pore-water modeling. Vertical transport in the peat was slow and dominated by diffusion leading to the buildup of DIC and CH 4 with depth (5500 μmol L -1 DIC, 500 μmol L -1 CH 4). Highest DIC and CH 4 production rates occurred close to the water table (decomposition constant kd ˜ 10 -3-10 -4 a -1) or in some distinct zones at depth ( kd ˜ 10 -4 a -1). Deeper into the peat, decomposition proceeded very slowly at about kd = 10 -7 a -1. This pattern could be related to thermodynamic and transport constraints. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (-20 to -25 kJ mol -1 CH 4). The methanogenic precursor acetate also accumulated (150 μmol L -1). In line with these findings, CH 4 was formed by hydrogenotrophic methanogenesis at Gibbs free energies of -35 to -40 kJ mol -1 CH 4. This was indicated by an isotopic fractionation α-CH of 1.069-1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol -1 substrate. Although methanogenesis was apparently limited by some other factor in some peat layers, transport and thermodynamic constraints likely impeded respiratory processes in the deeper peat. Constraints on the removal of DIC and CH 4 may thus slow decomposition and contribute to the sustained burial of C in northern peatlands.

QRS analysis using wavelet transformation for the prediction of response to cardiac resynchronization therapy: a prospective pilot study.

PubMed

Vassilikos, Vassilios P; Mantziari, Lilian; Dakos, Georgios; Kamperidis, Vasileios; Chouvarda, Ioanna; Chatzizisis, Yiannis S; Kalpidis, Panagiotis; Theofilogiannakos, Efstratios; Paraskevaidis, Stelios; Karvounis, Haralambos; Mochlas, Sotirios; Maglaveras, Nikolaos; Styliadis, Ioannis H

2014-01-01

Wider QRS and left bundle branch block morphology are related to response to cardiac resynchronization therapy (CRT). A novel time-frequency analysis of the QRS complex may provide additional information in predicting response to CRT. Signal-averaged electrocardiograms were prospectively recorded, before CRT, in orthogonal leads and QRS decomposition in three frequency bands was performed using the Morlet wavelet transformation. Thirty eight patients (age 65±10years, 31 males) were studied. CRT responders (n=28) had wider baseline QRS compared to non-responders and lower QRS energies in all frequency bands. The combination of QRS duration and mean energy in the high frequency band had the best predicting ability (AUC 0.833, 95%CI 0.705-0.962, p=0.002) followed by the maximum energy in the high frequency band (AUC 0.811, 95%CI 0.663-0.960, p=0.004). Wavelet transformation of the QRS complex is useful in predicting response to CRT. © 2013.

Thermal Decomposition Mechanism of CL-20 at Different Temperatures by ReaxFF Reactive Molecular Dynamics Simulations.

PubMed

Wang, Fuping; Chen, Lang; Geng, Deshen; Wu, Junying; Lu, Jianying; Wang, Chen

2018-04-26

Hexanitrohexaazaisowurtzitane (CL-20) has a high detonation velocity and pressure, but its sensitivity is also high, which somewhat limits its applications. Therefore, it is important to understand the mechanism and characteristics of thermal decomposition of CL-20. In this study, a ε-CL-20 supercell was constructed and ReaxFF-lg reactive molecular dynamics simulations were performed to investigate thermal decomposition of ε-CL-20 at various temperatures (2000, 2500, 2750, 3000, 3250, and 3500 K). The mechanism of thermal decomposition of CL-20 was analyzed from the aspects of potential energy evolution, the primary reactions, and the intermediate and final product species. The effect of temperature on thermal decomposition of CL-20 is also discussed. The initial reaction path of thermal decomposition of CL-20 is N-NO 2 cleavage to form NO 2 , followed by C-N cleavage, leading to the destruction of the cage structure. A small number of clusters appear in the early reactions and disappear at the end of the reactions. The initial reaction path of CL-20 decomposition is the same at different temperatures. However, as the temperature increases, the decomposition rate of CL-20 increases and the cage structure is destroyed earlier. The temperature greatly affects the rate constants of H 2 O and N 2 , but it has little effect on the rate constants of CO 2 and H 2 .

Effect of charged and excited states on the decomposition of 1,1-diamino-2,2-dinitroethylene molecules

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

Kimmel, Anna V.; Sushko, Peter V.; Shluger, Alexander L.

The authors have calculated the electronic structure of individual 1,1-diamino-2,2-dinitroethylene molecules (FOX-7) in the gas phase by means of density functional theory with the hybrid B3LYP functional and 6-31+G(d,p) basis set and considered their dissociation pathways. Positively and negatively charged states as well as the lowest excited states of the molecule were simulated. They found that charging and excitation can not only reduce the activation barriers for decomposition reactions but also change the dominating chemistry from endo- to exothermic type. In particular, they found that there are two competing primary initiation mechanisms of FOX-7 decomposition: C-NO{sub 2} bond fission andmore » C-NO{sub 2} to CONO isomerization. Electronic excitation or charging of FOX-7 disfavors CONO formation and, thus, terminates this channel of decomposition. However, if CONO is formed from the neutral FOX-7 molecule, charge trapping and/or excitation results in spontaneous splitting of an NO group accompanied by the energy release. Intramolecular hydrogen transfer is found to be a rare event in FOX-7 unless free electrons are available in the vicinity of the molecule, in which case HONO formation is a feasible exothermic reaction with a relatively low energy barrier. The effect of charged and excited states on other possible reactions is also studied. Implications of the obtained results to FOX-7 decomposition in condensed state are discussed.« less

Microbial genomics, transcriptomics and proteomics: new discoveries in decomposition research using complementary methods.

PubMed

Baldrian, Petr; López-Mondéjar, Rubén

2014-02-01

Molecular methods for the analysis of biomolecules have undergone rapid technological development in the last decade. The advent of next-generation sequencing methods and improvements in instrumental resolution enabled the analysis of complex transcriptome, proteome and metabolome data, as well as a detailed annotation of microbial genomes. The mechanisms of decomposition by model fungi have been described in unprecedented detail by the combination of genome sequencing, transcriptomics and proteomics. The increasing number of available genomes for fungi and bacteria shows that the genetic potential for decomposition of organic matter is widespread among taxonomically diverse microbial taxa, while expression studies document the importance of the regulation of expression in decomposition efficiency. Importantly, high-throughput methods of nucleic acid analysis used for the analysis of metagenomes and metatranscriptomes indicate the high diversity of decomposer communities in natural habitats and their taxonomic composition. Today, the metaproteomics of natural habitats is of interest. In combination with advanced analytical techniques to explore the products of decomposition and the accumulation of information on the genomes of environmentally relevant microorganisms, advanced methods in microbial ecophysiology should increase our understanding of the complex processes of organic matter transformation.

Does energy consumption contribute to environmental pollutants? Evidence from SAARC countries.

PubMed

Akhmat, Ghulam; Zaman, Khalid; Shukui, Tan; Irfan, Danish; Khan, Muhammad Mushtaq

2014-05-01

The objective of the study is to examine the causal relationship between energy consumption and environmental pollutants in selected South Asian Association for Regional Cooperation (SAARC) countries, namely, Bangladesh, India, Nepal, Pakistan, and Srilanka, over the period of 1975-2011. The results indicate that energy consumption acts as an important driver to increase environmental pollutants in SAARC countries. Granger causality runs from energy consumption to environmental pollutants, but not vice versa, except carbon dioxide (CO2) emissions in Nepal where there exists a bidirectional causality between CO2 and energy consumption. Methane emissions in Bangladesh, Pakistan, and Srilanka and extreme temperature in India and Srilanka do not Granger cause energy consumption via both routes, which holds neutrality hypothesis. Variance decomposition analysis shows that among all the environmental indicators, CO2 in Bangladesh and Nepal exerts the largest contribution to changes in electric power consumption. Average precipitation in India, methane emissions in Pakistan, and extreme temperature in Srilanka exert the largest contribution.

An optimization model for energy generation and distribution in a dynamic facility

NASA Technical Reports Server (NTRS)

Lansing, F. L.

1981-01-01

An analytical model is described using linear programming for the optimum generation and distribution of energy demands among competing energy resources and different economic criteria. The model, which will be used as a general engineering tool in the analysis of the Deep Space Network ground facility, considers several essential decisions for better design and operation. The decisions sought for the particular energy application include: the optimum time to build an assembly of elements, inclusion of a storage medium of some type, and the size or capacity of the elements that will minimize the total life-cycle cost over a given number of years. The model, which is structured in multiple time divisions, employ the decomposition principle for large-size matrices, the branch-and-bound method in mixed-integer programming, and the revised simplex technique for efficient and economic computer use.

Molecular Mechanisms in the shock induced decomposition of FOX-7

NASA Astrophysics Data System (ADS)

Mishra, Ankit; Tiwari, Subodh C.; Nakano, Aiichiro; Vashishta, Priya; Kalia, Rajiv; CACS Team

Experimental and first principle computational studies on FOX 7 have either involved a very small system consisting of a few atoms or they did not take into account the decomposition mechanisms under extreme conditions of temperature and pressure. We have performed a large-scale reactive MD simulation using ReaxFF-lg force field to study the shock decomposition of FOX 7. The chemical composition of the principal decomposition products correlates well with experimental observations. Furthermore, we observed that the production of N2 and H2O was inter molecular in nature and was through different chemical pathways. Moreover, the production of CO and CO2 was delayed due to production of large stable C,O atoms cluster. These critical insights into the initial processes involved in the shock induced decomposition of FOX-7 will greatly help in understanding the factors playing an important role in the insensitiveness of this high energy material. This research is supported by AFOSR Award No. FA9550-16-1-0042.

The functionalization of limonite to prepare NZVI and its application in decomposition of p-nitrophenol

NASA Astrophysics Data System (ADS)

Liu, Haibo; Chen, Tianhu; Xie, Qiaoqin; Zou, Xuehua; Chen, Chen; Frost, Ray L.

2015-09-01

Nano zero valent iron (NZVI) was prepared by reducing natural limonite using hydrogen. X-ray fluorescence, thermogravimetry, X-ray diffraction, transmission electron microscope, temperature programmed reduction (TPR), field emission scanning electron microscope/energy disperse spectroscopy (FESEM/EDS) were utilized to characterize the natural limonite and reduced limonite. The ratios of Fe:O before and after reducing was determined using EDS. The reactivity of the NZVI was assessed by decomposition of p-nitrophenol ( p-NP) and was compared with commercial iron powder. In this study, the results of TPR and FESEM/EDS indicated that NZVI can be prepared by reducing natural limonite using hydrogen. Most importantly, this NZVI was proved to have a good performance on decomposition of p-NP and the process of p-NP decomposition agreed well with the pseudo-first-order kinetic model. The reactivity of this NZVI for decomposition of p-NP was greatly superior to that of commercial iron powder.

Decomposition

USGS Publications Warehouse

Middleton, Beth A.

2014-01-01

A cornerstone of ecosystem ecology, decomposition was recognized as a fundamental process driving the exchange of energy in ecosystems by early ecologists such as Lindeman 1942 and Odum 1960). In the history of ecology, studies of decomposition were incorporated into the International Biological Program in the 1960s to compare the nature of organic matter breakdown in various ecosystem types. Such studies still have an important role in ecological studies of today. More recent refinements have brought debates on the relative role microbes, invertebrates and environment in the breakdown and release of carbon into the atmosphere, as well as how nutrient cycling, production and other ecosystem processes regulated by decomposition may shift with climate change. Therefore, this bibliography examines the primary literature related to organic matter breakdown, but it also explores topics in which decomposition plays a key supporting role including vegetation composition, latitudinal gradients, altered ecosystems, anthropogenic impacts, carbon storage, and climate change models. Knowledge of these topics is relevant to both the study of ecosystem ecology as well projections of future conditions for human societies.

X-Ray Thomson Scattering Without the Chihara Decomposition

NASA Astrophysics Data System (ADS)

Magyar, Rudolph; Baczewski, Andrew; Shulenburger, Luke; Hansen, Stephanie B.; Desjarlais, Michael P.; Sandia National Laboratories Collaboration

X-Ray Thomson Scattering is an important experimental technique used in dynamic compression experiments to measure the properties of warm dense matter. The fundamental property probed in these experiments is the electronic dynamic structure factor that is typically modeled using an empirical three-term decomposition (Chihara, J. Phys. F, 1987). One of the crucial assumptions of this decomposition is that the system's electrons can be either classified as bound to ions or free. This decomposition may not be accurate for materials in the warm dense regime. We present unambiguous first principles calculations of the dynamic structure factor independent of the Chihara decomposition that can be used to benchmark these assumptions. Results are generated using a finite-temperature real-time time-dependent density functional theory applied for the first time in these conditions. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Security Administration under contract DE-AC04-94AL85000.

Energetics of lithium ion battery failure.

PubMed

Lyon, Richard E; Walters, Richard N

2016-11-15

The energy released by failure of rechargeable 18-mm diameter by 65-mm long cylindrical (18650) lithium ion cells/batteries was measured in a bomb calorimeter for 4 different commercial cathode chemistries over the full range of charge using a method developed for this purpose. Thermal runaway was induced by electrical resistance (Joule) heating of the cell in the nitrogen-filled pressure vessel (bomb) to preclude combustion. The total energy released by cell failure, ΔHf, was assumed to be comprised of the stored electrical energy E (cell potential×charge) and the chemical energy of mixing, reaction and thermal decomposition of the cell components, ΔUrxn. The contribution of E and ΔUrxn to ΔHf was determined and the mass of volatile, combustible thermal decomposition products was measured in an effort to characterize the fire safety hazard of rechargeable lithium ion cells. Published by Elsevier B.V.

Computer simulations of alkali-acetate solutions: Accuracy of the forcefields in difference concentrations

NASA Astrophysics Data System (ADS)

Ahlstrand, Emma; Zukerman Schpector, Julio; Friedman, Ran

2017-11-01

When proteins are solvated in electrolyte solutions that contain alkali ions, the ions interact mostly with carboxylates on the protein surface. Correctly accounting for alkali-carboxylate interactions is thus important for realistic simulations of proteins. Acetates are the simplest carboxylates that are amphipathic, and experimental data for alkali acetate solutions are available and can be compared with observables obtained from simulations. We carried out molecular dynamics simulations of alkali acetate solutions using polarizable and non-polarizable forcefields and examined the ion-acetate interactions. In particular, activity coefficients and association constants were studied in a range of concentrations (0.03, 0.1, and 1M). In addition, quantum-mechanics (QM) based energy decomposition analysis was performed in order to estimate the contribution of polarization, electrostatics, dispersion, and QM (non-classical) effects on the cation-acetate and cation-water interactions. Simulations of Li-acetate solutions in general overestimated the binding of Li+ and acetates. In lower concentrations, the activity coefficients of alkali-acetate solutions were too high, which is suggested to be due to the simulation protocol and not the forcefields. Energy decomposition analysis suggested that improvement of the forcefield parameters to enable accurate simulations of Li-acetate solutions can be achieved but may require the use of a polarizable forcefield. Importantly, simulations with some ion parameters could not reproduce the correct ion-oxygen distances, which calls for caution in the choice of ion parameters when protein simulations are performed in electrolyte solutions.

Rapid and interference-free analysis of nine B-group vitamins in energy drinks using trilinear component modeling of liquid chromatography-mass spectrometry data.

PubMed

Hu, Yong; Wu, Hai-Long; Yin, Xiao-Li; Gu, Hui-Wen; Xiao, Rong; Xie, Li-Xia; Liu, Zhi; Fang, Huan; Wang, Li; Yu, Ru-Qin

2018-04-01

The aim of the present work was to develop a rapid and interference-free method based on liquid chromatography-mass spectrometry (LC-MS) for the simultaneous determination of nine B-group vitamins in various energy drinks. A smart and green strategy that modeled the three-way data array of LC-MS with second-order calibration methods based on alternating trilinear decomposition (ATLD) and alternating penalty trilinear decomposition (APTLD) algorithms was developed. By virtue of "mathematical separation" and "second-order advantage", the proposed strategy successfully solved the co-eluted peaks and unknown interferents in LC-MS analysis with the elution time less than 4.5min and simple sample preparation. Satisfactory quantitative results were obtained by the ATLD-LC-MS and APTLD-LC-MS methods for the spiked recovery assays, with the average spiked recoveries ranging from 87.2-113.9% to 92.0-111.7%, respectively. These results acquired from the proposed methods were confirmed by the LC-MS/MS method, which shows a quite good consistency with each other. All these results demonstrated that the developed chemometrics-assisted LC-MS strategy had advantages of being rapid, green, accurate and low-cost, and it could be an attractive alternative for the determination of multiple vitamins in complex food matrices, which required no laborious sample preparation, tedious condition optimization or more sophisticated instrumentations. Copyright © 2017 Elsevier B.V. All rights reserved.

Excited electronic state decomposition mechanisms and dynamics of nitramine energetic materials and model systems

NASA Astrophysics Data System (ADS)

Greenfield, Margo

Energetic materials play an important role in aeronautics, the weapon industry, and the propellant industry due to their broad applications as explosives and fuels. RDX (1,3,5-trinitrohexahydro-s-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine), and CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) are compounds which contain high energy density. Although RDX and HMX have been studied extensively over the past several decades a complete understanding of their decomposition mechanisms and dynamics is unknown. Time of flight mass spectroscopy (TOFMS) UV photodissociation (ns) experiments of gas phase RDX, HMX, and CL-20 generate the NO molecule as the initial decomposition product. Four different vibronic transitions of the initial decomposition product, the NO molecule, are observed: A2Sigma(upsilon'=0)←X 2pi(upsilon"=0,1,2,3). Simulations of the rovibronic intensities for the A←X transitions demonstrate that NO dissociated from RDX, HMX, and CL-20 is rotationally cold (˜20 K) and vibrationally hot (˜1800 K). Conversely, experiments on the five model systems (nitromethane, dimethylnitramine (DMNA), nitropyrrolidine, nitropiperidine and dinitropiperazine) produce rotationally hot and vibrationally cold spectra. Laser induced fluorescence (LIF) experiments are performed to rule out the possible decomposition product OH, generated along with NO, perhaps from the suggested HONO elimination mechanism. The OH radical is not observed in the fluorescence experiments, indicating the HONO decomposition intermediate is not an important pathway for the excited electronic state decomposition of cyclic nitramines. The NO molecule is also employed to measure the dynamics of the excited state decomposition. A 226 nm, 180 fs light pulse is utilized to photodissociate the gas phase systems. Stable ion states of DMNA and nitropyrrolidine are observed while the energetic materials and remaining model systems present the NO molecule as the only observed product. Pump-probe transients of the resonant A←X (0-0) transition of the NO molecule show a constant signal indicating these materials decompose faster than the time duration of the 226 nm laser light. Calculational results together with the experimental results indicate the energetic materials decompose through an internal conversion to very highly excited (˜5 eV of vibrational energy) vibrational states of their ground electronic state, while the model systems follow an excited electronic state decomposition pathway.

Laser Ignition of Nitramine Composite Propellants and Crack Propagation and Branching in Burning Solid Propellants

DTIC Science & Technology

1987-10-01

34 Proceedings of the 16th JANNAF Com- bustion Meeting, Sept. 1979, Vol. II, pp. 13-34. 44. Schroeder , M. A., " Critical Analysis of Nitramine Decomposition...34 Proceedings of the 19th JANNAF Combustion Meeting, Oct. 1982. 47. Schroeder , M. A., " Critical Analysis of Nitramine Decomposition Data: Ac- tivation...the surface of the propellant. This is consis- tent with the decomposition mechanism considered by Boggs[48] and Schroeder [43J. They concluded that the

Free energy decomposition of protein-protein interactions.

PubMed

Noskov, S Y; Lim, C

2001-08-01

A free energy decomposition scheme has been developed and tested on antibody-antigen and protease-inhibitor binding for which accurate experimental structures were available for both free and bound proteins. Using the x-ray coordinates of the free and bound proteins, the absolute binding free energy was computed assuming additivity of three well-defined, physical processes: desolvation of the x-ray structures, isomerization of the x-ray conformation to a nearby local minimum in the gas-phase, and subsequent noncovalent complex formation in the gas phase. This free energy scheme, together with the Generalized Born model for computing the electrostatic solvation free energy, yielded binding free energies in remarkable agreement with experimental data. Two assumptions commonly used in theoretical treatments; viz., the rigid-binding approximation (which assumes no conformational change upon complexation) and the neglect of vdW interactions, were found to yield large errors in the binding free energy. Protein-protein vdW and electrostatic interactions between complementary surfaces over a relatively large area (1400--1700 A(2)) were found to drive antibody-antigen and protease-inhibitor binding.

Analysis of the total kinetic energy of fission fragments with the Langevin equation

NASA Astrophysics Data System (ADS)

Usang, M. D.; Ivanyuk, F. A.; Ishizuka, C.; Chiba, S.

2017-12-01

We analyzed the total kinetic energy (TKE) of fission fragments with three-dimensional Langevin calculations for a series of actinides and Fm isotopes at various excitation energies. This allowed us to establish systematic trends of TKE with Z2/A1 /3 of the fissioning system and as a function of excitation energy. In the mass-energy distributions of fission fragments we see the contributions from the standard, super-long, and super-short (in the case of 258Fm) fission modes. For the fission fragments mass distribution of 258Fm we obtained a single peak mass distribution. The decomposition of TKE into the prescission kinetic energy and Coulomb repulsion showed that decrease of TKE with growing excitation energy is accompanied by a decrease of prescission kinetic energy. It was also found that transport coefficients (friction and inertia tensors) calculated by a microscopic model and by macroscopic models give drastically different behaviors of TKE as a function of excitation energy. The results obtained with microscopic transport coefficients are much closer to experimental data than those calculated with macroscopic ones.

Multi-Centrality Graph Spectral Decompositions and Their Application to Cyber Intrusion Detection

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

Chen, Pin-Yu; Choudhury, Sutanay; Hero, Alfred

Many modern datasets can be represented as graphs and hence spectral decompositions such as graph principal component analysis (PCA) can be useful. Distinct from previous graph decomposition approaches based on subspace projection of a single topological feature, e.g., the centered graph adjacency matrix (graph Laplacian), we propose spectral decomposition approaches to graph PCA and graph dictionary learning that integrate multiple features, including graph walk statistics, centrality measures and graph distances to reference nodes. In this paper we propose a new PCA method for single graph analysis, called multi-centrality graph PCA (MC-GPCA), and a new dictionary learning method for ensembles ofmore » graphs, called multi-centrality graph dictionary learning (MC-GDL), both based on spectral decomposition of multi-centrality matrices. As an application to cyber intrusion detection, MC-GPCA can be an effective indicator of anomalous connectivity pattern and MC-GDL can provide discriminative basis for attack classification.« less

More on boundary holographic Witten diagrams

NASA Astrophysics Data System (ADS)

Sato, Yoshiki

2018-01-01

In this paper we discuss geodesic Witten diagrams in general holographic conformal field theories with boundary or defect. In boundary or defect conformal field theory, two-point functions are nontrivial and can be decomposed into conformal blocks in two distinct ways; ambient channel decomposition and boundary channel decomposition. In our previous work [A. Karch and Y. Sato, J. High Energy Phys. 09 (2017) 121., 10.1007/JHEP09(2017)121] we only consider two-point functions of same operators. We generalize our previous work to a situation where operators in two-point functions are different. We obtain two distinct decomposition for two-point functions of different operators.

Separating and Recycling Plastic, Glass, and Gallium from Waste Solar Cell Modules by Nitrogen Pyrolysis and Vacuum Decomposition.

PubMed

Zhang, Lingen; Xu, Zhenming

2016-09-06

Many countries have gained benefits through the solar cells industry due to its high efficiency and nonpolluting power generation associated with solar energy. Accordingly, the market of solar cell modules is expanding rapidly in recent decade. However, how to environmentally friendly and effectively recycle waste solar cell modules is seldom concerned. Based on nitrogen pyrolysis and vacuum decomposition, this work can successfully recycle useful organic components, glass, and gallium from solar cell modules. The results were summarized as follows: (i) nitrogen pyrolysis process can effectively decompose plastic. Organic conversion rate approached 100% in the condition of 773 K, 30 min, and 0.5 L/min N2 flow rate. But, it should be noted that pyrolysis temperature should not exceed 773 K, and harmful products would be increased with the increasing of temperature, such as benzene and its derivatives by GC-MS measurement; (ii) separation principle, products analysis, and optimization of vacuum decomposition were discussed. Gallium can be well recycled under temperature of 1123 K, system pressure of 1 Pa and reaction time of 40 min. This technology is quite significant in accordance with the "Reduce, Reuse, and Recycle Principle" for solid waste, and provides an opportunity for sustainable development of photovoltaic industry.

Kinetics of Thermal Unimolecular Decomposition of Acetic Anhydride: An Integrated Deterministic and Stochastic Model.

PubMed

Mai, Tam V-T; Duong, Minh V; Nguyen, Hieu T; Lin, Kuang C; Huynh, Lam K

2017-04-27

An integrated deterministic and stochastic model within the master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) framework was first used to characterize temperature- and pressure-dependent behaviors of thermal decomposition of acetic anhydride in a wide range of conditions (i.e., 300-1500 K and 0.001-100 atm). Particularly, using potential energy surface and molecular properties obtained from high-level electronic structure calculations at CCSD(T)/CBS, macroscopic thermodynamic properties and rate coefficients of the title reaction were derived with corrections for hindered internal rotation and tunneling treatments. Being in excellent agreement with the scattered experimental data, the results from deterministic and stochastic frameworks confirmed and complemented each other to reveal that the main decomposition pathway proceeds via a 6-membered-ring transition state with the 0 K barrier of 35.2 kcal·mol -1 . This observation was further understood and confirmed by the sensitivity analysis on the time-resolved species profiles and the derived rate coefficients with respect to the ab initio barriers. Such an agreement suggests the integrated model can be confidently used for a wide range of conditions as a powerful postfacto and predictive tool in detailed chemical kinetic modeling and simulation for the title reaction and thus can be extended to complex chemical reactions.

Multiwavelet grading of prostate pathological images

NASA Astrophysics Data System (ADS)

Soltanian-Zadeh, Hamid; Jafari-Khouzani, Kourosh

2002-05-01

We have developed image analysis methods to automatically grade pathological images of prostate. The proposed method generates Gleason grades to images, where each image is assigned a grade between 1 and 5. This is done using features extracted from multiwavelet transformations. We extract energy and entropy features from submatrices obtained in the decomposition. Next, we apply a k-NN classifier to grade the image. To find optimal multiwavelet basis, preprocessing, and classifier, we use features extracted by different multiwavelets with either critically sampled preprocessing or repeated row preprocessing and different k-NN classifiers and compare their performances, evaluated by total misclassification rate (TMR). To evaluate sensitivity to noise, we add white Gaussian noise to images and compare the results (TMR's). We applied proposed methods to 100 images. We evaluated the first and second levels of decomposition using Geronimo, Hardin, and Massopust (GHM), Chui and Lian (CL), and Shen (SA4) multiwavelets. We also evaluated k-NN classifier for k=1,2,3,4,5. Experimental results illustrate that first level of decomposition is quite noisy. They also show that critically sampled preprocessing outperforms repeated row preprocessing and has less sensitivity to noise. Finally, comparison studies indicate that SA4 multiwavelet and k-NN classifier (k=1) generates optimal results (with smallest TMR of 3%).

Mechanochemical spinodal decomposition: a phenomenological theory of phase transformations in multi-component, crystalline solids

DOE PAGES

Rudraraju, Shiva; Van der Ven, Anton; Garikipati, Krishna

2016-06-10

Here, we present a phenomenological treatment of diffusion-driven martensitic phase transformations in multi-component crystalline solids that arise from non-convex free energies in mechanical and chemical variables. The treatment describes diffusional phase transformations that are accompanied by symmetry-breaking structural changes of the crystal unit cell and reveals the importance of a mechanochemical spinodal, defined as the region in strain-composition space, where the free-energy density function is non-convex. The approach is relevant to phase transformations wherein the structural order parameters can be expressed as linear combinations of strains relative to a high-symmetry reference crystal. The governing equations describing mechanochemical spinodal decomposition aremore » variationally derived from a free-energy density function that accounts for interfacial energy via gradients of the rapidly varying strain and composition fields. A robust computational framework for treating the coupled, higher-order diffusion and nonlinear strain gradient elasticity problems is presented. Because the local strains in an inhomogeneous, transforming microstructure can be finite, the elasticity problem must account for geometric nonlinearity. An evaluation of available experimental phase diagrams and first-principles free energies suggests that mechanochemical spinodal decomposition should occur in metal hydrides such as ZrH 2-2c. The rich physics that ensues is explored in several numerical examples in two and three dimensions, and the relevance of the mechanism is discussed in the context of important electrode materials for Li-ion batteries and high-temperature ceramics.« less

Liquid fuel reforming using microwave plasma at atmospheric pressure

NASA Astrophysics Data System (ADS)

Miotk, Robert; Hrycak, Bartosz; Czylkowski, Dariusz; Dors, Miroslaw; Jasinski, Mariusz; Mizeraczyk, Jerzy

2016-06-01

Hydrogen is expected to be one of the most promising energy carriers. Due to the growing interest in hydrogen production technologies, in this paper we present the results of experimental investigations of thermal decomposition and dry reforming of two alcohols (ethanol and isopropanol) in the waveguide-supplied metal-cylinder-based nozzleless microwave (915 MHz) plasma source (MPS). The hydrogen production experiments were preceded by electrodynamics properties investigations of the used MPS and plasma spectroscopic diagnostics. All experimental tests were performed with the working gas (nitrogen or carbon dioxide) flow rate ranging from 1200 to 3900 normal litres per hour and an absorbed microwave power up to 5 kW. The alcohols were introduced into the plasma using an induction heating vaporizer. The ethanol thermal decomposition resulted in hydrogen selectivity up to 100%. The hydrogen production rate was up to 1150 NL(H2) h-1 and the energy yield was 267 NL(H2) kWh-1 of absorbed microwave energy. Due to intense soot production, the thermal decomposition process was not appropriate for isopropanol conversion. Considering the dry reforming process, using isopropanol was more efficient in hydrogen production than ethanol. The rate and energy yield of hydrogen production were up to 1116 NL(H2) h-1 and 223 NL(H2) kWh-1 of microwave energy used, respectively. However, the hydrogen selectivity was no greater than 37%. Selected results given by the experiment were compared with the results of numerical modeling.

Nonlinear mode decomposition: A noise-robust, adaptive decomposition method

NASA Astrophysics Data System (ADS)

Iatsenko, Dmytro; McClintock, Peter V. E.; Stefanovska, Aneta

2015-09-01

The signals emanating from complex systems are usually composed of a mixture of different oscillations which, for a reliable analysis, should be separated from each other and from the inevitable background of noise. Here we introduce an adaptive decomposition tool—nonlinear mode decomposition (NMD)—which decomposes a given signal into a set of physically meaningful oscillations for any wave form, simultaneously removing the noise. NMD is based on the powerful combination of time-frequency analysis techniques—which, together with the adaptive choice of their parameters, make it extremely noise robust—and surrogate data tests used to identify interdependent oscillations and to distinguish deterministic from random activity. We illustrate the application of NMD to both simulated and real signals and demonstrate its qualitative and quantitative superiority over other approaches, such as (ensemble) empirical mode decomposition, Karhunen-Loève expansion, and independent component analysis. We point out that NMD is likely to be applicable and useful in many different areas of research, such as geophysics, finance, and the life sciences. The necessary matlab codes for running NMD are freely available for download.

Explosive decomposition of ethylene oxide at elevated condition: effect of ignition energy, nitrogen dilution, and turbulence.

PubMed

Pekalski, A A; Zevenbergen, J F; Braithwaite, M; Lemkowitz, S M; Pasman, H J

2005-02-14

Experimental and theoretical investigation of explosive decomposition of ethylene oxide (EO) at fixed initial experimental parameters (T=100 degrees C, P=4 bar) in a 20-l sphere was conducted. Safety-related parameters, namely the maximum explosion pressure, the maximum rate of pressure rise, and the Kd values, were experimentally determined for pure ethylene oxide and ethylene oxide diluted with nitrogen. The influence of the ignition energy on the explosion parameters was also studied. All these dependencies are quantified in empirical formulas. Additionally, the effect of turbulence on explosive decomposition of ethylene oxide was investigated. In contrast to previous studies, it is found that turbulence significantly influences the explosion severity parameters, mostly the rate of pressure rise. Thermodynamic models are used to calculate the maximum explosion pressure of pure and of nitrogen-diluted ethylene oxide, at different initial temperatures. Soot formation was experimentally observed. Relation between the amounts of soot formed and the explosion pressure was experimentally observed and was calculated.

The application of microwave digestion in decomposing some refractory ore samples with solid fusion agent.

PubMed

Lu, Yan; Li, Gang; Liu, Wei; Yuan, Hongyan; Xiao, Dan

2018-08-15

It is known that most of the refractory ore are the basis of national economy and widely applied in various fields, however, the complexity of the chemical composition and the diversity of the crystallinity in the mineral phases make the sample pre-treatment of refractory ore still remains a challenge. In this work, the complete decomposition of the refractory ore sample can be achieved just by exposing the solid fusion agent and the refractory ore sample in the microwave irradiation environment for a few minutes, and induced by a drop of water. A digestion time of 15 min for 3.0 g solid fusion agent mixture of sodium peroxide/sodium carbonate (Na 2 O 2 /Na 2 CO 3 ) in a corundum crucible via microwave heating is sufficient to decompose 0.1 g refractory ore sample. An excellent microwave digestion solid agent should meet the following conditions, a good decomposition ability, an outstanding ability of absorbing microwave energy and converting it into heat quickly, a higher melting point than the decomposing temperature of the ore sample. In the research, the induction effect of water plays an important role for the microwave digestion. The energy which is released by the reaction of water and the solid fusion agent (Na 2 O 2 ) is the key to decompose refractory ore samples with solid fusion agent, which replenished the total energy required for the microwave digestion and made the microwave digestion completed successfully. This microwave digestion technique has good reproducibility and precision, RSD % for Mo, Fe, Ti, Cr and W in the refractory ore samples were all better than 6, except RSD % for Be of about 8 because of the influence of matrix-effect. Meanwhile, the analysis results of the elements in the refractory ore samples provided by the microwave digestion technique were all in good agreement with the analysis results provided by the traditional fusion method except for Cr in the mixture ore samples. In the study, the non-linear dependence of the electromagnetic and thermal properties of the solid fusion agent on temperature under microwave irradiation and the selective heating of microwave are fully applied in this simple microwave technique. Comparing to the traditional fusion decomposition method, this microwave digestion technique is a simple, economical, fast and energy-saving sample pre-treatment technique. Copyright © 2018 Elsevier B.V. All rights reserved.

Thermal behavior of vehicle plastic blends contained acrylonitrile-butadiene-styrene (ABS) in pyrolysis using TG-FTIR.

PubMed

Liu, Guicai; Liao, Yanfen; Ma, Xiaoqian

2017-03-01

As important plastic blends in End-of-Life vehicles (ELV), pyrolysis profiles of ABS/PVC, ABS/PA6 and ABS/PC were investigated using thermogravimetric-Fourier transform infrared spectrometer (TG-FTIR). Also, CaCO 3 was added as plastic filler to discuss its effects on the pyrolysis of these plastics. The results showed that the interaction between ABS and PVC made PVC pyrolysis earlier and HCl emission slightly accelerated. The mixing of ABS and PA6 made their decomposition temperature closer, and ketones in PA6 pyrolysis products were reduced. The presence of ABS made PC pyrolysis earlier, and phenyl compounds in PC pyrolysis products could be transferred into alcohol or H 2 O. The interaction between ABS and other polymers in pyrolysis could be attributed to the intermolecular radical transfer, and free radicals from the polymer firstly decomposed led to a fast initiation the decomposition of the other polymer. As plastic filler, CaCO 3 promoted the thermal decomposition of PA6 and PC, and had no obvious effects on ABS and PVC pyrolysis process. Also, CaCO 3 made the pyrolysis products from PA6 and PC further decomposed into small-molecule compounds like CO 2 . The kinetics analysis showed that isoconversional method like Starink method was more suitable for these polymer blends. Starink method showed the average activation energy of ABS50/PVC50, ABS50/PA50 and ABS50/PC50 was 186.63kJ/mol, 239.61kJ/mol and 248.95kJ/mol, respectively, and the interaction among them could be reflected by the activation energy variation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Atomic and molecular adsorption on Au(111)

DOE PAGES

Santiago-Rodriguez, Yohaselly; Herron, Jeffrey A.; Curet-Arana, Maria C.; ...

2014-05-02

Periodic self-consistent density functional theory (DFT-GGA) calculations were used to study the adsorption of several atomic species, molecular species and molecular fragments on the Au(111) surface with a coverage of 1/4 monolayer (ML). Binding geometries, binding energies, and diffusion barriers were calculated for 27 species. Furthermore, we calculated the surface deformation energy associated with the binding events. The binding strength for all the analyzed species can be ordered as follows: NH 3 < NO < CO < CH 3 < HCO < NH 2 < COOH < OH < HCOO < CNH 2 < H < N < NH

Laurdan spectrum decomposition as a tool for the analysis of surface bilayer structure and polarity: a study with DMPG, peptides and cholesterol.

PubMed

Lúcio, Aline D; Vequi-Suplicy, Cíntia C; Fernandez, Roberto M; Lamy, M Teresa

2010-03-01

The highly hydrophobic fluorophore Laurdan (6-dodecanoyl-2-(dimethylaminonaphthalene)) has been widely used as a fluorescent probe to monitor lipid membranes. Actually, it monitors the structure and polarity of the bilayer surface, where its fluorescent moiety is supposed to reside. The present paper discusses the high sensitivity of Laurdan fluorescence through the decomposition of its emission spectrum into two Gaussian bands, which correspond to emissions from two different excited states, one more solvent relaxed than the other. It will be shown that the analysis of the area fraction of each band is more sensitive to bilayer structural changes than the largely used parameter called Generalized Polarization, possibly because the latter does not completely separate the fluorescence emission from the two different excited states of Laurdan. Moreover, it will be shown that this decomposition should be done with the spectrum as a function of energy, and not wavelength. Due to the presence of the two emission bands in Laurdan spectrum, fluorescence anisotropy should be measured around 480 nm, to be able to monitor the fluorescence emission from one excited state only, the solvent relaxed state. Laurdan will be used to monitor the complex structure of the anionic phospholipid DMPG (dimyristoyl phosphatidylglycerol) at different ionic strengths, and the alterations caused on gel and fluid membranes due to the interaction of cationic peptides and cholesterol. Analyzing both the emission spectrum decomposition and anisotropy it was possible to distinguish between effects on the packing and on the hydration of the lipid membrane surface. It could be clearly detected that a more potent analog of the melanotropic hormone alpha-MSH (Ac-Ser(1)-Tyr(2)-Ser(3)-Met(4)-Glu(5)-His(6)-Phe(7)-Arg(8)-Trp(9)-Gly(10)-Lys(11)-Pro(12)-Val(13)-NH(2)) was more effective in rigidifying the bilayer surface of fluid membranes than the hormone, though the hormone significantly decreases the bilayer surface hydration.

Substrate decomposition in galvanic displacement reaction: Contrast between gold and silver nanoparticle formation

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

Ghosh, Tapas; Satpati, Biswarup, E-mail: biswarup.satpati@saha.ac.in; Kabiraj, D.

We have investigated substrate decomposition during formation of silver and gold nanoparticles in galvanic displacement reaction on germanium surfaces. Silver and gold nanoparticles were synthesized by electroless deposition on sputter coated germanium thin film (∼ 200 nm) grown initially on silicon substrate. The nanoparticles formation and the substrate corrosion were studied using scanning transmission electron microscopy (STEM) and the energy dispersive X-ray (EDX) spectroscopy.

Proteomic analysis reveals large amounts of decomposition enzymes and major metabolic pathways involved in algicidal process of Trametes versicolor F21a.

PubMed

Gao, Xueyan; Wang, Congyan; Dai, Wei; Ren, Shenrong; Tao, Fang; He, Xingbing; Han, Guomin; Wang, Wei

2017-06-20

A recent algicidal mode indicates that fungal mycelia can wrap and eliminate almost all co-cultivated algal cells within a short time span. However, the underlying molecular mechanism is rarely understood. We applied proteomic analysis to investigate the algicidal process of Trametes versicolor F21a and identified 3,754 fungal proteins. Of these, 30 fungal enzymes with endo- or exoglycosidase activities such as β-1,3-glucanase, α-galactosidase, α-glucosidase, alginate lyase and chondroitin lyase were significantly up-regulated. These proteins belong to Glycoside Hydrolases, Auxiliary Activities, Carbohydrate Esterases and Polysaccharide Lyases, suggesting that these enzymes may degrade lipopolysaccharides, peptidoglycans and alginic acid of algal cells. Additionally, peptidase, exonuclease, manganese peroxidase and cytochrome c peroxidase, which decompose proteins and DNA or convert other small molecules of algal cells, could be other major decomposition enzymes. Gene Ontology and KEGG pathway enrichment analysis demonstrated that pyruvate metabolism and tricarboxylic acid cycle pathways play a critical role in response to adverse environment via increasing energy production to synthesize lytic enzymes or uptake molecules. Carbon metabolism, selenocompound metabolism, sulfur assimilation and metabolism, as well as several amino acid biosynthesis pathways could play vital roles in the synthesis of nutrients required by fungal mycelia.

[Relationships between decomposition rate of leaf litter and initial quality across the alpine timberline ecotone in Western Sichuan, China].

PubMed

Yang, Lin; Deng, Chang-chun; Chen Ya-mei; He, Run-lian; Zhang, Jian; Liu, Yang

2015-12-01

The relationships between litter decomposition rate and their initial quality of 14 representative plants in the alpine forest ecotone of western Sichuan were investigated in this paper. The decomposition rate k of the litter ranged from 0.16 to 1.70. Woody leaf litter and moss litter decomposed much slower, and shrubby litter decomposed a little faster. Then, herbaceous litters decomposed fastest among all plant forms. There were significant linear regression relationships between the litter decomposition rate and the N content, lignin content, phenolics content, C/N, C/P and lignin/N. Lignin/N and hemicellulose content could explain 78.4% variation of the litter decomposition rate (k) by path analysis. The lignin/N could explain 69.5% variation of k alone, and the direct path coefficient of lignin/N on k was -0.913. Principal component analysis (PCA) showed that the contribution rate of the first sort axis to k and the decomposition time (t) reached 99.2%. Significant positive correlations existed between lignin/N, lignin content, C/N, C/P and the first sort axis, and the closest relationship existed between lignin/N and the first sort axis (r = 0.923). Lignin/N was the key quality factor affecting plant litter decomposition rate across the alpine timberline ecotone, with the higher the initial lignin/N, the lower the decomposition rate of leaf litter.

Derivation of energy-based base shear force coefficient considering hysteretic behavior and P-delta effects

NASA Astrophysics Data System (ADS)

Ucar, Taner; Merter, Onur

2018-01-01

A modified energy-balance equation accounting for P-delta effects and hysteretic behavior of reinforced concrete members is derived. Reduced hysteretic properties of structural components due to combined stiffness and strength degradation and pinching effects, and hysteretic damping are taken into account in a simple manner by utilizing plastic energy and seismic input energy modification factors. Having a pre-selected yield mechanism, energy balance of structure in inelastic range is considered. P-delta effects are included in derived equation by adding the external work of gravity loads to the work of equivalent inertia forces and equating the total external work to the modified plastic energy. Earthquake energy input to multi degree of freedom (MDOF) system is approximated by using the modal energy-decomposition. Energy-based base shear coefficients are verified by means of both pushover analysis and nonlinear time history (NLTH) analysis of several RC frames having different number of stories. NLTH analyses of frames are performed by using the time histories of ten scaled ground motions compatible with elastic design acceleration spectrum and fulfilling duration/amplitude related requirements of Turkish Seismic Design Code. The observed correlation between energy-based base shear force coefficients and the average base shear force coefficients of NLTH analyses provides a reasonable confidence in estimation of nonlinear base shear force capacity of frames by using the derived equation.

Density-functional theory computer simulations of CZTS{sub 0.25}Se{sub 0.75} alloy phase diagrams

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

Chagarov, E.; Sardashti, K.; Kummel, A. C.

2016-08-14

Density-functional theory simulations of CZTS, CZTSe, and CZTS{sub 0.25}Se{sub 0.75} photovoltaic compounds have been performed to investigate the stability of the CZTS{sub 0.25}Se{sub 0.75} alloy vs. decomposition into CZTS, CZTSe, and other secondary compounds. The Gibbs energy for vibrational contributions was estimated by calculating phonon spectra and thermodynamic properties at finite temperatures. It was demonstrated that the CZTS{sub 0.25}Se{sub 0.75} alloy is stabilized not by enthalpy of formation but primarily by the mixing contributions to the Gibbs energy. The Gibbs energy gains/losses for several decomposition reactions were calculated as a function of temperature with/without intermixing and vibration contributions to themore » Gibbs energy. A set of phase diagrams was built in the multidimensional space of chemical potentials at 300 K and 900 K temperatures to demonstrate alloy stability and boundary compounds at various chemical conditions. It demonstrated for CZTS{sub 0.25}Se{sub 0.75} that the chemical potentials for stability differ between typical processing temperature (∼900 K) and operating temperature (300 K). This implies that as cooling progresses, the flux/concentration of S should be increased in MBE growth to maintain the CZTS{sub 0.25}Se{sub 0.75} in a thermodynamically stable state to minimize phase decomposition.« less

Exploring Patterns of Soil Organic Matter Decomposition with Students and the Public Through the Global Decomposition Project (GDP)

NASA Astrophysics Data System (ADS)

Wood, J. H.; Natali, S.

2014-12-01

The Global Decomposition Project (GDP) is a program designed to introduce and educate students and the general public about soil organic matter and decomposition through a standardized protocol for collecting, reporting, and sharing data. This easy-to-use hands-on activity focuses on questions such as "How do environmental conditions control decomposition of organic matter in soil?" and "Why do some areas accumulate organic matter and others do not?" Soil organic matter is important to local ecosystems because it affects soil structure, regulates soil moisture and temperature, and provides energy and nutrients to soil organisms. It is also important globally because it stores a large amount of carbon, and when microbes "eat", or decompose organic matter they release greenhouse gasses such as carbon dioxide and methane into the atmosphere, which affects the earth's climate. The protocol describes a commonly used method to measure decomposition using a paper made of cellulose, a component of plant cell walls. Participants can receive pre-made cellulose decomposition bags, or make decomposition bags using instructions in the protocol and easily obtained materials (e.g., window screen and lignin-free paper). Individual results will be shared with all participants and the broader public through an online database. We will present decomposition bag results from a research site in Alaskan tundra, as well as from a middle-school-student led experiment in California. The GDP demonstrates how scientific methods can be extended to educate broader audiences, while at the same time, data collected by students and the public can provide new insight into global patterns of soil decomposition. The GDP provides a pathway for scientists and educators to interact and reach meaningful education and research goals.

A Dual Super-Element Domain Decomposition Approach for Parallel Nonlinear Finite Element Analysis

NASA Astrophysics Data System (ADS)

Jokhio, G. A.; Izzuddin, B. A.

2015-05-01

This article presents a new domain decomposition method for nonlinear finite element analysis introducing the concept of dual partition super-elements. The method extends ideas from the displacement frame method and is ideally suited for parallel nonlinear static/dynamic analysis of structural systems. In the new method, domain decomposition is realized by replacing one or more subdomains in a "parent system," each with a placeholder super-element, where the subdomains are processed separately as "child partitions," each wrapped by a dual super-element along the partition boundary. The analysis of the overall system, including the satisfaction of equilibrium and compatibility at all partition boundaries, is realized through direct communication between all pairs of placeholder and dual super-elements. The proposed method has particular advantages for matrix solution methods based on the frontal scheme, and can be readily implemented for existing finite element analysis programs to achieve parallelization on distributed memory systems with minimal intervention, thus overcoming memory bottlenecks typically faced in the analysis of large-scale problems. Several examples are presented in this article which demonstrate the computational benefits of the proposed parallel domain decomposition approach and its applicability to the nonlinear structural analysis of realistic structural systems.

Spinodal decomposition in amorphous metal-silicate thin films: Phase diagram analysis and interface effects on kinetics

NASA Astrophysics Data System (ADS)

Kim, H.; McIntyre, P. C.

2002-11-01

Among several metal silicate candidates for high permittivity gate dielectric applications, the mixing thermodynamics of the ZrO2-SiO2 system were analyzed, based on previously published experimental phase diagrams. The driving force for spinodal decomposition was investigated in an amorphous silicate that was treated as a supercooled liquid solution. A subregular model was used for the excess free energy of mixing of the liquid, and measured invariant points were adopted for the calculations. The resulting simulated ZrO2-SiO2 phase diagram matched the experimental results reasonably well and indicated that a driving force exists for amorphous Zr-silicate compositions between approx40 mol % and approx90 mol % SiO2 to decompose into a ZrO2-rich phase (approx20 mol % SiO2) and SiO2-rich phase (>98 mol % SiO2) through diffusional phase separation at a temperature of 900 degC. These predictions are consistent with recent experimental reports of phase separation in amorphous Zr-silicate thin films. Other metal-silicate systems were also investigated and composition ranges for phase separation in amorphous Hf, La, and Y silicates were identified from the published bulk phase diagrams. The kinetics of one-dimensional spinodal decomposition normal to the plane of the film were simulated for an initially homogeneous Zr-silicate dielectric layer. We examined the effects that local stresses and the capillary driving force for component segregation to the interface have on the rate of spinodal decomposition in amorphous metal-silicate thin films.

Complete Decomposition of Li2CO3 in Li-O2 Batteries Using Ir/B4C as Noncarbon-Based Oxygen Electrode.

PubMed

Song, Shidong; Xu, Wu; Zheng, Jianming; Luo, Langli; Engelhard, Mark H; Bowden, Mark E; Liu, Bin; Wang, Chong-Min; Zhang, Ji-Guang

2017-03-08

Instability of carbon-based oxygen electrodes and incomplete decomposition of Li 2 CO 3 during charge process are critical barriers for rechargeable Li-O 2 batteries. Here we report the complete decomposition of Li 2 CO 3 in Li-O 2 batteries using the ultrafine iridium-decorated boron carbide (Ir/B 4 C) nanocomposite as a noncarbon based oxygen electrode. The systematic investigation on charging the Li 2 CO 3 preloaded Ir/B 4 C electrode in an ether-based electrolyte demonstrates that the Ir/B 4 C electrode can decompose Li 2 CO 3 with an efficiency close to 100% at a voltage below 4.37 V. In contrast, the bare B 4 C without Ir electrocatalyst can only decompose 4.7% of the preloaded Li 2 CO 3 . Theoretical analysis indicates that the high efficiency decomposition of Li 2 CO 3 can be attributed to the synergistic effects of Ir and B 4 C. Ir has a high affinity for oxygen species, which could lower the energy barrier for electrochemical oxidation of Li 2 CO 3 . B 4 C exhibits much higher chemical and electrochemical stability than carbon-based electrodes and high catalytic activity for Li-O 2 reactions. A Li-O 2 battery using Ir/B 4 C as the oxygen electrode material shows highly enhanced cycling stability than those using the bare B 4 C oxygen electrode. Further development of these stable oxygen-electrodes could accelerate practical applications of Li-O 2 batteries.

Thermal decomposition study of manganese sulfide (MnS) nanoparticles

NASA Astrophysics Data System (ADS)

Tailor, Jiten P.; Khimani, Ankurkumar J.; Chaki, Sunil H.; Deshpande, M. P.

2018-05-01

The as-synthesized manganese sulfide (MnS) nanoparticles were used for the thermal study. The nanoparticles were synthesized by simple wet chemical route at ambient temperature. The photoelectron binding energy and chemical composition of MnS nanoparticles was analyzed by X-ray photoelectron spectroscopy (XPS). The thermogravimetric (TG), differential thermogravimetric (DTG) and differential thermal analysis (DTA) were carried out on the as-synthesized MnS nanoparticles. The thermocurves were recorded in inert N2 atmosphere in the temperature range of ambient to 1173 K. The heating rates employed were 5, 10, 15 and 20 K/min. The thermodynamic parameters like activation energy (Ea), enthalpy change (ΔH), entropy change (ΔS) and change in Gibbs free energy (ΔG) of as-synthesized MnS nanoparticles were determined using Kissinger method. The obtained XPS and thermal results are discussed.

Relationship between the Decomposition Process of Coarse Woody Debris and Fungal Community Structure as Detected by High-Throughput Sequencing in a Deciduous Broad-Leaved Forest in Japan

PubMed Central

Yamashita, Satoshi; Masuya, Hayato; Abe, Shin; Masaki, Takashi; Okabe, Kimiko

2015-01-01

We examined the relationship between the community structure of wood-decaying fungi, detected by high-throughput sequencing, and the decomposition rate using 13 years of data from a forest dynamics plot. For molecular analysis and wood density measurements, drill dust samples were collected from logs and stumps of Fagus and Quercus in the plot. Regression using a negative exponential model between wood density and time since death revealed that the decomposition rate of Fagus was greater than that of Quercus. The residual between the expected value obtained from the regression curve and the observed wood density was used as a decomposition rate index. Principal component analysis showed that the fungal community compositions of both Fagus and Quercus changed with time since death. Principal component analysis axis scores were used as an index of fungal community composition. A structural equation model for each wood genus was used to assess the effect of fungal community structure traits on the decomposition rate and how the fungal community structure was determined by the traits of coarse woody debris. Results of the structural equation model suggested that the decomposition rate of Fagus was affected by two fungal community composition components: one that was affected by time since death and another that was not affected by the traits of coarse woody debris. In contrast, the decomposition rate of Quercus was not affected by coarse woody debris traits or fungal community structure. These findings suggest that, in the case of Fagus coarse woody debris, the fungal community structure is related to the decomposition process of its host substrate. Because fungal community structure is affected partly by the decay stage and wood density of its substrate, these factors influence each other. Further research on interactive effects is needed to improve our understanding of the relationship between fungal community structure and the woody debris decomposition process. PMID:26110605

Parallel processing methods for space based power systems

NASA Technical Reports Server (NTRS)

Berry, F. C.

1993-01-01

This report presents a method for doing load-flow analysis of a power system by using a decomposition approach. The power system for the Space Shuttle is used as a basis to build a model for the load-flow analysis. To test the decomposition method for doing load-flow analysis, simulations were performed on power systems of 16, 25, 34, 43, 52, 61, 70, and 79 nodes. Each of the power systems was divided into subsystems and simulated under steady-state conditions. The results from these tests have been found to be as accurate as tests performed using a standard serial simulator. The division of the power systems into different subsystems was done by assigning a processor to each area. There were 13 transputers available, therefore, up to 13 different subsystems could be simulated at the same time. This report has preliminary results for a load-flow analysis using a decomposition principal. The report shows that the decomposition algorithm for load-flow analysis is well suited for parallel processing and provides increases in the speed of execution.

Random-Phase Approximation Methods

NASA Astrophysics Data System (ADS)

Chen, Guo P.; Voora, Vamsee K.; Agee, Matthew M.; Balasubramani, Sree Ganesh; Furche, Filipp

2017-05-01

Random-phase approximation (RPA) methods are rapidly emerging as cost-effective validation tools for semilocal density functional computations. We present the theoretical background of RPA in an intuitive rather than formal fashion, focusing on the physical picture of screening and simple diagrammatic analysis. A new decomposition of the RPA correlation energy into plasmonic modes leads to an appealing visualization of electron correlation in terms of charge density fluctuations. Recent developments in the areas of beyond-RPA methods, RPA correlation potentials, and efficient algorithms for RPA energy and property calculations are reviewed. The ability of RPA to approximately capture static correlation in molecules is quantified by an analysis of RPA natural occupation numbers. We illustrate the use of RPA methods in applications to small-gap systems such as open-shell d- and f-element compounds, radicals, and weakly bound complexes, where semilocal density functional results exhibit strong functional dependence.

Comparative analysis of characteristic electron energy loss spectra and inelastic scattering cross-section spectra of Fe

NASA Astrophysics Data System (ADS)

Parshin, A. S.; Igumenov, A. Yu.; Mikhlin, Yu. L.; Pchelyakov, O. P.; Zhigalov, V. S.

2016-05-01

The inelastic electron scattering cross section spectra of Fe have been calculated based on experimental spectra of characteristic reflection electron energy loss as dependences of the product of the inelastic mean free path by the differential inelastic electron scattering cross section on the electron energy loss. It has been shown that the inelastic electron scattering cross-section spectra have certain advantages over the electron energy loss spectra in the analysis of the interaction of electrons with substance. The peaks of energy loss in the spectra of characteristic electron energy loss and inelastic electron scattering cross sections have been determined from the integral and differential spectra. It has been shown that the energy of the bulk plasmon is practically independent of the energy of primary electrons in the characteristic electron energy loss spectra and monotonically increases with increasing energy of primary electrons in the inelastic electron scattering cross-section spectra. The variation in the maximum energy of the inelastic electron scattering cross-section spectra is caused by the redistribution of intensities over the peaks of losses due to various excitations. The inelastic electron scattering cross-section spectra have been analyzed using the decomposition of the spectra into peaks of the energy loss. This method has been used for the quantitative estimation of the contributions from different energy loss processes to the inelastic electron scattering cross-section spectra of Fe and for the determination of the nature of the energy loss peaks.

Very high pressure combustion; Reaction propagation rates of nitromethane within a diamond anvil cell

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

Rice, S.F.; Foltz, M.F.

1991-11-01

This paper reports on the combustion-front propagation rate of nitromethane that has been examined to pressures of 40 GPa. A new and general technique involving pulsed laser ignition of an energetic material within a diamond anvil cell and a method for monitoring the rapid decomposition of nitromethane and other explosives to more stable chemical products is described in detail. Nitromethane is shown to exhibit a flame propagation rate that increases smoothly to 100 m/s at 30 GPa as a function of pressure. Above 30 GPa, the final solid-state combustion products change dramatically and the flame propagation rate begins to decrease.more » The combustion-front propagation rate is analyzed in terms of an existing condensed-phase model that predicts a relationship between the front propagation rate, U, and the pressure derivative of the chemical kinetic activation energy, dE{sub a}/dP, such that a plot of logU{sup 2} vs. P should be linear. The activation energy is analyzed to yield an effective volume of activation, {Delta}V, of {minus}3.4 ml/mol. The chemical kinetic parameters determined from the combustion-front propagation rate analysis of solid high-pressure nitromethane is compared with results from other thermal decomposition studies of this prototypic molecular explosive.« less

A Gaussian quadrature method for total energy analysis in electronic state calculations

NASA Astrophysics Data System (ADS)

Fukushima, Kimichika

This article reports studies by Fukushima and coworkers since 1980 concerning their highly accurate numerical integral method using Gaussian quadratures to evaluate the total energy in electronic state calculations. Gauss-Legendre and Gauss-Laguerre quadratures were used for integrals in the finite and infinite regions, respectively. Our previous article showed that, for diatomic molecules such as CO and FeO, elliptic coordinates efficiently achieved high numerical integral accuracy even with a numerical basis set including transition metal atomic orbitals. This article will generalize straightforward details for multiatomic systems with direct integrals in each decomposed elliptic coordinate determined from the nuclear positions of picked-up atom pairs. Sample calculations were performed for the molecules O3 and H2O. This article will also try to present, in another coordinate, a numerical integral by partially using the Becke's decomposition published in 1988, but without the Becke's fuzzy cell generated by the polynomials of internuclear distance between the pair atoms. Instead, simple nuclear weights comprising exponential functions around nuclei are used. The one-center integral is performed with a Gaussian quadrature pack in a spherical coordinate, included in the author's original program in around 1980. As for this decomposition into one-center integrals, sample calculations are carried out for Li2.

Silver-mordenite for radiologic gas capture from complex streams. Dual catalytic CH 3I decomposition and I confinement

DOE PAGES

Nenoff, Tina M.; Rodriguez, Mark A.; Soelberg, Nick R.; ...

2014-05-09

The selective capture of radiological iodine ( 129I) is a persistent concern for safe nuclear energy. In these nuclear fuel reprocessing scenarios, the gas streams to be treated are extremely complex, containing several distinct iodine-containing molecules amongst a large variety of other species. Silver-containing mordenite (MOR) is a longstanding benchmark for radioiodine capture, reacting with molecular iodine (I 2) to form AgI. However the mechanisms for organoiodine capture is not well understood. Here we investigate the capture of methyl iodide from complex mixed gas streams by combining chemical analysis of the effluent gas stream with in depth characterization of themore » recovered sorbent. Tools applied include infrared spectroscopy, thermogravimetric analysis with mass spectrometry, micro X-ray fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. Moreover, the MOR zeolite catalyzes decomposition of the methyl iodide through formation of surface methoxy species (SMS), which subsequently reacts with water in the mixed gas stream to form methanol, and with methanol to form dimethyl ether, which are both detected downstream in the effluent. The liberated iodine reacts with Ag in the MOR pore to the form subnanometer AgI clusters, smaller than the MOR pores, suggesting that the iodine is both physically and chemically confined within the zeolite.« less

Photoelectron spectra of the decomposition of ethylene on /110/ tungsten

NASA Technical Reports Server (NTRS)

Plummer, E. W.; Waclawski, B. J.; Vorburger, T. V.

1974-01-01

The experimental apparatus used in the investigation consisted of an ultrahigh-vacuum chamber, a triple-grid, a microwave-excited resonance lamp, and an electron energy analyzer. The chemical nature of the chemisorbed species was studied, taking into account the energy distribution of photoemitted electrons, work function determinations, and low-energy electron diffraction patterns.

Low-temperature solvothermal synthesis of EuS hollow microspheres

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

Peng, Yong; Wang, Hong; Li, Peng

2014-09-15

Graphical abstract: Synthesis of EuS hollow microspheres at low-temperature via solvothermal method for the first time. - Highlights: • We adopt an improved method to synthesise the (Phen)Eu(Et{sub 2}CNS{sub 2}){sub 3} in deionized water. • We have successfully synthesised the EuS hollow microsphere at 230 °C in acetonitrile. • The price of acetonitrile is more inexpensive, so the price of preparation was reduced. - Abstract: EuS crystals are synthesized by low-temperature solvothermal decomposition of the single source precursor complex (Phen)Eu(Et{sub 2}CNS{sub 2}){sub 3} in acetonitrile. X-ray powder diffraction, scanning electron microscopy, granulocyte diameter statistical analysis, surface energy-dispersive X-ray spectroscopy analysis,more » and UV–vis absorption spectroscopy are used to characterize the structure and properties of the obtained EuS crystals. The results show that the formed EuS crystals are uniform hollow microspheres with a typical cubic phase structure of rock salt and the average particle size of 2.01 μm. The mechanisms for the thermal decomposition of the precursor complex and the formation of the EuS hollow microspheres are postulated based on the experimental observations and previous reports.« less

Synthesis of hierarchical flower-like Co3O4 superstructure and its excellent catalytic property for ammonium perchlorate decomposition

NASA Astrophysics Data System (ADS)

Li, Gang; Bai, Weiyang

2018-04-01

Hierarchical flower-like cobalt tetroxide (Co3O4) was successfully synthesized via a facile precipitation method in combination with heat treatment of the cobalt oxalate precursor. The samples were systematically characterized by thermo gravimetric analysis and derivative thermo gravimetric analysis (TGA-DTG), X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and N2 adsorption-desorption measurements. The results indicate that the as-fabricated Co3O4 exhibits uniform flower-like morphologies with diameters of 8-12 μm, which are constructed by one-dimensional nanowires. Furthermore, catalytic effect of this hierarchical porous Co3O4 on ammonium perchlorate (AP) pyrolysis was investigated using differential scanning calorimetry (DSC) techniques. It is found that the pyrolysis temperature of AP shifts 142 °C downward with a 2 wt% addition content of Co3O4. Meanwhile, the addition of Co3O4 results in a dramatic reduction of the apparent activation energy of AP pyrolysis from 216 kJ mol-1 to 152 kJ mol-1, determined by the Kissinger correlation. The results endorse this material as a potential catalyst in AP decomposition.

Acoustics flow analysis in circular duct using sound intensity and dynamic mode decomposition

NASA Astrophysics Data System (ADS)

Weyna, S.

2014-08-01

Sound intensity generation in hard-walled duct with acoustic flow (no mean-flow) is treated experimentally and shown graphically. In paper, numerous methods of visualization illustrating the vortex flow (2D, 3D) can graphically explain diffraction and scattering phenomena occurring inside the duct and around open end area. Sound intensity investigation in annular duct gives a physical picture of sound waves in any duct mode. In the paper, modal energy analysis are discussed with particular reference to acoustics acoustic orthogonal decomposition (AOD). The image of sound intensity fields before and above "cut-off" frequency region are found to compare acoustic modes which might resonate in duct. The experimental results show also the effects of axial and swirling flow. However acoustic field is extremely complicated, because pressures in non-propagating (cut-off) modes cooperate with the particle velocities in propagating modes, and vice versa. Measurement in cylindrical duct demonstrates also the cut-off phenomenon and the effect of reflection from open end. The aim of experimental study was to obtain information on low Mach number flows in ducts in order to improve physical understanding and validate theoretical CFD and CAA models that still may be improved.

Fault detection, isolation, and diagnosis of self-validating multifunctional sensors.

PubMed

Yang, Jing-Li; Chen, Yin-Sheng; Zhang, Li-Li; Sun, Zhen

2016-06-01

A novel fault detection, isolation, and diagnosis (FDID) strategy for self-validating multifunctional sensors is presented in this paper. The sparse non-negative matrix factorization-based method can effectively detect faults by using the squared prediction error (SPE) statistic, and the variables contribution plots based on SPE statistic can help to locate and isolate the faulty sensitive units. The complete ensemble empirical mode decomposition is employed to decompose the fault signals to a series of intrinsic mode functions (IMFs) and a residual. The sample entropy (SampEn)-weighted energy values of each IMFs and the residual are estimated to represent the characteristics of the fault signals. Multi-class support vector machine is introduced to identify the fault mode with the purpose of diagnosing status of the faulty sensitive units. The performance of the proposed strategy is compared with other fault detection strategies such as principal component analysis, independent component analysis, and fault diagnosis strategies such as empirical mode decomposition coupled with support vector machine. The proposed strategy is fully evaluated in a real self-validating multifunctional sensors experimental system, and the experimental results demonstrate that the proposed strategy provides an excellent solution to the FDID research topic of self-validating multifunctional sensors.

Failure Analysis of Short-Circuited Lithium-Ion Battery with Nickel-Manganese-Cobalt/Graphite Electrode.

PubMed

Lee, Seung-Mi; Kim, Jea-Yeon; Byeon, Jai-Won

2018-09-01

Accidental failures and explosions of lithium-ion batteries have been reported in recent years. To determine the root causes and mechanisms of these failures from the perspective of material degradation, failure analysis was conducted for an intentionally shorted lithium-ion battery. The battery was subjected to electrical overcharging and mechanical pressing to simulate internal short-circuiting. After in situ measurement of the temperature increase during the short-circuiting of the electrodes, the disassembled battery components (i.e., the anode, cathode, and separator) were analyzed by scanning electron microscopy and energy-dispersive X-ray spectroscopy. Regardless of the simulated short-circuit method (mechanical or electrical), damage was observed in the shorted batteries. Numerous small cracks and chemical reaction products were observed on the electrode surface, along with pore shielding on the separator. The event of short-circuiting increased the surface temperature of the battery to approximately 90 °C, which prompted the deterioration and decomposition of the electrolyte, thus affecting the overall battery performance; this was attributed to the decomposition of the lithium salt at 60 °C. The gas generation due to the breakdown of the electrolyte causes pressure accumulation inside the cell; therefore, the electrolyte leaks.

Breast Tissue Characterization with Photon-counting Spectral CT Imaging: A Postmortem Breast Study

PubMed Central

Ding, Huanjun; Klopfer, Michael J.; Ducote, Justin L.; Masaki, Fumitaro

2014-01-01

Purpose To investigate the feasibility of breast tissue characterization in terms of water, lipid, and protein contents with a spectral computed tomographic (CT) system based on a cadmium zinc telluride (CZT) photon-counting detector by using postmortem breasts. Materials and Methods Nineteen pairs of postmortem breasts were imaged with a CZT-based photon-counting spectral CT system with beam energy of 100 kVp. The mean glandular dose was estimated to be in the range of 1.8–2.2 mGy. The images were corrected for pulse pile-up and other artifacts by using spectral distortion corrections. Dual-energy decomposition was then applied to characterize each breast into water, lipid, and protein contents. The precision of the three-compartment characterization was evaluated by comparing the composition of right and left breasts, where the standard error of the estimations was determined. The results of dual-energy decomposition were compared by using averaged root mean square to chemical analysis, which was used as the reference standard. Results The standard errors of the estimations of the right-left correlations obtained from spectral CT were 7.4%, 6.7%, and 3.2% for water, lipid, and protein contents, respectively. Compared with the reference standard, the average root mean square error in breast tissue composition was 2.8%. Conclusion Spectral CT can be used to accurately quantify the water, lipid, and protein contents in breast tissue in a laboratory study by using postmortem specimens. © RSNA, 2014 PMID:24814180

Decomposition of dimethylamine gas with dielectric barrier discharge.

PubMed

Ye, Zhaolian; Zhao, Jie; Huang, Hong ying; Ma, Fei; Zhang, Renxi

2013-09-15

The decomposition of dimethylamine (DMA) with gas under high flow rate was investigated with dielectric barrier discharge (DBD) technology. Different parameters including removal efficiency, energy yield, carbon balance and CO2 selectivity, secondary products, as well as pathways and mechanisms of DMA degradation were studied. The experimental results showed that removal efficiency of DMA depended on applied voltage and gas flow rate, but had no obvious correlation with initial concentration. Excellent energy performance was obtained using present DBD technology for DMA abatement. When experiment conditions were controlled at: gas flow rate of 14.9 m(3)/h, initial concentration of 2104 mg/m(3), applied voltage of 4.8 kV, removal efficiency of DMA and energy yield can reach 85.2% and 953.9 g/kWh, respectively. However, carbon balance (around 40%) was not ideal due to shorter residence time (about 0.1s), implying that some additional conditions should be considered to improve the total oxidation of DMA. Moreover, secondary products in outlet gas stream were detected via gas chromatogram-mass spectrum and the amounts of NO3(-) and NO2(-) were analyzed by ion chromatogram. The obtained data demonstrated that NOx might be suppressed due to reductive NH radical form DMA dissociation. The likely reaction pathways and mechanisms for the removal of DMA were suggested based on products analysis. Experimental results demonstrated the application potential of DBD as a clean technology for organic nitrogen-containing gas elimination from gas streams. Copyright © 2013 Elsevier B.V. All rights reserved.

Wigner-Ville distribution and Gabor transform in Doppler ultrasound signal processing.

PubMed

Ghofrani, S; Ayatollahi, A; Shamsollahi, M B

2003-01-01

Time-frequency distributions have been used extensively for nonstationary signal analysis, they describe how the frequency content of a signal is changing in time. The Wigner-Ville distribution (WVD) is the best known. The draw back of WVD is cross-term artifacts. An alternative to the WVD is Gabor transform (GT), a signal decomposition method, which displays the time-frequency energy of a signal on a joint t-f plane without generating considerable cross-terms. In this paper the WVD and GT of ultrasound echo signals are computed analytically.

A general framework of noise suppression in material decomposition for dual-energy CT

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

Petrongolo, Michael; Dong, Xue; Zhu, Lei, E-mail: leizhu@gatech.edu

Purpose: As a general problem of dual-energy CT (DECT), noise amplification in material decomposition severely reduces the signal-to-noise ratio on the decomposed images compared to that on the original CT images. In this work, the authors propose a general framework of noise suppression in material decomposition for DECT. The method is based on an iterative algorithm recently developed in their group for image-domain decomposition of DECT, with an extension to include nonlinear decomposition models. The generalized framework of iterative DECT decomposition enables beam-hardening correction with simultaneous noise suppression, which improves the clinical benefits of DECT. Methods: The authors propose tomore » suppress noise on the decomposed images of DECT using convex optimization, which is formulated in the form of least-squares estimation with smoothness regularization. Based on the design principles of a best linear unbiased estimator, the authors include the inverse of the estimated variance–covariance matrix of the decomposed images as the penalty weight in the least-squares term. Analytical formulas are derived to compute the variance–covariance matrix for decomposed images with general-form numerical or analytical decomposition. As a demonstration, the authors implement the proposed algorithm on phantom data using an empirical polynomial function of decomposition measured on a calibration scan. The polynomial coefficients are determined from the projection data acquired on a wedge phantom, and the signal decomposition is performed in the projection domain. Results: On the Catphan{sup ®}600 phantom, the proposed noise suppression method reduces the average noise standard deviation of basis material images by one to two orders of magnitude, with a superior performance on spatial resolution as shown in comparisons of line-pair images and modulation transfer function measurements. On the synthesized monoenergetic CT images, the noise standard deviation is reduced by a factor of 2–3. By using nonlinear decomposition on projections, the authors’ method effectively suppresses the streaking artifacts of beam hardening and obtains more uniform images than their previous approach based on a linear model. Similar performance of noise suppression is observed in the results of an anthropomorphic head phantom and a pediatric chest phantom generated by the proposed method. With beam-hardening correction enabled by their approach, the image spatial nonuniformity on the head phantom is reduced from around 10% on the original CT images to 4.9% on the synthesized monoenergetic CT image. On the pediatric chest phantom, their method suppresses image noise standard deviation by a factor of around 7.5, and compared with linear decomposition, it reduces the estimation error of electron densities from 33.3% to 8.6%. Conclusions: The authors propose a general framework of noise suppression in material decomposition for DECT. Phantom studies have shown the proposed method improves the image uniformity and the accuracy of electron density measurements by effective beam-hardening correction and reduces noise level without noticeable resolution loss.« less

Linear and nonlinear causal relationship between energy consumption and economic growth in China: New evidence based on wavelet analysis

PubMed Central

2018-01-01

The energy-growth nexus has important policy implications for economic development. The results from many past studies that investigated the causality direction of this nexus can lead to misleading policy guidance. Using data on China from 1953 to 2013, this study shows that an application of causality test on the time series of energy consumption and national output has masked a lot of information. The Toda-Yamamoto test with bootstrapped critical values and the newly proposed non-linear causality test reveal no causal relationship. However, a further application of these tests using series in different time-frequency domain obtained from wavelet decomposition indicates that while energy consumption Granger causes economic growth in the short run, the reverse is true in the medium term. A bidirectional causal relationship is found for the long run. This approach has proven to be superior in unveiling information on the energy-growth nexus that are useful for policy planning over different time horizons. PMID:29782534

Stabilization of the Thermal Decomposition of Poly(Propylene Carbonate) Through Copper Ion Incorporation and Use in Self-Patterning

NASA Astrophysics Data System (ADS)

Spencer, Todd J.; Chen, Yu-Chun; Saha, Rajarshi; Kohl, Paul A.

2011-06-01

Incorporation of copper ions into poly(propylene carbonate) (PPC) films cast from γ-butyrolactone (GBL), trichloroethylene (TCE) or methylene chloride (MeCl) solutions containing a photo-acid generator is shown to stabilize the PPC from thermal decomposition. Copper ions were introduced into the PPC mixtures by bringing the polymer mixture into contact with copper metal. The metal was oxidized and dissolved into the PPC mixture. The dissolved copper interferes with the decomposition mechanism of PPC, raising its decomposition temperature. Thermogravimetric analysis shows that copper ions make PPC more stable by up to 50°C. Spectroscopic analysis indicates that copper ions may stabilize terminal carboxylic acid groups, inhibiting PPC decomposition. The change in thermal stability based on PPC exposure to patterned copper substrates was used to provide a self-aligned patterning method for PPC on copper traces without the need for an additional photopatterning registration step. Thermal decomposition of PPC is then used to create air isolation regions around the copper traces. The spatial resolution of the self-patterning PPC process is limited by the lateral diffusion of the copper ions within the PPC. The concentration profiles of copper within the PPC, patterning resolution, and temperature effects on the PPC decomposition have been studied.

Technical Report Department of Energy Grant #SC0004335 “Tracking Down Cheaters. Molecular Analysis of Carbon Consumption by Organisms That Do Not Contribute to Extracellular Enzyme Pools”

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

Blackwood, Christopher

2015-05-31

The overriding objective of our work is to integrate physiological and community ecology of belowground organisms into understanding of soil carbon dynamics to improve predictions of terrestrial ecosystem models. This includes using metagenomics and metatranscriptomics-based methods to understand microbial interactions affecting decomposition and soil carbon dynamics. The focus of the majority of the work directly related to this project was on “cheating”, a poorly understood microbial interaction with a potentially large effect on decomposition. Model organisms were used to determine the types of organisms that cheat based on their known niche and genomic characteristics. In addition, we study plant andmore » microbial traits and plant-microbe interactions that affect species distributions and soil carbon, and also develop bioinformatics tools to increase the power of ecological inferences that can be obtained from omics-based sequence data.« less

Data decomposition of Monte Carlo particle transport simulations via tally servers

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

Romano, Paul K.; Siegel, Andrew R.; Forget, Benoit

An algorithm for decomposing large tally data in Monte Carlo particle transport simulations is developed, analyzed, and implemented in a continuous-energy Monte Carlo code, OpenMC. The algorithm is based on a non-overlapping decomposition of compute nodes into tracking processors and tally servers. The former are used to simulate the movement of particles through the domain while the latter continuously receive and update tally data. A performance model for this approach is developed, suggesting that, for a range of parameters relevant to LWR analysis, the tally server algorithm should perform with minimal overhead on contemporary supercomputers. An implementation of the algorithmmore » in OpenMC is then tested on the Intrepid and Titan supercomputers, supporting the key predictions of the model over a wide range of parameters. We thus conclude that the tally server algorithm is a successful approach to circumventing classical on-node memory constraints en route to unprecedentedly detailed Monte Carlo reactor simulations.« less

Neural image analysis for estimating aerobic and anaerobic decomposition of organic matter based on the example of straw decomposition

NASA Astrophysics Data System (ADS)

Boniecki, P.; Nowakowski, K.; Slosarz, P.; Dach, J.; Pilarski, K.

2012-04-01

The purpose of the project was to identify the degree of organic matter decomposition by means of a neural model based on graphical information derived from image analysis. Empirical data (photographs of compost content at various stages of maturation) were used to generate an optimal neural classifier (Boniecki et al. 2009, Nowakowski et al. 2009). The best classification properties were found in an RBF (Radial Basis Function) artificial neural network, which demonstrates that the process is non-linear.

THE SPITZER SURVEY OF STELLAR STRUCTURE IN GALAXIES (S{sup 4}G): MULTI-COMPONENT DECOMPOSITION STRATEGIES AND DATA RELEASE

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

Salo, Heikki; Laurikainen, Eija; Laine, Jarkko

The Spitzer Survey of Stellar Structure in Galaxies (S{sup 4}G) is a deep 3.6 and 4.5 μm imaging survey of 2352 nearby (<40 Mpc) galaxies. We describe the S{sup 4}G data analysis pipeline 4, which is dedicated to two-dimensional structural surface brightness decompositions of 3.6 μm images, using GALFIT3.0. Besides automatic 1-component Sérsic fits, and 2-component Sérsic bulge + exponential disk fits, we present human-supervised multi-component decompositions, which include, when judged appropriate, a central point source, bulge, disk, and bar components. Comparison of the fitted parameters indicates that multi-component models are needed to obtain reliable estimates for the bulge Sérsicmore » index and bulge-to-total light ratio (B/T), confirming earlier results. Here, we describe the preparations of input data done for decompositions, give examples of our decomposition strategy, and describe the data products released via IRSA and via our web page (www.oulu.fi/astronomy/S4G-PIPELINE4/MAIN). These products include all the input data and decomposition files in electronic form, making it easy to extend the decompositions to suit specific science purposes. We also provide our IDL-based visualization tools (GALFIDL) developed for displaying/running GALFIT-decompositions, as well as our mask editing procedure (MASK-EDIT) used in data preparation. A detailed analysis of the bulge, disk, and bar parameters derived from multi-component decompositions will be published separately.« less

Multidisciplinary Optimization Methods for Aircraft Preliminary Design

NASA Technical Reports Server (NTRS)

Kroo, Ilan; Altus, Steve; Braun, Robert; Gage, Peter; Sobieski, Ian

1994-01-01

This paper describes a research program aimed at improved methods for multidisciplinary design and optimization of large-scale aeronautical systems. The research involves new approaches to system decomposition, interdisciplinary communication, and methods of exploiting coarse-grained parallelism for analysis and optimization. A new architecture, that involves a tight coupling between optimization and analysis, is intended to improve efficiency while simplifying the structure of multidisciplinary, computation-intensive design problems involving many analysis disciplines and perhaps hundreds of design variables. Work in two areas is described here: system decomposition using compatibility constraints to simplify the analysis structure and take advantage of coarse-grained parallelism; and collaborative optimization, a decomposition of the optimization process to permit parallel design and to simplify interdisciplinary communication requirements.

Impact of joint statistical dual-energy CT reconstruction of proton stopping power images: Comparison to image- and sinogram-domain material decomposition approaches.

PubMed

Zhang, Shuangyue; Han, Dong; Politte, David G; Williamson, Jeffrey F; O'Sullivan, Joseph A

2018-05-01

The purpose of this study was to assess the performance of a novel dual-energy CT (DECT) approach for proton stopping power ratio (SPR) mapping that integrates image reconstruction and material characterization using a joint statistical image reconstruction (JSIR) method based on a linear basis vector model (BVM). A systematic comparison between the JSIR-BVM method and previously described DECT image- and sinogram-domain decomposition approaches is also carried out on synthetic data. The JSIR-BVM method was implemented to estimate the electron densities and mean excitation energies (I-values) required by the Bethe equation for SPR mapping. In addition, image- and sinogram-domain DECT methods based on three available SPR models including BVM were implemented for comparison. The intrinsic SPR modeling accuracy of the three models was first validated. Synthetic DECT transmission sinograms of two 330 mm diameter phantoms each containing 17 soft and bony tissues (for a total of 34) of known composition were then generated with spectra of 90 and 140 kVp. The estimation accuracy of the reconstructed SPR images were evaluated for the seven investigated methods. The impact of phantom size and insert location on SPR estimation accuracy was also investigated. All three selected DECT-SPR models predict the SPR of all tissue types with less than 0.2% RMS errors under idealized conditions with no reconstruction uncertainties. When applied to synthetic sinograms, the JSIR-BVM method achieves the best performance with mean and RMS-average errors of less than 0.05% and 0.3%, respectively, for all noise levels, while the image- and sinogram-domain decomposition methods show increasing mean and RMS-average errors with increasing noise level. The JSIR-BVM method also reduces statistical SPR variation by sixfold compared to other methods. A 25% phantom diameter change causes up to 4% SPR differences for the image-domain decomposition approach, while the JSIR-BVM method and sinogram-domain decomposition methods are insensitive to size change. Among all the investigated methods, the JSIR-BVM method achieves the best performance for SPR estimation in our simulation phantom study. This novel method is robust with respect to sinogram noise and residual beam-hardening effects, yielding SPR estimation errors comparable to intrinsic BVM modeling error. In contrast, the achievable SPR estimation accuracy of the image- and sinogram-domain decomposition methods is dominated by the CT image intensity uncertainties introduced by the reconstruction and decomposition processes. © 2018 American Association of Physicists in Medicine.

Innovative PCDD/F-containing gas stream generating system applied in catalytic decomposition of gaseous dioxins over V2O5-WO3/TiO2-based catalysts.

PubMed

Yang, Chia Cheng; Chang, Shu Hao; Hong, Bao Zhen; Chi, Kai Hsien; Chang, Moo Been

2008-10-01

Development of effective PCDD/F (polychlorinated dibenzo-p-dioxin and dibenzofuran) control technologies is essential for environmental engineers and researchers. In this study, a PCDD/F-containing gas stream generating system was developed to investigate the efficiency and effectiveness of innovative PCDD/F control technologies. The system designed and constructed can stably generate the gas stream with the PCDD/F concentration ranging from 1.0 to 100ng TEQ Nm(-3) while reproducibility test indicates that the PCDD/F recovery efficiencies are between 93% and 112%. This new PCDD/F-containing gas stream generating device is first applied in the investigation of the catalytic PCDD/F control technology. The catalytic decomposition of PCDD/Fs was evaluated with two types of commercial V(2)O(5)-WO(3)/TiO(2)-based catalysts (catalyst A and catalyst B) at controlled temperature, water vapor content, and space velocity. 84% and 91% PCDD/F destruction efficiencies are achieved with catalysts A and B, respectively, at 280 degrees C with the space velocity of 5000h(-1). The results also indicate that the presence of water vapor inhibits PCDD/F decomposition due to its competition with PCDD/F molecules for adsorption on the active vanadia sites for both catalysts. In addition, this study combined integral reaction and Mars-Van Krevelen model to calculate the activation energies of OCDD and OCDF decomposition. The activation energies of OCDD and OCDF decomposition via catalysis are calculated as 24.8kJmol(-1) and 25.2kJmol(-1), respectively.

Two-electron/24-center (2e/24c) bonding in novel diradical π-dimers.

PubMed

Gao, Feng-Wei; Zhong, Rong-Lin; Sun, Shi-Ling; Xu, Hong-Liang; Su, Zhong-Min

2016-10-26

A series of diradical π-dimers 2 with interesting pancake-shaped 2e/24c π-π bonding character were designed and investigated based on the famous phenalenyl (PLY) π-dimer with 2e/12c π-π bonding character. The position of stronger interaction between two layers of radicals was found by the Wiberg bond index (WBI) maximum component. Further, the different contributions of the interaction energy were analyzed quantitatively by energy decomposition analysis (EDA). Among these new diradical π-dimers, 2180 has the smallest layer distance and the largest interaction between two layers of radicals. The unusual PLY analogues can provide new insights into the unique features of two-electron/multicenter (2e/mc) π-π bonding.

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

Horn, Paul R., E-mail: prhorn@berkeley.edu; Mao, Yuezhi; Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu

In energy decomposition analysis of Kohn-Sham density functional theory calculations, the so-called frozen (or pre-polarization) interaction energy contains contributions from permanent electrostatics, dispersion, and Pauli repulsion. The standard classical approach to separate them suffers from several well-known limitations. We introduce an alternative scheme that employs valid antisymmetric electronic wavefunctions throughout and is based on the identification of individual fragment contributions to the initial supersystem wavefunction as determined by an energetic optimality criterion. The density deformations identified with individual fragments upon formation of the initial supersystem wavefunction are analyzed along with the distance dependence of the new and classical terms formore » test cases that include the neon dimer, ammonia borane, water-Na{sup +}, water-Cl{sup −}, and the naphthalene dimer.« less

Thermal decomposition hazard evaluation of hydroxylamine nitrate.

PubMed

Wei, Chunyang; Rogers, William J; Mannan, M Sam

2006-03-17

Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine family and it is a liquid propellant when combined with alkylammonium nitrate fuel in an aqueous solution. Low concentrations of HAN are used primarily in the nuclear industry as a reductant in nuclear material processing and for decontamination of equipment. Also, HAN has been involved in several incidents because of its instability and autocatalytic decomposition behavior. This paper presents calorimetric measurement for the thermal decomposition of 24 mass% HAN/water. Gas phase enthalpy of formation of HAN is calculated using both semi-empirical methods with MOPAC and high-level quantum chemical methods of Gaussian 03. CHETAH is used to estimate the energy release potential of HAN. A Reactive System Screening Tool (RSST) and an Automatic Pressure Tracking Adiabatic Calorimeter (APTAC) are used to characterize thermal decomposition of HAN and to provide guidance about safe conditions for handling and storing of HAN.

Catalytic Decomposition of Hydroxylammonium Nitrate Ionic Liquid: Enhancement of NO Formation.

PubMed

Chambreau, Steven D; Popolan-Vaida, Denisia M; Vaghjiani, Ghanshyam L; Leone, Stephen R

2017-05-18

Hydroxylammonium nitrate (HAN) is a promising candidate to replace highly toxic hydrazine in monopropellant thruster space applications. The reactivity of HAN aerosols on heated copper and iridium targets was investigated using tunable vacuum ultraviolet photoionization time-of-flight aerosol mass spectrometry. The reaction products were identified by their mass-to-charge ratios and their ionization energies. Products include NH 3 , H 2 O, NO, hydroxylamine (HA), HNO 3 , and a small amount of NO 2 at high temperature. No N 2 O was detected under these experimental conditions, despite the fact that N 2 O is one of the expected products according to the generally accepted thermal decomposition mechanism of HAN. Upon introduction of iridium catalyst, a significant enhancement of the NO/HA ratio was observed. This observation indicates that the formation of NO via decomposition of HA is an important pathway in the catalytic decomposition of HAN.

Decomposition of Copper (II) Sulfate Pentahydrate: A Sequential Gravimetric Analysis.

ERIC Educational Resources Information Center

Harris, Arlo D.; Kalbus, Lee H.

1979-01-01

Describes an improved experiment of the thermal dehydration of copper (II) sulfate pentahydrate. The improvements described here are control of the temperature environment and a quantitative study of the decomposition reaction to a thermally stable oxide. Data will suffice to show sequential gravimetric analysis. (Author/SA)

Generalized decompositions of dynamic systems and vector Lyapunov functions

NASA Astrophysics Data System (ADS)

Ikeda, M.; Siljak, D. D.

1981-10-01

The notion of decomposition is generalized to provide more freedom in constructing vector Lyapunov functions for stability analysis of nonlinear dynamic systems. A generalized decomposition is defined as a disjoint decomposition of a system which is obtained by expanding the state-space of a given system. An inclusion principle is formulated for the solutions of the expansion to include the solutions of the original system, so that stability of the expansion implies stability of the original system. Stability of the expansion can then be established by standard disjoint decompositions and vector Lyapunov functions. The applicability of the new approach is demonstrated using the Lotka-Volterra equations.

Megavoltage cargo radiography with dual energy material decomposition

NASA Astrophysics Data System (ADS)

Shikhaliev, Polad M.

2018-02-01

Megavoltage (MV) radiography has important applications in imaging large cargos for detecting illicit materials. A useful feature of MV radiography is the possibility of decomposing and quantifying materials with different atomic numbers. This can be achieved by imaging cargo at two different X-ray energies, or dual energy (DE) radiography. The performance of both single energy and DE radiography depends on beam energy, beam filtration, radiation dose, object size, and object content. The purpose of this work was to perform comprehensive qualitative and quantitative investigations of the image quality in MV radiography depending on the above parameters. A digital phantom was designed including Fe background with thicknesses of 2cm, 6cm, and 18cm, and materials samples of Polyethylene, Fe, Pb, and U. The single energy images were generated at x-ray beam energies 3.5MV, 6MV, and 9MV. The DE material decomposed images were generated using interlaced low and high energy beams 3.5/6MV and 6/9MV. The X-ray beams were filtered by low-Z (Polyethylene) and high-Z (Pb) filters with variable thicknesses. The radiation output of the accelerator was kept constant for all beam energies. The image quality metrics was signal-to-noise ratio (SNR) of the particular sample over a particular background. It was found that the SNR depends on the above parameters in a complex way, but can be optimized by selecting a particular set of parameters. For some imaging setups increased filter thicknesses, while strongly absorbing the beams, increased the SNR of material decomposed images. Beam hardening due to polyenergetic x-ray spectra resulted in material decomposition errors, but this could be addressed using region of interest decomposition. It was shown that it is not feasible to separate the materials with close atomic numbers using the DE method. Particularly, Pb and U were difficult to decompose, at least at the dose levels allowed by radiation source and safety requirements.

SU-F-I-41: Calibration-Free Material Decomposition for Dual-Energy CT

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

Zhao, W; Xing, L; Zhang, Q

2016-06-15

Purpose: To eliminate tedious phantom calibration or manually region of interest (ROI) selection as required in dual-energy CT material decomposition, we establish a new projection-domain material decomposition framework with incorporation of energy spectrum. Methods: Similar to the case of dual-energy CT, the integral of the basis material image in our model is expressed as a linear combination of basis functions, which are the polynomials of high- and low-energy raw projection data. To yield the unknown coefficients of the linear combination, the proposed algorithm minimizes the quadratic error between the high- and low-energy raw projection data and the projection calculated usingmore » material images. We evaluate the algorithm with an iodine concentration numerical phantom at different dose and iodine concentration levels. The x-ray energy spectra of the high and low energy are estimated using an indirect transmission method. The derived monochromatic images are compared with the high- and low-energy CT images to demonstrate beam hardening artifacts reduction. Quantitative results were measured and compared to the true values. Results: The differences between the true density value used for simulation and that were obtained from the monochromatic images, are 1.8%, 1.3%, 2.3%, and 2.9% for the dose levels from standard dose to 1/8 dose, and are 0.4%, 0.7%, 1.5%, and 1.8% for the four iodine concentration levels from 6 mg/mL to 24 mg/mL. For all of the cases, beam hardening artifacts, especially streaks shown between dense inserts, are almost completely removed in the monochromatic images. Conclusion: The proposed algorithm provides an effective way to yield material images and artifacts-free monochromatic images at different dose levels without the need for phantom calibration or ROI selection. Furthermore, the approach also yields accurate results when the concentration of the iodine concentrate insert is very low, suggesting the algorithm is robust with respect to the low-contrast scenario.« less

Adaptive Fourier decomposition based R-peak detection for noisy ECG Signals.

PubMed

Ze Wang; Chi Man Wong; Feng Wan

2017-07-01

An adaptive Fourier decomposition (AFD) based R-peak detection method is proposed for noisy ECG signals. Although lots of QRS detection methods have been proposed in literature, most detection methods require high signal quality. The proposed method extracts the R waves from the energy domain using the AFD and determines the R-peak locations based on the key decomposition parameters, achieving the denoising and the R-peak detection at the same time. Validated by clinical ECG signals in the MIT-BIH Arrhythmia Database, the proposed method shows better performance than the Pan-Tompkin (PT) algorithm in both situations of a native PT and the PT with a denoising process.

Thermal Decomposition of IMX-104: Ingredient Interactions Govern Thermal Insensitivity

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

Maharrey, Sean; Wiese-Smith, Deneille; Highley, Aaron M.

2015-04-01

This report summarizes initial studies into the chemical basis of the thermal insensitivity of INMX-104. The work follows upon similar efforts investigating this behavior for another DNAN-based insensitive explosive, IMX-101. The experiments described demonstrate a clear similarity between the ingredient interactions that were shown to lead to the thermal insensitivity observed in IMX-101 and those that are active in IMX-104 at elevated temperatures. Specifically, the onset of decomposition of RDX is shifted to a lower temperature based on the interaction of the RDX with liquid DNAN. This early onset of decomposition dissipates some stored energy that is then unavailable formore » a delayed, more violent release.« less

Initial mechanisms for the dissociation of carbon from electronically-excited nitrotoluene molecules

NASA Astrophysics Data System (ADS)

Yuan, Bing; Eilers, Hergen

2017-12-01

We calculated the photoinduced decomposition of various nitrotoluene molecules, resulting in the formation of atomic carbon, at the B3LYP/6-311++G(d,p) level of theory using Gaussian 09. In addition, we used TD-DFT (B3LYP/6-311++G(d,p)) to calculate the excitation energies. The results confirm our previously reported experimental results. Specifically, we show that the absorption of 226 nm (5.49 eV) light can lead to the decomposition of nitrotoluene molecules and the formation of atomic carbon. One 226 nm photon is sufficient for the dissociation of carbon from 2-NT and 4-NT molecules. During the dissociation process, the CH3 group provides the dissociated carbon atom and the NO2 group accepts the H atoms from either the CH3 group or the benzene ring before carbon exits the molecular system. For the second and third carbon dissociation of 2-NT, the energy barriers are 6.70 eV and 7.43 eV, respectively, and two 226 nm photons would need to be absorbed by the molecule. If extra NO is present during the first carbon dissociation of 2-NT, it gets involved in the last two decomposition steps and forms a C=NH-N=O structure which stabilizes the decomposition products and lowers the energy barrier from 5.22 eV to 4.70 eV. However, for the second and third carbon dissociation of 2-NT, the NO molecules have no apparent effect. For nitrotoluene molecules with two or three NO2 groups (i.e., 2,4-DNT, 2,6-DNT, 3,4-DNT, and 2,4,6-TNT), the first carbon dissociation energies are between 5.26 eV and 5.57 eV. The carbon dissociation pathways for these molecules are similar to those of 2-NT. In 2,4-DNT, the lowest energy barriers for the second and third carbon dissociation are 6.54 eV and 6.60 eV, respectively, which are about 1 eV higher than the energy barrier for the first carbon dissociation. In case of 2,4-DNT/NO and 2,4,6-TNT/NO, NO acts as a catalyst in the first carbon dissociation processes and forms a C=NH-N=O structure which lowers the energy barriers by 0.48 eV and 0.89 eV, respectively.

Characteristic of retained austenite decomposition during tempering and its effect on impact toughness in SA508 Gr.3 steel

NASA Astrophysics Data System (ADS)

Yan, Guanghua; Han, Lizhan; Li, Chuanwei; Luo, Xiaomeng; Gu, Jianfeng

2017-01-01

Retained austenite(RA) usually presents in the quenched Nuclear Pressure-Vessel SA508 Gr.3 steel. In the present work, the characteristic of RA decomposition and its effect on the impact toughness were investigated by microstructure observation, dilatometric experiments and Charpy impact tests. The results show that the RA transformed into martensite and bainite during tempering at 230 °C and 400 °C respectively, while mixture of long rod carbides and ferrite formed at 650 °C. The long rod carbides formed from RA decomposition decrease the critical cleavage stress for initiation of micro-cracks, and deteriorate the impact toughness of the steel. Pre-tempering at a low temperature such as 230 °C or 400 °C leading to the decomposition of RA into martensite or baintie can eliminate the deterioration of the toughness caused by direct decomposition into long rod carbides. The absorbed energy indicate that pre-tempering at 400 °C can drive dramatically improvement in the toughness of the steel.

Augmenting the decomposition of EMG signals using supervised feature extraction techniques.

PubMed

Parsaei, Hossein; Gangeh, Mehrdad J; Stashuk, Daniel W; Kamel, Mohamed S

2012-01-01

Electromyographic (EMG) signal decomposition is the process of resolving an EMG signal into its constituent motor unit potential trains (MUPTs). In this work, the possibility of improving the decomposing results using two supervised feature extraction methods, i.e., Fisher discriminant analysis (FDA) and supervised principal component analysis (SPCA), is explored. Using the MUP labels provided by a decomposition-based quantitative EMG system as a training data for FDA and SPCA, the MUPs are transformed into a new feature space such that the MUPs of a single MU become as close as possible to each other while those created by different MUs become as far as possible. The MUPs are then reclassified using a certainty-based classification algorithm. Evaluation results using 10 simulated EMG signals comprised of 3-11 MUPTs demonstrate that FDA and SPCA on average improve the decomposition accuracy by 6%. The improvement for the most difficult-to-decompose signal is about 12%, which shows the proposed approach is most beneficial in the decomposition of more complex signals.

TENSOR DECOMPOSITIONS AND SPARSE LOG-LINEAR MODELS

PubMed Central

Johndrow, James E.; Bhattacharya, Anirban; Dunson, David B.

2017-01-01

Contingency table analysis routinely relies on log-linear models, with latent structure analysis providing a common alternative. Latent structure models lead to a reduced rank tensor factorization of the probability mass function for multivariate categorical data, while log-linear models achieve dimensionality reduction through sparsity. Little is known about the relationship between these notions of dimensionality reduction in the two paradigms. We derive several results relating the support of a log-linear model to nonnegative ranks of the associated probability tensor. Motivated by these findings, we propose a new collapsed Tucker class of tensor decompositions, which bridge existing PARAFAC and Tucker decompositions, providing a more flexible framework for parsimoniously characterizing multivariate categorical data. Taking a Bayesian approach to inference, we illustrate empirical advantages of the new decompositions. PMID:29332971

Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating Li XFePO 4 electrode particles

DOE PAGES

Heo, Tae Wook; Chen, Long-Qing; Wood, Brandon C.

2015-04-08

In this paper, we present a comprehensive phase-field model for simulating diffusion-mediated kinetic phase behaviors near the surface of a solid particle. The model incorporates elastic inhomogeneity and anisotropy, diffusion mobility anisotropy, interfacial energy anisotropy, and Cahn–Hilliard diffusion kinetics. The free energy density function is formulated based on the regular solution model taking into account the possible solute-surface interaction near the surface. The coherency strain energy is computed using the Fourier-spectral iterative-perturbation method due to the strong elastic inhomogeneity with a zero surface traction boundary condition. Employing a phase-separating Li XFePO 4 electrode particle for Li-ion batteries as a modelmore » system, we perform parametric three-dimensional computer simulations. The model permits the observation of surface phase behaviors that are different from the bulk counterpart. For instance, it reproduces the theoretically well-established surface modes of spinodal decomposition of an unstable solid solution: the surface mode of coherent spinodal decomposition and the surface-directed spinodal decomposition mode. We systematically investigate the influences of major factors on the kinetic surface phase behaviors during the diffusional process. Finally, our simulation study provides insights for tailoring the internal phase microstructure of a particle by controlling the surface phase morphology.« less

Probing the thermal stability and the decomposition mechanism of a magnesium-fullerene polymer via X-ray Raman spectroscopy, X-ray diffraction and molecular dynamics simulations.

PubMed

Aramini, Matteo; Niskanen, Johannes; Cavallari, Chiara; Pontiroli, Daniele; Musazay, Abdurrahman; Krisch, Michael; Hakala, Mikko; Huotari, Simo

2016-02-21

We report the microscopic view of the thermal structural stability of the magnesium intercalated fullerene polymer Mg2C60. With the application of X-ray Raman spectroscopy and X-ray diffraction, we study in detail the decomposition pathways of the polymer system upon annealing at temperatures between 300 and 700 °C. We show that there are at least two energy scales involved in the decomposition reaction. Intermolecular carbon bonds, which are responsible for the formation of a 2D fullerene polymer, are broken with a relatively modest thermal energy, while the long-range order of the original polymer remains intact. With an increased thermal energy, the crystal structure in turn is found to undergo a transition to a novel intercalated cubic phase that is stable up to the highest temperature studied here. The local structure surrounding magnesium ions gets severely modified close to, possibly at, the phase transition. We used density functional theory based calculations to study the thermodynamic and kinetic aspects of the collapse of the fullerene network, and to explain the intermediate steps as well as the reaction pathways in the break-up of this peculiar C60 intermolecular bonding architecture.

Eigenvalue Solvers for Modeling Nuclear Reactors on Leadership Class Machines

DOE PAGES

Slaybaugh, R. N.; Ramirez-Zweiger, M.; Pandya, Tara; ...

2018-02-20

In this paper, three complementary methods have been implemented in the code Denovo that accelerate neutral particle transport calculations with methods that use leadership-class computers fully and effectively: a multigroup block (MG) Krylov solver, a Rayleigh quotient iteration (RQI) eigenvalue solver, and a multigrid in energy (MGE) preconditioner. The MG Krylov solver converges more quickly than Gauss Seidel and enables energy decomposition such that Denovo can scale to hundreds of thousands of cores. RQI should converge in fewer iterations than power iteration (PI) for large and challenging problems. RQI creates shifted systems that would not be tractable without the MGmore » Krylov solver. It also creates ill-conditioned matrices. The MGE preconditioner reduces iteration count significantly when used with RQI and takes advantage of the new energy decomposition such that it can scale efficiently. Each individual method has been described before, but this is the first time they have been demonstrated to work together effectively. The combination of solvers enables the RQI eigenvalue solver to work better than the other available solvers for large reactors problems on leadership-class machines. Using these methods together, RQI converged in fewer iterations and in less time than PI for a full pressurized water reactor core. These solvers also performed better than an Arnoldi eigenvalue solver for a reactor benchmark problem when energy decomposition is needed. The MG Krylov, MGE preconditioner, and RQI solver combination also scales well in energy. Finally, this solver set is a strong choice for very large and challenging problems.« less

Phantom-less bone mineral density (BMD) measurement using dual energy computed tomography-based 3-material decomposition

NASA Astrophysics Data System (ADS)

Hofmann, Philipp; Sedlmair, Martin; Krauss, Bernhard; Wichmann, Julian L.; Bauer, Ralf W.; Flohr, Thomas G.; Mahnken, Andreas H.

2016-03-01

Osteoporosis is a degenerative bone disease usually diagnosed at the manifestation of fragility fractures, which severely endanger the health of especially the elderly. To ensure timely therapeutic countermeasures, noninvasive and widely applicable diagnostic methods are required. Currently the primary quantifiable indicator for bone stability, bone mineral density (BMD), is obtained either by DEXA (Dual-energy X-ray absorptiometry) or qCT (quantitative CT). Both have respective advantages and disadvantages, with DEXA being considered as gold standard. For timely diagnosis of osteoporosis, another CT-based method is presented. A Dual Energy CT reconstruction workflow is being developed to evaluate BMD by evaluating lumbar spine (L1-L4) DE-CT images. The workflow is ROI-based and automated for practical use. A dual energy 3-material decomposition algorithm is used to differentiate bone from soft tissue and fat attenuation. The algorithm uses material attenuation coefficients on different beam energy levels. The bone fraction of the three different tissues is used to calculate the amount of hydroxylapatite in the trabecular bone of the corpus vertebrae inside a predefined ROI. Calibrations have been performed to obtain volumetric bone mineral density (vBMD) without having to add a calibration phantom or to use special scan protocols or hardware. Accuracy and precision are dependent on image noise and comparable to qCT images. Clinical indications are in accordance with the DEXA gold standard. The decomposition-based workflow shows bone degradation effects normally not visible on standard CT images which would induce errors in normal qCT results.

Eigenvalue Solvers for Modeling Nuclear Reactors on Leadership Class Machines

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

Slaybaugh, R. N.; Ramirez-Zweiger, M.; Pandya, Tara

In this paper, three complementary methods have been implemented in the code Denovo that accelerate neutral particle transport calculations with methods that use leadership-class computers fully and effectively: a multigroup block (MG) Krylov solver, a Rayleigh quotient iteration (RQI) eigenvalue solver, and a multigrid in energy (MGE) preconditioner. The MG Krylov solver converges more quickly than Gauss Seidel and enables energy decomposition such that Denovo can scale to hundreds of thousands of cores. RQI should converge in fewer iterations than power iteration (PI) for large and challenging problems. RQI creates shifted systems that would not be tractable without the MGmore » Krylov solver. It also creates ill-conditioned matrices. The MGE preconditioner reduces iteration count significantly when used with RQI and takes advantage of the new energy decomposition such that it can scale efficiently. Each individual method has been described before, but this is the first time they have been demonstrated to work together effectively. The combination of solvers enables the RQI eigenvalue solver to work better than the other available solvers for large reactors problems on leadership-class machines. Using these methods together, RQI converged in fewer iterations and in less time than PI for a full pressurized water reactor core. These solvers also performed better than an Arnoldi eigenvalue solver for a reactor benchmark problem when energy decomposition is needed. The MG Krylov, MGE preconditioner, and RQI solver combination also scales well in energy. Finally, this solver set is a strong choice for very large and challenging problems.« less

Evaluating litter decomposition and soil organic matter dynamics in earth system models: contrasting analysis of long-term litter decomposition and steady-state soil carbon

NASA Astrophysics Data System (ADS)

Bonan, G. B.; Wieder, W. R.

2012-12-01

Decomposition is a large term in the global carbon budget, but models of the earth system that simulate carbon cycle-climate feedbacks are largely untested with respect to litter decomposition. Here, we demonstrate a protocol to document model performance with respect to both long-term (10 year) litter decomposition and steady-state soil carbon stocks. First, we test the soil organic matter parameterization of the Community Land Model version 4 (CLM4), the terrestrial component of the Community Earth System Model, with data from the Long-term Intersite Decomposition Experiment Team (LIDET). The LIDET dataset is a 10-year study of litter decomposition at multiple sites across North America and Central America. We show results for 10-year litter decomposition simulations compared with LIDET for 9 litter types and 20 sites in tundra, grassland, and boreal, conifer, deciduous, and tropical forest biomes. We show additional simulations with DAYCENT, a version of the CENTURY model, to ask how well an established ecosystem model matches the observations. The results reveal large discrepancy between the laboratory microcosm studies used to parameterize the CLM4 litter decomposition and the LIDET field study. Simulated carbon loss is more rapid than the observations across all sites, despite using the LIDET-provided climatic decomposition index to constrain temperature and moisture effects on decomposition. Nitrogen immobilization is similarly biased high. Closer agreement with the observations requires much lower decomposition rates, obtained with the assumption that nitrogen severely limits decomposition. DAYCENT better replicates the observations, for both carbon mass remaining and nitrogen, without requirement for nitrogen limitation of decomposition. Second, we compare global observationally-based datasets of soil carbon with simulated steady-state soil carbon stocks for both models. The models simulations were forced with observationally-based estimates of annual litterfall and model-derived climatic decomposition index. While comparison with the LIDET 10-year litterbag study reveals sharp contrasts between CLM4 and DAYCENT, simulations of steady-state soil carbon show less difference between models. Both CLM4 and DAYCENT significantly underestimate soil carbon. Sensitivity analyses highlight causes of the low soil carbon bias. The terrestrial biogeochemistry of earth system models must be critically tested with observations, and the consequences of particular model choices must be documented. Long-term litter decomposition experiments such as LIDET provide a real-world process-oriented benchmark to evaluate models and can critically inform model development. Analysis of steady-state soil carbon estimates reveal additional, but here different, inferences about model performance.

Nonlocal low-rank and sparse matrix decomposition for spectral CT reconstruction

NASA Astrophysics Data System (ADS)

Niu, Shanzhou; Yu, Gaohang; Ma, Jianhua; Wang, Jing

2018-02-01

Spectral computed tomography (CT) has been a promising technique in research and clinics because of its ability to produce improved energy resolution images with narrow energy bins. However, the narrow energy bin image is often affected by serious quantum noise because of the limited number of photons used in the corresponding energy bin. To address this problem, we present an iterative reconstruction method for spectral CT using nonlocal low-rank and sparse matrix decomposition (NLSMD), which exploits the self-similarity of patches that are collected in multi-energy images. Specifically, each set of patches can be decomposed into a low-rank component and a sparse component, and the low-rank component represents the stationary background over different energy bins, while the sparse component represents the rest of the different spectral features in individual energy bins. Subsequently, an effective alternating optimization algorithm was developed to minimize the associated objective function. To validate and evaluate the NLSMD method, qualitative and quantitative studies were conducted by using simulated and real spectral CT data. Experimental results show that the NLSMD method improves spectral CT images in terms of noise reduction, artifact suppression and resolution preservation.

Introducing Network Analysis into Science Education: Methodological Research Examining Secondary School Students' Understanding of "Decomposition"

ERIC Educational Resources Information Center

Schizas, Dimitrios; Katrana, Evagelia; Stamou, George

2013-01-01

In the present study we used the technique of word association tests to assess students' cognitive structures during the learning period. In particular, we tried to investigate what students living near a protected area in Greece (Dadia forest) knew about the phenomenon of decomposition. Decomposition was chosen as a stimulus word because it…

Microbial ecological succession during municipal solid waste decomposition.

PubMed

Staley, Bryan F; de Los Reyes, Francis L; Wang, Ling; Barlaz, Morton A

2018-04-28

The decomposition of landfilled refuse proceeds through distinct phases, each defined by varying environmental factors such as volatile fatty acid concentration, pH, and substrate quality. The succession of microbial communities in response to these changing conditions was monitored in a laboratory-scale simulated landfill to minimize measurement difficulties experienced at field scale. 16S rRNA gene sequences retrieved at separate stages of decomposition showed significant succession in both Bacteria and methanogenic Archaea. A majority of Bacteria sequences in landfilled refuse belong to members of the phylum Firmicutes, while Proteobacteria levels fluctuated and Bacteroidetes levels increased as decomposition proceeded. Roughly 44% of archaeal sequences retrieved under conditions of low pH and high acetate were strictly hydrogenotrophic (Methanomicrobiales, Methanobacteriales). Methanosarcina was present at all stages of decomposition. Correspondence analysis showed bacterial population shifts were attributed to carboxylic acid concentration and solids hydrolysis, while archaeal populations were affected to a higher degree by pH. T-RFLP analysis showed specific taxonomic groups responded differently and exhibited unique responses during decomposition, suggesting that species composition and abundance within Bacteria and Archaea are highly dynamic. This study shows landfill microbial demographics are highly variable across both spatial and temporal transects.

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

Yuan, Bing; Bernstein, Elliot R., E-mail: erb@lamar.colostate.edu

Unimolecular decomposition of nitrogen-rich energetic molecules 1,2-bis(1H-tetrazol-1-yl)ethane (1-DTE), 1,2-bis(1H-tetrazol-5-yl)ethane (5-DET), N,N-bis(1H-tetrazol-5-yl)amine (BTA), and 5,5’-bis(tetrazolyl)hydrazine (BTH) has been explored via 283 nm two photon laser excitation. The maximum absorption wavelength in the UV-vis spectra of all four materials is around 186–222 nm. The N{sub 2} molecule, with a cold rotational temperature (<30 K), is observed as an initial decomposition product from the four molecules, subsequent to UV excitation. Initial decomposition mechanisms for these four electronically excited isolated molecules are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersectionsmore » play an essential role in the decomposition mechanism. The tetrazole ring opens on the S{sub 1} excited state and through conical intersections (S{sub 1}/S{sub 0}){sub CI}, N{sub 2} product is formed on the ground state potential energy surface without rotational excitation. The tetrazole rings of all four energetic molecules open at the N1—N2 ring bond with the lowest energy barrier: the C—N bond opening has higher energy barrier than that for any of the N—N ring bonds. Therefore, the tetrazole rings open at their N—N bonds to release N{sub 2}. The vibrational temperatures of N{sub 2} product from all four energetic materials are hot based on theoretical calculations. The different groups (CH{sub 2}—CH{sub 2}, NH—NH, and NH) joining the tetrazole rings can cause apparent differences in explosive behavior of 1-DTE, 5-DTE, BTA, and BTH. Conical intersections, non-Born-Oppenheimer interactions, and dynamics are the key features for excited electronic state chemistry of organic molecules, in general, and energetic molecules, in particular.« less

Energy & Energetics

DTIC Science & Technology

2012-06-22

mechanical and structural failure and decomposition in ultra-fast time regimes. Our research teams are exploring novel ways to convert mechanical ...energy to thermal energy by examining initiation mechanisms , multi-phase combustion, detonation and the mechanisms that lead to the release of energy...understanding of the mechanisms of structural stability by doping Fe in LiCoPO4 and effectiveness of HFiP in stopping further oxidation of electrolytes are

A Posteriori Error Analysis and Uncertainty Quantification for Adaptive Multiscale Operator Decomposition Methods for Multiphysics Problems

DTIC Science & Technology

2014-04-01

Barrier methods for critical exponent problems in geometric analysis and mathematical physics, J. Erway and M. Holst, Submitted for publication ...TR-14-33 A Posteriori Error Analysis and Uncertainty Quantification for Adaptive Multiscale Operator Decomposition Methods for Multiphysics...Problems Approved for public release, distribution is unlimited. April 2014 HDTRA1-09-1-0036 Donald Estep and Michael

Bond Order Conservation Strategies in Catalysis Applied to the NH 3 Decomposition Reaction

DOE PAGES

Yu, Liang; Abild-Pedersen, Frank

2016-12-14

On the basis of an extensive set of density functional theory calculations, it is shown that a simple scheme provides a fundamental understanding of variations in the transition state energies and structures of reaction intermediates on transition metal surfaces across the periodic table. The scheme is built on the bond order conservation principle and requires a limited set of input data, still achieving transition state energies as a function of simple descriptors with an error smaller than those of approaches based on linear fits to a set of calculated transition state energies. Here, we have applied this approach together withmore » linear scaling of adsorption energies to obtain the energetics of the NH 3 decomposition reaction on a series of stepped fcc(211) transition metal surfaces. Moreover, this information is used to establish a microkinetic model for the formation of N 2 and H 2, thus providing insight into the components of the reaction that determines the activity.« less

Global Existence Results for Viscoplasticity at Finite Strain

NASA Astrophysics Data System (ADS)

Mielke, Alexander; Rossi, Riccarda; Savaré, Giuseppe

2018-01-01

We study a model for rate-dependent gradient plasticity at finite strain based on the multiplicative decomposition of the strain tensor, and investigate the existence of global-in-time solutions to the related PDE system. We reveal its underlying structure as a generalized gradient system, where the driving energy functional is highly nonconvex and features the geometric nonlinearities related to finite-strain elasticity as well as the multiplicative decomposition of finite-strain plasticity. Moreover, the dissipation potential depends on the left-invariant plastic rate, and thus depends on the plastic state variable. The existence theory is developed for a class of abstract, nonsmooth, and nonconvex gradient systems, for which we introduce suitable notions of solutions, namely energy-dissipation-balance and energy-dissipation-inequality solutions. Hence, we resort to the toolbox of the direct method of the calculus of variations to check that the specific energy and dissipation functionals for our viscoplastic models comply with the conditions of the general theory.

Electron attachment to trinitrotoluene (TNT) embedded in He droplets: complete freezing of dissociation intermediates in an extended range of electron energies.

PubMed

Mauracher, Andreas; Schöbel, Harald; Ferreira da Silva, Filipe; Edtbauer, Achim; Mitterdorfer, Christian; Denifl, Stephan; Märk, Tilmann D; Illenberger, Eugen; Scheier, Paul

2009-10-01

Electron attachment to the explosive trinitrotoluene (TNT) embedded in Helium droplets (TNT@He) generates the non-decomposed complexes (TNT)(n)(-), but no fragment ions in the entire energy range 0-12 eV. This strongly contrasts the behavior of single TNT molecules in the gas phase at ambient temperatures, where electron capture leads to a variety of different fragmentation products via different dissociative electron attachment (DEA) reactions. Single TNT molecules decompose by attachment of an electron at virtually no extra energy reflecting the explosive nature of the compound. The complete freezing of dissociation intermediates in TNT embedded in the droplet is explained by the particular mechanisms of DEA in nitrobenzenes, which is characterized by complex rearrangement processes in the transient negative ion (TNI) prior to decomposition. These mechanisms provide the condition for effective energy withdrawal from the TNI into the dissipative environment thereby completely suppressing its decomposition.

Apparatus for hydrogen and carbon production via carbon aerosol-catalyzed dissociation of hydrocarbons

NASA Technical Reports Server (NTRS)

Tabatabaie-Raissi, Ali (Inventor); Muradov, Nazim Z. (Inventor); Smith, Franklyn (Inventor)

2012-01-01

A novel process and apparatus is disclosed for sustainable, continuous production of hydrogen and carbon by catalytic dissociation or decomposition of hydrocarbons at elevated temperatures using in-situ generated carbon particles. Carbon particles are produced by decomposition of carbonaceous materials in response to an energy input. The energy input can be provided by at least one of a non-oxidative and oxidative means. The non-oxidative means of the energy input includes a high temperature source, or different types of plasma, such as, thermal, non-thermal, microwave, corona discharge, glow discharge, dielectric barrier discharge, or radiation sources, such as, electron beam, gamma, ultraviolet (UV). The oxidative means of the energy input includes oxygen, air, ozone, nitrous oxide (NO.sub.2) and other oxidizing agents. The method, apparatus and process of the present invention is applicable to any gaseous or liquid hydrocarbon fuel and it produces no or significantly less CO.sub.2 emissions compared to conventional processes.

A decomposition model and voxel selection framework for fMRI analysis to predict neural response of visual stimuli.

PubMed

Raut, Savita V; Yadav, Dinkar M

2018-03-28

This paper presents an fMRI signal analysis methodology using geometric mean curve decomposition (GMCD) and mutual information-based voxel selection framework. Previously, the fMRI signal analysis has been conducted using empirical mean curve decomposition (EMCD) model and voxel selection on raw fMRI signal. The erstwhile methodology loses frequency component, while the latter methodology suffers from signal redundancy. Both challenges are addressed by our methodology in which the frequency component is considered by decomposing the raw fMRI signal using geometric mean rather than arithmetic mean and the voxels are selected from EMCD signal using GMCD components, rather than raw fMRI signal. The proposed methodologies are adopted for predicting the neural response. Experimentations are conducted in the openly available fMRI data of six subjects, and comparisons are made with existing decomposition models and voxel selection frameworks. Subsequently, the effect of degree of selected voxels and the selection constraints are analyzed. The comparative results and the analysis demonstrate the superiority and the reliability of the proposed methodology.

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

Dong, X; Petrongolo, M; Wang, T

Purpose: A general problem of dual-energy CT (DECT) is that the decomposition is sensitive to noise in the two sets of dual-energy projection data, resulting in severely degraded qualities of decomposed images. We have previously proposed an iterative denoising method for DECT. Using a linear decomposition function, the method does not gain the full benefits of DECT on beam-hardening correction. In this work, we expand the framework of our iterative method to include non-linear decomposition models for noise suppression in DECT. Methods: We first obtain decomposed projections, which are free of beam-hardening artifacts, using a lookup table pre-measured on amore » calibration phantom. First-pass material images with high noise are reconstructed from the decomposed projections using standard filter-backprojection reconstruction. Noise on the decomposed images is then suppressed by an iterative method, which is formulated in the form of least-square estimation with smoothness regularization. Based on the design principles of a best linear unbiased estimator, we include the inverse of the estimated variance-covariance matrix of the decomposed images as the penalty weight in the least-square term. Analytical formulae are derived to compute the variance-covariance matrix from the measured decomposition lookup table. Results: We have evaluated the proposed method via phantom studies. Using non-linear decomposition, our method effectively suppresses the streaking artifacts of beam-hardening and obtains more uniform images than our previous approach based on a linear model. The proposed method reduces the average noise standard deviation of two basis materials by one order of magnitude without sacrificing the spatial resolution. Conclusion: We propose a general framework of iterative denoising for material decomposition of DECT. Preliminary phantom studies have shown the proposed method improves the image uniformity and reduces noise level without resolution loss. In the future, we will perform more phantom studies to further validate the performance of the purposed method. This work is supported by a Varian MRA grant.« less

About decomposition approach for solving the classification problem

NASA Astrophysics Data System (ADS)

Andrianova, A. A.

2016-11-01

This article describes the features of the application of an algorithm with using of decomposition methods for solving the binary classification problem of constructing a linear classifier based on Support Vector Machine method. Application of decomposition reduces the volume of calculations, in particular, due to the emerging possibilities to build parallel versions of the algorithm, which is a very important advantage for the solution of problems with big data. The analysis of the results of computational experiments conducted using the decomposition approach. The experiment use known data set for binary classification problem.

Systematic study of imidazoles inhibiting IDO1 via the integration of molecular mechanics and quantum mechanics calculations.

PubMed

Zou, Yi; Wang, Fang; Wang, Yan; Guo, Wenjie; Zhang, Yihua; Xu, Qiang; Lai, Yisheng

2017-05-05

Indoleamine 2,3-dioxygenase 1 (IDO1) is regarded as an attractive target for cancer immunotherapy. To rationalize the detailed interactions between IDO1 and its inhibitors at the atomic level, an integrated computational approach by combining molecular mechanics and quantum mechanics methods was employed in this report. Specifically, the binding modes of 20 inhibitors was initially investigated using the induced fit docking (IFD) protocol, which outperformed other two docking protocols in terms of correctly predicting ligand conformations. Secondly, molecular dynamics (MD) simulations and MM/PBSA free energy calculations were employed to determine the dynamic binding process and crucial residues were confirmed through close contact analysis, hydrogen-bond analysis and binding free energy decomposition calculations. Subsequent quantum mechanics and nonbonding interaction analysis were carried out to provide in-depth explanations on the critical role of those key residues, and Arg231 and 7-propionate of the heme group were major contributors to ligand binding, which lowed a great amount of interaction energy. We anticipate that these findings will be valuable for enzymatic studies and rational drug design. Copyright © 2017. Published by Elsevier Masson SAS.

GHGs and air pollutants embodied in China's international trade: Temporal and spatial index decomposition analysis.

PubMed

Liu, Zhengyan; Mao, Xianqiang; Song, Peng

2017-01-01

Temporal index decomposition analysis and spatial index decomposition analysis were applied to understand the driving forces of the emissions embodied in China's exports and net exports during 2002-2011, respectively. The accumulated emissions embodied in exports accounted for approximately 30% of the total emissions in China; although the contribution of the sectoral total emissions intensity (technique effect) declined, the scale effect was largely responsible for the mounting emissions associated with export, and the composition effect played a largely insignificant role. Calculations of the emissions embodied in net exports suggest that China is generally in an environmentally inferior position compared with its major trade partners. The differences in the economy-wide emission intensities between China and its major trade partners were the biggest contribution to this reality, and the trade balance effect played a less important role. However, a lower degree of specialization in pollution intensive products in exports than in imports helped to reduce slightly the emissions embodied in net exports. The temporal index decomposition analysis results suggest that China should take effective measures to optimize export and supply-side structure and reduce the total emissions intensity. According to spatial index decomposition analysis, it is suggested that a more aggressive import policy was useful for curbing domestic and global emissions, and the transfer of advanced production technologies and emission control technologies from developed to developing countries should be a compulsory global environmental policy option to mitigate the possible leakage of pollution emissions caused by international trade.

Thermal Decomposition Behaviors and Burning Characteristics of AN/Nitramine-Based Composite Propellant

NASA Astrophysics Data System (ADS)

Naya, Tomoki; Kohga, Makoto

2015-04-01

Ammonium nitrate (AN) has attracted much attention due to its clean burning nature as an oxidizer. However, an AN-based composite propellant has the disadvantages of low burning rate and poor ignitability. In this study, we added nitramine of cyclotrimethylene trinitramine (RDX) or cyclotetramethylene tetranitramine (HMX) as a high-energy material to AN propellants to overcome these disadvantages. The thermal decomposition and burning rate characteristics of the prepared propellants were examined as the ratio of AN and nitramine was varied. In the thermal decomposition process, AN/RDX propellants showed unique mass loss peaks in the lower temperature range that were not observed for AN or RDX propellants alone. AN and RDX decomposed continuously as an almost single oxidizer in the AN/RDX propellant. In contrast, AN/HMX propellants exhibited thermal decomposition characteristics similar to those of AN and HMX, which decomposed almost separately in the thermal decomposition of the AN/HMX propellant. The ignitability was improved and the burning rate increased by the addition of nitramine for both AN/RDX and AN/HMX propellants. The increased burning rates of AN/RDX propellants were greater than those of AN/HMX. The difference in the thermal decomposition and burning characteristics was caused by the interaction between AN and RDX.

PROCESS FOR CONTROLLING ANIMAL GROWTH RATE

DOEpatents

Visek, W.J.

1962-04-10

A method of injecting growing animals with the enzyme urease subcutaneously in increasing dosages is described; this generates within the blood anti-urease which enters the intestinal tract and inhibits the enzymatic decomposition of urea by urease in that location. Ammonia, one of the decomposition products, is thereby kept from diffusing through the intestinal walls into the blood, and this greatly reduces the energy requirements of the liver for removing the ammonia, thereby increasing the feeding efficiency of the animals. (AEC)

Multi-scale Methods in Quantum Field Theory

NASA Astrophysics Data System (ADS)

Polyzou, W. N.; Michlin, Tracie; Bulut, Fatih

2018-05-01

Daubechies wavelets are used to make an exact multi-scale decomposition of quantum fields. For reactions that involve a finite energy that take place in a finite volume, the number of relevant quantum mechanical degrees of freedom is finite. The wavelet decomposition has natural resolution and volume truncations that can be used to isolate the relevant degrees of freedom. The application of flow equation methods to construct effective theories that decouple coarse and fine scale degrees of freedom is examined.

Multi-material decomposition of spectral CT images

NASA Astrophysics Data System (ADS)

Mendonça, Paulo R. S.; Bhotika, Rahul; Maddah, Mahnaz; Thomsen, Brian; Dutta, Sandeep; Licato, Paul E.; Joshi, Mukta C.

2010-04-01

Spectral Computed Tomography (Spectral CT), and in particular fast kVp switching dual-energy computed tomography, is an imaging modality that extends the capabilities of conventional computed tomography (CT). Spectral CT enables the estimation of the full linear attenuation curve of the imaged subject at each voxel in the CT volume, instead of a scalar image in Hounsfield units. Because the space of linear attenuation curves in the energy ranges of medical applications can be accurately described through a two-dimensional manifold, this decomposition procedure would be, in principle, limited to two materials. This paper describes an algorithm that overcomes this limitation, allowing for the estimation of N-tuples of material-decomposed images. The algorithm works by assuming that the mixing of substances and tissue types in the human body has the physicochemical properties of an ideal solution, which yields a model for the density of the imaged material mix. Under this model the mass attenuation curve of each voxel in the image can be estimated, immediately resulting in a material-decomposed image triplet. Decomposition into an arbitrary number of pre-selected materials can be achieved by automatically selecting adequate triplets from an application-specific material library. The decomposition is expressed in terms of the volume fractions of each constituent material in the mix; this provides for a straightforward, physically meaningful interpretation of the data. One important application of this technique is in the digital removal of contrast agent from a dual-energy exam, producing a virtual nonenhanced image, as well as in the quantification of the concentration of contrast observed in a targeted region, thus providing an accurate measure of tissue perfusion.

A unified material decomposition framework for quantitative dual- and triple-energy CT imaging.

PubMed

Zhao, Wei; Vernekohl, Don; Han, Fei; Han, Bin; Peng, Hao; Yang, Yong; Xing, Lei; Min, James K

2018-04-21

Many clinical applications depend critically on the accurate differentiation and classification of different types of materials in patient anatomy. This work introduces a unified framework for accurate nonlinear material decomposition and applies it, for the first time, in the concept of triple-energy CT (TECT) for enhanced material differentiation and classification as well as dual-energy CT (DECT). We express polychromatic projection into a linear combination of line integrals of material-selective images. The material decomposition is then turned into a problem of minimizing the least-squares difference between measured and estimated CT projections. The optimization problem is solved iteratively by updating the line integrals. The proposed technique is evaluated by using several numerical phantom measurements under different scanning protocols. The triple-energy data acquisition is implemented at the scales of micro-CT and clinical CT imaging with commercial "TwinBeam" dual-source DECT configuration and a fast kV switching DECT configuration. Material decomposition and quantitative comparison with a photon counting detector and with the presence of a bow-tie filter are also performed. The proposed method provides quantitative material- and energy-selective images examining realistic configurations for both DECT and TECT measurements. Compared to the polychromatic kV CT images, virtual monochromatic images show superior image quality. For the mouse phantom, quantitative measurements show that the differences between gadodiamide and iodine concentrations obtained using TECT and idealized photon counting CT (PCCT) are smaller than 8 and 1 mg/mL, respectively. TECT outperforms DECT for multicontrast CT imaging and is robust with respect to spectrum estimation. For the thorax phantom, the differences between the concentrations of the contrast map and the corresponding true reference values are smaller than 7 mg/mL for all of the realistic configurations. A unified framework for both DECT and TECT imaging has been established for the accurate extraction of material compositions using currently available commercial DECT configurations. The novel technique is promising to provide an urgently needed solution for several CT-based diagnostic and therapy applications, especially for the diagnosis of cardiovascular and abdominal diseases where multicontrast imaging is involved. © 2018 American Association of Physicists in Medicine.

Ab initio molecular dynamics study on the initial chemical events in nitramines: thermal decomposition of CL-20.

PubMed

Isayev, Olexandr; Gorb, Leonid; Qasim, Mo; Leszczynski, Jerzy

2008-09-04

CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane or HNIW) is a high-energy nitramine explosive. To improve atomistic understanding of the thermal decomposition of CL-20 gas and solid phases, we performed a series of ab initio molecular dynamics simulations. We found that during unimolecular decomposition, unlike other nitramines (e.g., RDX, HMX), CL-20 has only one distinct initial reaction channelhomolysis of the N-NO2 bond. We did not observe any HONO elimination reaction during unimolecular decomposition, whereas the ring-breaking reaction was followed by NO 2 fission. Therefore, in spite of limited sampling, that provides a mostly qualitative picture, we proposed here a scheme of unimolecular decomposition of CL-20. The averaged product population over all trajectories was estimated at four HCN, two to four NO2, two to four NO, one CO, and one OH molecule per one CL-20 molecule. Our simulations provide a detailed description of the chemical processes in the initial stages of thermal decomposition of condensed CL-20, allowing elucidation of key features of such processes as composition of primary reaction products, reaction timing, and Arrhenius behavior of the system. The primary reactions leading to NO2, NO, N 2O, and N2 occur at very early stages. We also estimated potential activation barriers for the formation of NO2, which essentially determines overall decomposition kinetics and effective rate constants for NO2 and N2. The calculated solid-phase decomposition pathways correlate with available condensed-phase experimental data.

Influence of crystal orientation and ion bombardment on the nitrogen diffusivity in single-crystalline austenitic stainless steel

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

Martinavicius, A.; Abrasonis, G.; Moeller, W.

2011-10-01

The nitrogen diffusivity in single-crystalline AISI 316L austenitic stainless steel (ASS) during ion nitriding has been investigated at different crystal orientations ((001), (110), (111)) under variations of ion flux (0.3-0.7 mA cm{sup -2}), ion energy (0.5-1.2 keV), and temperature (370-430 deg. C). The nitrogen depth profiles obtained from nuclear reaction analysis are in excellent agreement with fits using the model of diffusion under the influence of traps, from which diffusion coefficients were extracted. At fixed ion energy and flux, the diffusivity varies by a factor up to 2.5 at different crystal orientations. At (100) orientation, it increases linearly with increasingmore » ion flux or energy. The findings are discussed on the basis of atomistic mechanisms of interstitial diffusion, potential lattice distortions, local decomposition, and ion-induced lattice vibrational excitations.« less

Real Gas Computation Using an Energy Relaxation Method and High-Order WENO Schemes

NASA Technical Reports Server (NTRS)

Montarnal, Philippe; Shu, Chi-Wang

1998-01-01

In this paper, we use a recently developed energy relaxation theory by Coquel and Perthame and high order weighted essentially non-oscillatory (WENO) schemes to simulate the Euler equations of real gas. The main idea is an energy decomposition into two parts: one part is associated with a simpler pressure law and the other part (the nonlinear deviation) is convected with the flow. A relaxation process is performed for each time step to ensure that the original pressure law is satisfied. The necessary characteristic decomposition for the high order WENO schemes is performed on the characteristic fields based on the first part. The algorithm only calls for the original pressure law once per grid point per time step, without the need to compute its derivatives or any Riemann solvers. Both one and two dimensional numerical examples are shown to illustrate the effectiveness of this approach.

Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II.

PubMed

Pathak, Vinay; Prasad, Ankush; Pospíšil, Pavel

2017-01-01

Singlet oxygen (1O2) is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII). Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex.

Formation of singlet oxygen by decomposition of protein hydroperoxide in photosystem II

PubMed Central

Pathak, Vinay; Prasad, Ankush

2017-01-01

Singlet oxygen (1O2) is formed by triplet-triplet energy transfer from triplet chlorophyll to O2 via Type II photosensitization reaction in photosystem II (PSII). Formation of triplet chlorophyll is associated with the change in spin state of the excited electron and recombination of triplet radical pair in the PSII antenna complex and reaction center, respectively. Here, we have provided evidence for the formation of 1O2 by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. Protein hydroperoxide is formed by protein oxidation initiated by highly oxidizing chlorophyll cation radical and hydroxyl radical formed by Type I photosensitization reaction. Under highly oxidizing conditions, protein hydroperoxide is oxidized to protein peroxyl radical which either cyclizes to dioxetane or recombines with another protein peroxyl radical to tetroxide. These highly unstable intermediates decompose to triplet carbonyls which transfer energy to O2 forming 1O2. Data presented in this study show for the first time that 1O2 is formed by decomposition of protein hydroperoxide in PSII membranes deprived of Mn4O5Ca complex. PMID:28732060

Coherent vorticity extraction in resistive drift-wave turbulence: Comparison of orthogonal wavelets versus proper orthogonal decomposition

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

Futatani, S.; Bos, W.J.T.; Del-Castillo-Negrete, Diego B

2011-01-01

We assess two techniques for extracting coherent vortices out of turbulent flows: the wavelet based Coherent Vorticity Extraction (CVE) and the Proper Orthogonal Decomposition (POD). The former decomposes the flow field into an orthogonal wavelet representation and subsequent thresholding of the coefficients allows one to split the flow into organized coherent vortices with non-Gaussian statistics and an incoherent random part which is structureless. POD is based on the singular value decomposition and decomposes the flow into basis functions which are optimal with respect to the retained energy for the ensemble average. Both techniques are applied to direct numerical simulation datamore » of two-dimensional drift-wave turbulence governed by Hasegawa Wakatani equation, considering two limit cases: the quasi-hydrodynamic and the quasi-adiabatic regimes. The results are compared in terms of compression rate, retained energy, retained enstrophy and retained radial flux, together with the enstrophy spectrum and higher order statistics. (c) 2010 Published by Elsevier Masson SAS on behalf of Academie des sciences.« less

Carbene-aerogen bonds: an ab initio study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Sabouri, Ayda

2017-04-01

Through the use of ab initio calculations, the possibility of formation of σ-hole interaction between ZO3 (Z = Ar, Kr and Xe) and carbene species is investigated. Since singlet carbenes show a negative electrostatic potential on their divalent carbon atom, they can favourably interact with the positive electrostatic potential generated by the σ-hole of Z atom of ZO3. The characteristic of this interaction, termed as 'carbene-aerogen' bond, is analysed in terms of geometric, interaction energies and electronic features. The energy decomposition analysis indicates that for all complexes analysed here, the electrostatic energy is more negative than the polarisation or dispersion energy term. According to the electron density analysis, some partial covalent character can be ascribed to XeṡṡṡC interactions. In addition, the carbene-aerogen bond exhibits cooperative effects with the HṡṡṡO hydrogen-bonding interaction in ternary complexes where both interactions coexist. For a given carbene, the amount of these cooperative effects increases with the size of the Z atom. The results obtained in this work may be helpful for the extension and future application of σ-hole intermolecular interactions as well as coordination chemistry.

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

Miller, David C.; Kempe, Michael D.; Muller, Matthew T.

We examined the durability of polymeric encapsulation materials using outdoor exposure at the nominal geometric concentration of 500 suns. The results for 36-month cumulative field deployment are presented for materials including: poly(ethylene-co-vinyl acetate), (EVA); polyvinyl butyral (PVB); ionomer; polyethylene/polyoctene copolymer (PO); thermoplastic polyurethane (TPU); poly(dimethylsiloxane) (PDMS); poly(diphenyl dimethyl siloxane) (PDPDMS); and poly(phenyl-methyl siloxane) (PPMS). Measurements of the field conditions including ambient temperature and ultraviolet (UV) dose were recorded at the test site during the experiment. Our measurements for the experiment included optical transmittance (with subsequent analysis of solar-weighted transmittance, UV cut-off wavelength, and yellowness index), mass, visual photography, photoelastic imaging,more » and fluorescence spectroscopy. While the results to date for EVA are presented and discussed, examination here focuses more on the siloxane materials. A specimen recently observed to fail by thermal decomposition is discussed in terms of the implementation of the experiment as well as its fluorescence signature, which was observed to become more pronounced with age. Modulated thermogravimetry (allowing determination of the activation energy of thermal decomposition) was performed on a subset of the siloxanes to quantify the propensity for decomposition at elevated temperatures. Supplemental, Pt-catalyst- and primer-solutions as well as peroxide-cured PDMS specimens were examined to assess the source of the luminescence. Furthermore, our results, including the change in optical transmittance, observed failure modes, and subsequent analyses of the failure modes are described in the conclusions.« less

Thermal decomposition and kinetics of coal and fermented cornstalk using thermogravimetric analysis.

PubMed

He, Yuyuan; Chang, Chun; Li, Pan; Han, Xiuli; Li, Hongliang; Fang, Shuqi; Chen, Junying; Ma, Xiaojian

2018-07-01

The thermal behavior and kinetics of Yiluo coal (YC) and the residues of fermented cornstalk (FC) were investigated in this study. The Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods were used for the kinetic analysis of the pyrolysis process. The results showed that the activation energy (E α ) was increased with the increase of the thermal conversion rate (α), and the average values of E α of YC, FC and the blend (m YC /m FC  = 6/4) were 304.26, 224.94 and 233.46 kJ/mol, respectively. The order reaction model function for the blend was also developed by the master-plots method. By comparing the E a and the enthalpy, it was found that the blend was favored to format activated complex due to the lower potential energy barrier. Meanwhile, the average value of Gibbs free energy of the blend was 169.83 kJ/mol, and the changes of entropies indicated that the pyrolysis process was evolved from ordered-state to disordered-state. Copyright © 2018 Elsevier Ltd. All rights reserved.

Decompositions of the polyhedral product functor with applications to moment-angle complexes and related spaces

PubMed Central

Bahri, A.; Bendersky, M.; Cohen, F. R.; Gitler, S.

2009-01-01

This article gives a natural decomposition of the suspension of a generalized moment-angle complex or partial product space which arises as the polyhedral product functor described below. The introduction and application of the smash product moment-angle complex provides a precise identification of the stable homotopy type of the values of the polyhedral product functor. One direct consequence is an analysis of the associated cohomology. For the special case of the complements of certain subspace arrangements, the geometrical decomposition implies the homological decomposition in earlier work of others as described below. Because the splitting is geometric, an analogous homological decomposition for a generalized moment-angle complex applies for any homology theory. Implied, therefore, is a decomposition for the Stanley–Reisner ring of a finite simplicial complex, and natural generalizations. PMID:19620727

Decompositions of the polyhedral product functor with applications to moment-angle complexes and related spaces.

PubMed

Bahri, A; Bendersky, M; Cohen, F R; Gitler, S

2009-07-28

This article gives a natural decomposition of the suspension of a generalized moment-angle complex or partial product space which arises as the polyhedral product functor described below. The introduction and application of the smash product moment-angle complex provides a precise identification of the stable homotopy type of the values of the polyhedral product functor. One direct consequence is an analysis of the associated cohomology. For the special case of the complements of certain subspace arrangements, the geometrical decomposition implies the homological decomposition in earlier work of others as described below. Because the splitting is geometric, an analogous homological decomposition for a generalized moment-angle complex applies for any homology theory. Implied, therefore, is a decomposition for the Stanley-Reisner ring of a finite simplicial complex, and natural generalizations.

Three geographic decomposition approaches in transportation network analysis

DOT National Transportation Integrated Search

1980-03-01

This document describes the results of research into the application of geographic decomposition techniques to practical transportation network problems. Three approaches are described for the solution of the traffic assignment problem. One approach ...

Application of Decomposition to Transportation Network Analysis

DOT National Transportation Integrated Search

1976-10-01

This document reports preliminary results of five potential applications of the decomposition techniques from mathematical programming to transportation network problems. The five application areas are (1) the traffic assignment problem with fixed de...

Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study

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

Hensley, Alyssa J.; Wockel, Claudia; Gleichweit, Christoph

Using a concerted effort from both experiment and theory, we determine the thermal decomposition mechanism for guaiacol on Pt(111), a reaction of interest in the area of bio-oil upgrading. This work serves as a demonstration of the power of combining in situ temperature-programmed X-ray photoelectron spectroscopy cos (TPXPS) and density functional theory (DFT) to elucidate complex reaction mechanisms occurring on heterogeneous surfaces. At low temperature (230 K), guaiacol was found to chemisorb with the aromatic ring parallel to the Pt(111) surface with five distinct carbon species and three oxygen species. As the temperature was increased, TPXPS showed several significant changesmore » to the surface species. The increase in the species associated with the decomposition of the functional groups of guaiacol is followed by their subsequent disappearance and an increase in the nonaromatic carbon signal. On the basis of an energetic analysis of the various mechanisms using DFT, along with the comparison of the experimentally and theoretically derived core-level binding energies, we determined that guaiacol's decomposition mechanism occurs via the dehydrogenation of both the methyl and hydroxyl functional groups, followed by demethylation of the CH2 or CH group to form 1,2-benzoquinone. Further heating to above 375 K likely breaks the aromatic ring and results in the rapid formation and desorption of CO, accounting for the disappearance of the 0 is signal above 450 K These results show that a knowledgeable application of TPXPS and DFT can result in the quantitative identification of surface species during complex reactions, providing insight useful for the design of future heterogeneous surfaces.« less

Gas Sensing Analysis of Ag-Decorated Graphene for Sulfur Hexafluoride Decomposition Products Based on the Density Functional Theory

PubMed Central

Zhang, Xiaoxing; Huang, Rong; Gui, Yingang; Zeng, Hong

2016-01-01

Detection of decomposition products of sulfur hexafluoride (SF6) is one of the best ways to diagnose early latent insulation faults in gas-insulated equipment, and the occurrence of sudden accidents can be avoided effectively by finding early latent faults. Recently, functionalized graphene, a kind of gas sensing material, has been reported to show good application prospects in the gas sensor field. Therefore, calculations were performed to analyze the gas sensing properties of intrinsic graphene (Int-graphene) and functionalized graphene-based material, Ag-decorated graphene (Ag-graphene), for decomposition products of SF6, including SO2F2, SOF2, and SO2, based on density functional theory (DFT). We thoroughly investigated a series of parameters presenting gas-sensing properties of adsorbing process about gas molecule (SO2F2, SOF2, SO2) and double gas molecules (2SO2F2, 2SOF2, 2SO2) on Ag-graphene, including adsorption energy, net charge transfer, electronic state density, and the highest and lowest unoccupied molecular orbital. The results showed that the Ag atom significantly enhances the electrochemical reactivity of graphene, reflected in the change of conductivity during the adsorption process. SO2F2 and SO2 gas molecules on Ag-graphene presented chemisorption, and the adsorption strength was SO2F2 > SO2, while SOF2 absorption on Ag-graphene was physical adsorption. Thus, we concluded that Ag-graphene showed good selectivity and high sensitivity to SO2F2. The results can provide a helpful guide in exploring Ag-graphene material in experiments for monitoring the insulation status of SF6-insulated equipment based on detecting decomposition products of SF6. PMID:27809269

Structural investigation of oxovanadium(IV) Schiff base complexes: X-ray crystallography, electrochemistry and kinetic of thermal decomposition.

PubMed

Asadi, Mozaffar; Asadi, Zahra; Savaripoor, Nooshin; Dusek, Michal; Eigner, Vaclav; Shorkaei, Mohammad Ranjkesh; Sedaghat, Moslem

2015-02-05

A series of new VO(IV) complexes of tetradentate N2O2 Schiff base ligands (L(1)-L(4)), were synthesized and characterized by FT-IR, UV-vis and elemental analysis. The structure of the complex VOL(1)⋅DMF was also investigated by X-ray crystallography which revealed a vanadyl center with distorted octahedral coordination where the 2-aza and 2-oxo coordinating sites of the ligand were perpendicular to the "-yl" oxygen. The electrochemical properties of the vanadyl complexes were investigated by cyclic voltammetry. A good correlation was observed between the oxidation potentials and the electron withdrawing character of the substituents on the Schiff base ligands, showing the following trend: MeO5-H>5-Br>5-Cl. Furthermore, the kinetic parameters of thermal decomposition were calculated by using the Coats-Redfern equation. According to the Coats-Redfern plots the kinetics of thermal decomposition of studied complexes is of the first-order in all stages, the free energy of activation for each following stage is larger than the previous one and the complexes have good thermal stability. The preparation of VOL(1)⋅DMF yielded also another compound, one kind of vanadium oxide [VO]X, with different habitus of crystals, (platelet instead of prisma) and without L(1) ligand, consisting of a V10O28 cage, diaminium moiety and dimethylamonium as a counter ions. Because its crystal structure was also new, we reported it along with the targeted complex. Copyright © 2014 Elsevier B.V. All rights reserved.

A density functional theory study on the adsorption and decomposition of methanol on B12N12 fullerene-like nanocage

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Nurazar, Roghaye

2014-03-01

The adsorption and dissociative reaction of methanol on B12N12 fullerene-like nanocage is investigated by using density functional calculations. Equilibrium geometries, adsorption energies, and electronic properties of CH3OH adsorption on the surface of the B12N12 were identified. The calculated adsorption energies range from -1.3 to -34.9 kcal/mol. It is found that the electrical conductivity of the nanocage can be modified upon the adsorption of CH3OH. The mechanism of methanol decomposition via CO and OH bond scissions is also studied. The results indicate that OH bond scission is the most favorable pathway on the B12N12 surface.

Plasma-assisted CO2 conversion: optimizing performance via microwave power modulation

NASA Astrophysics Data System (ADS)

Britun, Nikolay; Silva, Tiago; Chen, Guoxing; Godfroid, Thomas; van der Mullen, Joost; Snyders, Rony

2018-04-01

Significant improvement in the energy efficiency of plasma-assisted CO2 conversion is achieved with applied power modulation in a surfaguide microwave discharge. The obtained values of CO2 conversion and energy efficiency are, respectively, 0.23 and 0.33 for a 0.95 CO2  +  0.05 N2 gas mixture. Analysis of the energy relaxation mechanisms shows that power modulation can potentially affect the vibrational-translational energy exchange in plasma. In our case, however, this mechanism does not play a major role, likely due to the low degree of plasma non-equilibrium in the considered pressure range. Instead, the gas residence time in the discharge active zone together with plasma pulse duration are found to be the main factors affecting the CO2 conversion efficiency at low plasma pulse repetition rates. This effect is confirmed experimentally by the in situ time-resolved two-photon absorption laser-induced fluorescence measurements of CO molecular density produced in the discharge as a result of CO2 decomposition.

Polarimetric Decomposition Analysis of the Deepwater Horizon Oil Slick Using L-Band UAVSAR Data

NASA Technical Reports Server (NTRS)

Jones, Cathleen; Minchew, Brent; Holt, Benjamin

2011-01-01

We report here an analysis of the polarization dependence of L-band radar backscatter from the main slick of the Deepwater Horizon oil spill, with specific attention to the utility of polarimetric decomposition analysis for discrimination of oil from clean water and identification of variations in the oil characteristics. For this study we used data collected with the UAVSAR instrument from opposing look directions directly over the main oil slick. We find that both the Cloude-Pottier and Shannon entropy polarimetric decomposition methods offer promise for oil discrimination, with the Shannon entropy method yielding the same information as contained in the Cloude-Pottier entropy and averaged in tensity parameters, but with significantly less computational complexity

A data-driven method to enhance vibration signal decomposition for rolling bearing fault analysis

NASA Astrophysics Data System (ADS)

Grasso, M.; Chatterton, S.; Pennacchi, P.; Colosimo, B. M.

2016-12-01

Health condition analysis and diagnostics of rotating machinery requires the capability of properly characterizing the information content of sensor signals in order to detect and identify possible fault features. Time-frequency analysis plays a fundamental role, as it allows determining both the existence and the causes of a fault. The separation of components belonging to different time-frequency scales, either associated to healthy or faulty conditions, represents a challenge that motivates the development of effective methodologies for multi-scale signal decomposition. In this framework, the Empirical Mode Decomposition (EMD) is a flexible tool, thanks to its data-driven and adaptive nature. However, the EMD usually yields an over-decomposition of the original signals into a large number of intrinsic mode functions (IMFs). The selection of most relevant IMFs is a challenging task, and the reference literature lacks automated methods to achieve a synthetic decomposition into few physically meaningful modes by avoiding the generation of spurious or meaningless modes. The paper proposes a novel automated approach aimed at generating a decomposition into a minimal number of relevant modes, called Combined Mode Functions (CMFs), each consisting in a sum of adjacent IMFs that share similar properties. The final number of CMFs is selected in a fully data driven way, leading to an enhanced characterization of the signal content without any information loss. A novel criterion to assess the dissimilarity between adjacent CMFs is proposed, based on probability density functions of frequency spectra. The method is suitable to analyze vibration signals that may be periodically acquired within the operating life of rotating machineries. A rolling element bearing fault analysis based on experimental data is presented to demonstrate the performances of the method and the provided benefits.

Proper orthogonal decomposition-based spectral higher-order stochastic estimation

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

Baars, Woutijn J., E-mail: wbaars@unimelb.edu.au; Tinney, Charles E.

A unique routine, capable of identifying both linear and higher-order coherence in multiple-input/output systems, is presented. The technique combines two well-established methods: Proper Orthogonal Decomposition (POD) and Higher-Order Spectra Analysis. The latter of these is based on known methods for characterizing nonlinear systems by way of Volterra series. In that, both linear and higher-order kernels are formed to quantify the spectral (nonlinear) transfer of energy between the system's input and output. This reduces essentially to spectral Linear Stochastic Estimation when only first-order terms are considered, and is therefore presented in the context of stochastic estimation as spectral Higher-Order Stochastic Estimationmore » (HOSE). The trade-off to seeking higher-order transfer kernels is that the increased complexity restricts the analysis to single-input/output systems. Low-dimensional (POD-based) analysis techniques are inserted to alleviate this void as POD coefficients represent the dynamics of the spatial structures (modes) of a multi-degree-of-freedom system. The mathematical framework behind this POD-based HOSE method is first described. The method is then tested in the context of jet aeroacoustics by modeling acoustically efficient large-scale instabilities as combinations of wave packets. The growth, saturation, and decay of these spatially convecting wave packets are shown to couple both linearly and nonlinearly in the near-field to produce waveforms that propagate acoustically to the far-field for different frequency combinations.« less

Tympanal travelling waves in migratory locusts.

PubMed

Windmill, James F C; Göpfert, Martin C; Robert, Daniel

2005-01-01

Hearing animals, including many vertebrates and insects, have the capacity to analyse the frequency composition of sound. In mammals, frequency analysis relies on the mechanical response of the basilar membrane in the cochlear duct. These vibrations take the form of a slow vibrational wave propagating along the basilar membrane from base to apex. Known as von Békésy's travelling wave, this wave displays amplitude maxima at frequency-specific locations along the basilar membrane, providing a spatial map of the frequency of sound--a tonotopy. In their structure, insect auditory systems may not be as sophisticated at those of mammals, yet some are known to perform sound frequency analysis. In the desert locust, this analysis arises from the mechanical properties of the tympanal membrane. In effect, the spatial decomposition of incident sound into discrete frequency components involves a tympanal travelling wave that funnels mechanical energy to specific tympanal locations, where distinct groups of mechanoreceptor neurones project. Notably, observed tympanal deflections differ from those predicted by drum theory. Although phenomenologically equivalent, von Békésy's and the locust's waves differ in their physical implementation. von Békésy's wave is born from interactions between the anisotropic basilar membrane and the surrounding incompressible fluids, whereas the locust's wave rides on an anisotropic membrane suspended in air. The locust's ear thus combines in one structure the functions of sound reception and frequency decomposition.

Three-pattern decomposition of global atmospheric circulation: part I—decomposition model and theorems

NASA Astrophysics Data System (ADS)

Hu, Shujuan; Chou, Jifan; Cheng, Jianbo

2018-04-01

In order to study the interactions between the atmospheric circulations at the middle-high and low latitudes from the global perspective, the authors proposed the mathematical definition of three-pattern circulations, i.e., horizontal, meridional and zonal circulations with which the actual atmospheric circulation is expanded. This novel decomposition method is proved to accurately describe the actual atmospheric circulation dynamics. The authors used the NCEP/NCAR reanalysis data to calculate the climate characteristics of those three-pattern circulations, and found that the decomposition model agreed with the observed results. Further dynamical analysis indicates that the decomposition model is more accurate to capture the major features of global three dimensional atmospheric motions, compared to the traditional definitions of Rossby wave, Hadley circulation and Walker circulation. The decomposition model for the first time realized the decomposition of global atmospheric circulation using three orthogonal circulations within the horizontal, meridional and zonal planes, offering new opportunities to study the large-scale interactions between the middle-high latitudes and low latitudes circulations.

Ozone decomposition

PubMed Central

Batakliev, Todor; Georgiev, Vladimir; Anachkov, Metody; Rakovsky, Slavcho

2014-01-01

Catalytic ozone decomposition is of great significance because ozone is a toxic substance commonly found or generated in human environments (aircraft cabins, offices with photocopiers, laser printers, sterilizers). Considerable work has been done on ozone decomposition reported in the literature. This review provides a comprehensive summary of the literature, concentrating on analysis of the physico-chemical properties, synthesis and catalytic decomposition of ozone. This is supplemented by a review on kinetics and catalyst characterization which ties together the previously reported results. Noble metals and oxides of transition metals have been found to be the most active substances for ozone decomposition. The high price of precious metals stimulated the use of metal oxide catalysts and particularly the catalysts based on manganese oxide. It has been determined that the kinetics of ozone decomposition is of first order importance. A mechanism of the reaction of catalytic ozone decomposition is discussed, based on detailed spectroscopic investigations of the catalytic surface, showing the existence of peroxide and superoxide surface intermediates. PMID:26109880

Pressure-dependent decomposition kinetics of the energetic material HMX up to 3.6 GPa.

PubMed

Glascoe, Elizabeth A; Zaug, Joseph M; Burnham, Alan K

2009-12-03

The effect of pressure on the global thermal decomposition rate of the energetic material HMX was studied. HMX was precompressed in a diamond anvil cell (DAC) and heated at various rates. The parent species population was monitored as a function of time and temperature using Fourier transform infrared (FTIR) spectroscopy. Global decomposition rates were determined by fitting the fraction reacted to the extended-Prout-Tompkins nucleation-growth model and the Friedman isoconversional method. The results of these experiments and analysis indicate that pressure accelerates the decomposition at low-to-moderate pressures (i.e., between ambient pressure and 0.1 GPa) and decelerates the decomposition at higher pressures. The decomposition acceleration is attributed to pressure-enhanced autocatalysis, whereas the deceleration at high pressures is attributed to pressure-inhibiting bond homolysis step(s), which would result in an increase in volume. These results indicate that both the beta- and delta-polymorphs of HMX are sensitive to pressure in the thermally induced decomposition kinetics.

Statistical analysis of kinetic energy entrainment in a model wind turbine array boundary layer

NASA Astrophysics Data System (ADS)

Cal, Raul Bayoan; Hamilton, Nicholas; Kang, Hyung-Suk; Meneveau, Charles

2012-11-01

For large wind farms, kinetic energy must be entrained from the flow above the wind turbines to replenish wakes and enable power extraction in the array. Various statistical features of turbulence causing vertical entrainment of mean-flow kinetic energy are studied using hot-wire velocimetry data taken in a model wind farm in a scaled wind tunnel experiment. Conditional statistics and spectral decompositions are employed to characterize the most relevant turbulent flow structures and determine their length-scales. Sweep and ejection events are shown to be the largest contributors to the vertical kinetic energy flux, although their relative contribution depends upon the location in the wake. Sweeps are shown to be dominant in the region above the wind turbine array. A spectral analysis of the data shows that large scales of the flow, about the size of the rotor diameter in length or larger, dominate the vertical entrainment. The flow is more incoherent below the array, causing decreased vertical fluxes there. The results show that improving the rate of vertical kinetic energy entrainment into wind turbine arrays is a standing challenge and would require modifying the large-scale structures of the flow. This work was funded in part by the National Science Foundation (CBET-0730922, CBET-1133800 and CBET-0953053).

Effect of ceramic nanoparticles on the solid-state reaction mechanism of dolomite-zirconium oxide followed by neutron thermodiffraction measurements

NASA Astrophysics Data System (ADS)

Serena, S.; Caballero, A.; Turrillas, X.; Martin, D.; Sainz, M. A.

2009-05-01

Calcium zirconate-magnesium oxide material was obtained by solid-state reaction from mixed dolomite (CaMg(CO3)2) and zirconia (m-ZrO2) nanopowders. The nanopowders were obtained by high-energy milling, which produced an increase of the superficial free energy of the particles. The role of nanoparticles in the reaction process of monoclinic-zirconia and dolomite was analysed for the first time using neutron thermodiffraction and differential thermal analysis-thermogravimetric techniques. The neutron thermodiffraction of this mixture provides a clear description in situ of the different decomposition and reaction processes that occur in the nanopowders mixture. The results make it possible to analyze the effect of the nanoparticles on the reaction behaviour of these materials.

Kinetic Analysis of the Main Temperature Stage of Fast Pyrolysis

NASA Astrophysics Data System (ADS)

Yang, Xiaoxiao; Zhao, Yuying; Xu, Lanshu; Li, Rui

2017-10-01

Kinetics of the thermal decomposition of eucalyptus chips was evaluated using a high-rate thermogravimetric analyzer (BL-TGA) designed by our research group. The experiments were carried out under non-isothermal condition in order to determine the fast pyrolysis behavior of the main temperature stage (350-540ºC) at heating rates of 60, 120, 180, and 360ºC min-1. The Coats-Redfern integral method and four different reaction mechanism models were adopted to calculate the kinetic parameters including apparent activation energy and pre-exponential factor, and the Flynn-Wall-Ozawa method was employed to testify apparent activation energy. The results showed that estimation value was consistent with the values obtained by linear fitting equations, and the best-fit model for fast pyrolysis was found.

Vibration energy harvesting based monitoring of an operational bridge undergoing forced vibration and train passage

NASA Astrophysics Data System (ADS)

Cahill, Paul; Hazra, Budhaditya; Karoumi, Raid; Mathewson, Alan; Pakrashi, Vikram

2018-06-01

The application of energy harvesting technology for monitoring civil infrastructure is a bourgeoning topic of interest. The ability of kinetic energy harvesters to scavenge ambient vibration energy can be useful for large civil infrastructure under operational conditions, particularly for bridge structures. The experimental integration of such harvesters with full scale structures and the subsequent use of the harvested energy directly for the purposes of structural health monitoring shows promise. This paper presents the first experimental deployment of piezoelectric vibration energy harvesting devices for monitoring a full-scale bridge undergoing forced dynamic vibrations under operational conditions using energy harvesting signatures against time. The calibration of the harvesters is presented, along with details of the host bridge structure and the dynamic assessment procedures. The measured responses of the harvesters from the tests are presented and the use the harvesters for the purposes of structural health monitoring (SHM) is investigated using empirical mode decomposition analysis, following a bespoke data cleaning approach. Finally, the use of sequential Karhunen Loeve transforms to detect train passages during the dynamic assessment is presented. This study is expected to further develop interest in energy-harvesting based monitoring of large infrastructure for both research and commercial purposes.

An analysis of scatter decomposition

NASA Technical Reports Server (NTRS)

Nicol, David M.; Saltz, Joel H.

1990-01-01

A formal analysis of a powerful mapping technique known as scatter decomposition is presented. Scatter decomposition divides an irregular computational domain into a large number of equal sized pieces, and distributes them modularly among processors. A probabilistic model of workload in one dimension is used to formally explain why, and when scatter decomposition works. The first result is that if correlation in workload is a convex function of distance, then scattering a more finely decomposed domain yields a lower average processor workload variance. The second result shows that if the workload process is stationary Gaussian and the correlation function decreases linearly in distance until becoming zero and then remains zero, scattering a more finely decomposed domain yields a lower expected maximum processor workload. Finally it is shown that if the correlation function decreases linearly across the entire domain, then among all mappings that assign an equal number of domain pieces to each processor, scatter decomposition minimizes the average processor workload variance. The dependence of these results on the assumption of decreasing correlation is illustrated with situations where a coarser granularity actually achieves better load balance.

An optimization approach for fitting canonical tensor decompositions.

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

Dunlavy, Daniel M.; Acar, Evrim; Kolda, Tamara Gibson

Tensor decompositions are higher-order analogues of matrix decompositions and have proven to be powerful tools for data analysis. In particular, we are interested in the canonical tensor decomposition, otherwise known as the CANDECOMP/PARAFAC decomposition (CPD), which expresses a tensor as the sum of component rank-one tensors and is used in a multitude of applications such as chemometrics, signal processing, neuroscience, and web analysis. The task of computing the CPD, however, can be difficult. The typical approach is based on alternating least squares (ALS) optimization, which can be remarkably fast but is not very accurate. Previously, nonlinear least squares (NLS) methodsmore » have also been recommended; existing NLS methods are accurate but slow. In this paper, we propose the use of gradient-based optimization methods. We discuss the mathematical calculation of the derivatives and further show that they can be computed efficiently, at the same cost as one iteration of ALS. Computational experiments demonstrate that the gradient-based optimization methods are much more accurate than ALS and orders of magnitude faster than NLS.« less