EXAMINATION OF Zr AND Ti RECOMBINER LOOP SPECIMENS

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

Rittenhouse, P.L.

1958-12-19

Cold-worked specimens of iodide zirconium, Zircaloy-2, iodide titanium, and A-55 titanium were tested in a high-pressure recombiner loop in an attempt to duplicate anomalous results obtained in a prior recombiner loop. Hydrogen analyses and metallographic examinations were made on all specimens. The titanium materials and Zircaloy-2 picked up major amounts of hydrogen in the cell section. None of the materials tested showed appreciable hydrogen absorption in the recombiner section. Complete recrystallization occurred in all cell specimens while only Zircaloy-2, of the recombiner specimens, showed any degree of recrystallization. No explanation for this behavior can be given. A survnnary of themore » data obtained in previous recombiner loops is compared with the results of this loop. Conclusions were based on the results of three recombiner loops. Primarlly because of the hydrogen absorption data obtained in all three recombiner loops it is recommended that the zirconium and titunium materials tested not be used in environments similar to those encountered in high pressure recombiner loops. (auth)« less

The influence of strain rate and hydrogen on the plane-strain ductility of Zircaloy cladding

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

Link, T.M.; Motta, A.T.; Koss, D.A.

1998-03-01

The authors studied the ductility of unirradiated Zircaloy-4 cladding under loading conditions prototypical of those found in reactivity-initiated accidents (RIA), i.e.: near plane-strain deformation in the hoop direction (transverse to the cladding axis) at room temperature and 300 C and high strain rates. To conduct these studies, they developed a specimen configuration in which near plane-strain deformation is achieved in the gage section, and a testing methodology that allows one to determine both the limit strain at the onset of localized necking and the fracture strain. The experiments indicate that there is little effect of strain rate (10{sup {minus}3} tomore » 10{sup 2} s{sup {minus}1}) on the ductility of unhydrided Zircaloy tubing deformed under near plane-strain conditions at either room temperature or 300 C. Preliminary experiments on cladding containing 190 ppm hydrogen show only a small loss of fracture strain but no clear effect on limit strain. The experiments also indicate that there is a significant loss of Zircaloy ductility when surface flaws are present in the form of thickness imperfections.« less

Waterside corrosion of Zircaloy-clad fuel rods in a PWR environment

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

Garzarolli, F.; Jorde, D.; Manzel, R.

A data base of Zircaloy corrosion behavior under PWR operating conditions has been established from previously published reports as well as from new Kraftwerk Union (KWU) fuel examinations. The data show that the reactor environment increases the corrosion. ZrO/sub 2/ film thermal conductivity is another major factor that influences corrosion behavior. It was inferred from KWU film thickness data that the oxide film thermal conductivity may decrease once circumferential cracks develop in the layer. 57 refs.

Cyclic softening in annealed Zircaloy-2: Role of edge dislocation dipoles and vacancies

NASA Astrophysics Data System (ADS)

Sudhakar Rao, G.; Singh, S. R.; Krsjak, Vladimir; Singh, Vakil

2018-04-01

The mechanism of cyclic softening in annealed Zircaloy-2 at low strain amplitudes under strain controlled fatigue at room temperature is rationalized. The unusual softening due to continuous decrease in the phenomenological friction stress is found to be associated with decrease in the resistance against movement of dislocations because of the formation and easy glide of pure edge dislocation dipoles and consequent decrease in friction stress from reduction in the shear modulus. Positron annihilation spectroscopy data strongly support the increase in edge dislocation density containing jogs, from increased positron trapping and increase in annihilation lifetime.

Standard-less analysis of Zircaloy clad samples by an instrumental neutron activation method

NASA Astrophysics Data System (ADS)

Acharya, R.; Nair, A. G. C.; Reddy, A. V. R.; Goswami, A.

2004-03-01

A non-destructive method for analysis of irregular shape and size samples of Zircaloy has been developed using the recently standardized k0-based internal mono standard instrumental neutron activation analysis (INAA). The samples of Zircaloy-2 and -4 tubes, used as fuel cladding in Indian boiling water reactors (BWR) and pressurized heavy water reactors (PHWR), respectively, have been analyzed. Samples weighing in the range of a few tens of grams were irradiated in the thermal column of Apsara reactor to minimize neutron flux perturbations and high radiation dose. The method utilizes in situ relative detection efficiency using the γ-rays of selected activation products in the sample for overcoming γ-ray self-attenuation. Since the major and minor constituents (Zr, Sn, Fe, Cr and/or Ni) in these samples were amenable to NAA, the absolute concentrations of all the elements were determined using mass balance instead of using the concentration of the internal mono standard. Concentrations were also determined in a smaller size Zircaloy-4 sample by irradiating in the core position of the reactor to validate the present methodology. The results were compared with literature specifications and were found to be satisfactory. Values of sensitivities and detection limits have been evaluated for the elements analyzed.

The increase in fatigue crack growth rates observed for Zircaloy-4 in a PWR environment

NASA Astrophysics Data System (ADS)

Cockeram, B. V.; Kammenzind, B. F.

2018-02-01

Cyclic stresses produced during the operation of nuclear reactors can result in the extension of cracks by processes of fatigue. Although fatigue crack growth rate (FCGR) data for Zircaloy-4 in air are available, little testing has been performed in a PWR primary water environment. Test programs have been performed by Gee et al., in 1989 and Picker and Pickles in 1984 by the UK Atomic Energy Authority, and by Wisner et al., in 1994, that have shown an enhancement in FCGR for Zircaloy-2 and Zircaloy-4 in high-temperature water. In this work, FCGR testing is performed on Zircaloy-4 in a PWR environment in the hydrided and non-hydrided condition over a range of stress-intensity. Measurements of crack extension are performed using a direct current potential drop (DCPD) method. The cyclic rate in the PWR primary water environment is varied between 1 cycle per minute to 0.1 cycle per minute. Faster FCGR rates are observed in water in comparison to FCGR testing performed in air for the hydrided material. Hydrided and non-hydrided materials had similar FCGR values in air, but the non-hydrided material exhibited much lower rates of FCGR in a PWR primary water environment than for hydrided material. Hydrides are shown to exhibit an increased tendency for cracking or decohesion in a PWR primary water environment that results in an enhancement in FCGR values. The FCGR in the PWR primary water only increased slightly with decreasing cycle frequency in the range of 1 cycle per minute to 0.1 cycle per minute. Comparisons between the FCGR in water and air show the enhancement from the PWR environment is affected by the applied stress intensity.

Investigation of mechanical and microstructural properties of Zircaloy-4 under different experimental conditions

DOE PAGES

Silva, Chinthaka M.; Leonard, Keith J.; Van Abel, Eric; ...

2017-12-09

Here two types of Zircaloy-4 (alpha-annealed and beta-quenched) were investigated in their different forms. It was found that mechanical properties of Zircaloy-4 are affected significantly by welding and hydrogen-charging followed by neutron irradiation. Evaluation of microstructural properties of samples showed that these changes are mainly due to the formation of secondary phases such as hydrides—mostly along grain boundaries, dislocation channeling and their disruptions, and the increase in the type dislocation loops.

Investigation of mechanical and microstructural properties of Zircaloy-4 under different experimental conditions

NASA Astrophysics Data System (ADS)

Silva, Chinthaka M.; Leonard, Keith J.; Van Abel, Eric; Geringer, J. Wilna; Bryan, Chris D.

2018-02-01

Two types of Zircaloy-4 (alpha-annealed and beta-quenched) were investigated in their different forms. It was found that mechanical properties of Zircaloy-4 are affected significantly by welding and hydrogen-charging followed by neutron irradiation. Evaluation of microstructural properties of samples showed that these changes are mainly due to the formation of secondary phases such as hydrides-mostly along grain boundaries, dislocation channeling and their disruptions, and the increase in the type dislocation loops.

Transition joints between Zircaloy-2 and stainless steel by diffusion bonding

NASA Astrophysics Data System (ADS)

Bhanumurthy, K.; Krishnan, J.; Kale, G. B.; Banerjee, S.

1994-11-01

The diffusion bonding between Zircaloy-2 and stainless steel (AISI 304L) using niobium, nickel and copper as intermediate layers has been investigated in the temperature range of 750 to 900°C. Bonding was carried out in a vacuum hot press, under compressive loading. Electron probe microanalysis and metallographic analysis showed a good metallurgical compatibility and also indicated the absence of discontunities, micropores and intermetallic compounds at various interfaces. The bond strength of the diffusion bonded assembly was found to be about 400 MPa for the couples bonded at 870°C for 2 h. The dimple structure on the fractured surface is indicative of the ductile mode of failure of the bonded assembly.

Performance evaluation and post-irradiation examination of a novel LWR fuel composed of U0.17ZrH1.6 fuel pellets bonded to Zircaloy-2 cladding by lead bismuth eutectic

NASA Astrophysics Data System (ADS)

Balooch, Mehdi; Olander, Donald R.; Terrani, Kurt A.; Hosemann, Peter; Casella, Andrew M.; Senor, David J.; Buck, Edgar C.

2017-04-01

A novel light water reactor fuel has been designed and fabricated at the University of California, Berkeley; irradiated at the Massachusetts Institute of Technology Reactor; and examined within the Radiochemical Processing Laboratory at the Pacific Northwest National Laboratory. This fuel consists of U0.17ZrH1.6 fuel pellets core-drilled from TRIGA reactor fuel elements that are clad in Zircaloy-2 and bonded with lead-bismuth eutectic. The performance evaluation and post irradiation examination of this fuel are presented here.

The Influence of the In-Situ Clad Staining on the Corrosion of Zircaloy in PWR Water Environment

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

Kammenzind, B.F., Eklund, K.L. and Bajaj, R.

Zircaloy cladding tubes strain in-situ during service life in the corrosive environment of a Pressurized Water Reactor for a variety of reasons. First, the tube undergoes stress free growth due to the preferential alignment of irradiation induced vacancy loops on basal planes. Positive strains develop in the textured tubes along prism orientations while negative strains develop along basal orientations (Reference (a)). Second, early in life, free standing tubes will often shrink by creep in the diametrical direction under the external pressure of the water environment, but potentially grow later in life in the diametrical direction once the expanding fuel pelletmore » contacts the cladding inner wall (Reference (b)). Finally, the Zircaloy cladding absorbs hydrogen as a by product of the corrosion reaction (Reference (c)). Once above the solubility limit in Zircaloy, the hydride precipitates as zirconium hydride (References (c) through (j)). Both hydrogen in solid solution and precipitated as Zirconium hydride cause a volume expansion of the Zircaloy metal (Reference (k)). Few studies are reported on that have investigated the influence that in-situ clad straining has on corrosion of Zircaloy. If Zircaloy corrosion rates are governed by diffusion of anions through a thin passivating boundary layer at the oxide-to-metal interface (References (l) through (n)), in-situ straining of the cladding could accelerate the corrosion process by prematurely breaking that passivating oxide boundary layer. References (o) through (q) investigated the influence that an applied tensile stress has on the corrosion resistance of Zircaloy. Knights and Perkins, Reference (o), reported that the applied tensile stress increased corrosion rates above a critical stress level in 400 C and 475 C steam, but not at lower temperatures nor in dry oxygen environments. This latter observation suggested that hydrogen either in the oxide or at the oxide-to-metal interface is involved in the observed stress effect. Kim et al. (Reference (p)) and Kim and Kim (Reference (q)) more recently investigated the influence that an applied hoop stress has on the corrosion resistance of Zircaloy tubes in a 400 C steam and in a 350 C concentrated lithia water environment. Both of these studies found the applied tensile hoop stress to have no effect on cladding corrosion rates in the 400 C steam environment but to have accelerated corrosion in the lithiated water environment. In both cases, the corrosion acceleration in the lithiated water environment was attributed to the accumulation of the increased hydrogen picked up in the lithiated environment into the tensile regions of the test specimen. Dense hydride rims have been shown, independent of clad strain, to accelerate the corrosion of Zirconium alloys (References (r) and (s)), suggesting that the primary effect of applied stresses on the corrosion of Zircaloy in the above studies is through the accumulation of hydrogen at the oxide-to-metal interface and not through a direct mechanical breakdown of the passivating boundary layer. To further investigate the potential role of in-situ clad straining (or stress) on Zircaloy corrosion rates, two experimental studies were performed. First, several samples that were irradiated with and without an applied stress were destructively examined for the extent of corrosion occurring in strained and nonstrained regions of the test samples. The extent of corrosion was determined, posttest, by metallographic examination. Second, the corrosion process was monitored in-situ using electrochemical impedance spectroscopy on samples exposed out-of-reactor with and without an applied stress. Post test, these autoclave samples were also metallographically examined.« less

Growth and microstructure formation of isothermally-solidified Zircaloy-4 joints brazed by a Zr-Ti-Cu-Ni amorphous alloy ribbon

NASA Astrophysics Data System (ADS)

Kim, K. H.; Lim, C. H.; Lee, J. G.; Lee, M. K.; Rhee, C. K.

2013-10-01

The microstructure and growth characteristics of Zircaloy-4 joints brazed by a Zr48Ti16Cu17Ni19 (at.%) amorphous filler metal have been investigated with regard to the controlled isothermal solidification and intermetallic formation. Two typical joints were produced depending on the isothermal brazing temperature: (1) a dendritic growth structure including bulky segregation in the central zone (at 850 °C), and (2) a homogeneous dendritic structure throughout the joint without segregation (at 890 °C). The primary α-Zr phase was solidified isothermally, nucleating to grow into a joint with a cellular or dendritic structure. Also, the continuous Zr2Ni and particulate Zr2Cu phases were formed in the segregated center zone and at the intercellular region, respectively, owing to the different solubility and atomic mobility of the solute elements (Ti, Cu, and Ni) in the α-Zr matrix. A disappearance of the central Zr2Ni phase was also rate-controlled by the outward diffusion of the Cu and Ni elements. When the detrimental Zr2Ni intermetallic phase was eliminated by a complete isothermal solidification at 890 °C, the strengths of the joints were high enough to cause yielding and fracture in the base metal, exceeding those of the bulk Zircaloy-4, at room temperature as well as at elevated temperatures (up to 400 °C).

In situ monitored in-pile creep testing of zirconium alloys

NASA Astrophysics Data System (ADS)

Kozar, R. W.; Jaworski, A. W.; Webb, T. W.; Smith, R. W.

2014-01-01

The experiments described herein were designed to investigate the detailed irradiation creep behavior of zirconium based alloys in the HALDEN Reactor spectrum. The HALDEN Test Reactor has the unique capability to control both applied stress and temperature independently and externally for each specimen while the specimen is in-reactor and under fast neutron flux. The ability to monitor in situ the creep rates following a stress and temperature change made possible the characterization of creep behavior over a wide stress-strain-rate-temperature design space for two model experimental heats, Zircaloy-2 and Zircaloy-2 + 1 wt%Nb, with only 12 test specimens in a 100-day in-pile creep test program. Zircaloy-2 specimens with and without 1 wt% Nb additions were tested at irradiation temperatures of 561 K and 616 K and stresses ranging from 69 MPa to 455 MPa. Various steady state creep models were evaluated against the experimental results. The irradiation creep model proposed by Nichols that separates creep behavior into low, intermediate, and high stress regimes was the best model for predicting steady-state creep rates. Dislocation-based primary creep, rather than diffusion-based transient irradiation creep, was identified as the mechanism controlling deformation during the transitional period of evolving creep rate following a step change to different test conditions.

High- and Low-Temperature Deformation Behavior of Different Orientation Hot-Rolled Annealed Zircaloy-4

NASA Astrophysics Data System (ADS)

Zong, Yingying; Gen, Qingfeng; Jiang, Hongwei; Shan, Debin; Guo, Bin

2018-03-01

In this paper, the hot-rolled annealed Zircaloy-4 samples with different orientation were subjected to uniaxial compression with a strain rate of 0.001 s-1 to obtain the stress-strain curves of different initial orientation samples at different temperatures. Electron backscatter diffraction (EBSD) technique and transmission electron microscope (TEM) technique were used to analyze the microstructures and textures of compressed samples. The mechanical properties and microstructural evolution of rolling directions (RD), transverse directions (TD) and normal directions (ND) were investigated under the conditions of - 150 °C low temperature, room temperature and 200 °C high temperature (simulated lunar temperature environment). The results show that the strength of Zircaloy-4 decreases with the increase in deformation temperature, and the strength in three orientations is ND > TD > RD. The deformation mechanism of hot-rolled annealed Zircaloy-4 with different orientation is different. In RD, { 10\\bar{1}0} < {a} > prismatic slip has the highest Schmid factor (SF), so it is most easy to activate the slip, followed by TD orientation, and ND orientation is the most difficult to activate. The deformed grains abide slip→twinning→slip rule, and the different orientation Zircaloy-4 deformation mechanisms mainly are the twinning coordinated with the slip.

Corrosion behavior and oxide properties of Zr 1.1 wt%Nb 0.05 wt%Cu alloy

NASA Astrophysics Data System (ADS)

Park, Jeong-Yong; Choi, Byung-Kwon; Yoo, Seung Jo; Jeong, Yong Hwan

2006-12-01

The corrosion behavior and oxide properties of Zr-1.1 wt%Nb-0.05 wt%Cu (ZrNbCu) and Zircaloy-4 have been investigated. The corrosion rate of the ZrNbCu alloy was much lower than that of the Zirclaoy-4 in the 360 °C water and 360 °C PWR-simulating loop condition without a neutron flux and it was increased with an increase of the final annealing temperature from 470 °C to 570 °C. TEM observations revealed that the precipitates in the ZrNbCu were β-Nb and ZrNbFe-precipitate with β-Nb being more frequently observed and that the precipitates were more finely distributed in the ZrNbCu alloy. It was also observed that the oxides of the ZrNbCu and Zircaloy-4 consisted of two and seven layers, respectively, after 1000 days in the PWR-simulating loop condition and that the thickness of a fully-developed layer was higher in the ZrNbCu than in the Zircaloy-4. It was also found that the β-Nb in ZrNbCu was oxidized more slowly when compared to the Zr(Fe, Cr) 2 in Zirclaoy-4 when the precipitates in the oxide were observed by TEM. Cracks were observed in the vicinity of the oxidized Zr(Fe, Cr) 2, while no cracks were formed near β-Nb which had retained a metallic state. From the results obtained, it is suggested that the oxide formed on the ZrNbCu has a more protective nature against a corrosion when compared to that of the Zircaloy-4.

Nondestructive hydrogen analysis of steam-oxidized Zircaloy-4 by wide-angle neutron scattering

NASA Astrophysics Data System (ADS)

Yan, Yong; Qian, Shuo; Garrison, Ben; Smith, Tyler; Kim, Peter

2018-04-01

A nondestructive neutron scattering method to precisely measure the hydrogen content in high-temperature steam-oxidized Zircaloy-4 cladding was developed. Zircaloy-4 cladding was used to produce hydrided specimens with hydrogen content up to ≈500 wppm. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentrations were selected for the neutron study. The hydrided samples were then oxidized in steam up to ≈6.0 wt. % at 1100 °C. Optical microscopy shows that our hydriding procedure results in uniform distribution of circumferential hydrides across the wall thickness, and uniform oxide layers were formed on the sample surfaces by the steam oxidation. Small- and wide-angle neutron scattering were simultaneously performed to provide a quick (less than an hour per sample) measurement of the hydrogen content in various types of hydrided and oxidized Zircaloy-4. Our study demonstrates that the hydrogen in pre-oxidized Zircaloy-4 cladding can be measured very accurately by both small- and wide-angle neutron scattering. For steam-oxidized samples, the small-angle neutron scattering is contaminated with coherent scattering from additional structural features induced by the steam oxidation. However, the scattering intensity of the wide-angle neutron scattering increases proportionally with the hydrogen charged in the samples. The hydrogen content and wide-angle neutron scattering intensity are highly linearly correlated for the oxidized cladding samples examined in this work, and can be used to precisely determine the hydrogen content in steam-oxidized Zircaloy-4 samples. Hydrogen contents determined by neutron scattering of oxidation samples were also found to be consistent with the results of chemical analysis within acceptable margins for error.

Nondestructive hydrogen analysis of steam-oxidized Zircaloy-4 by wide-angle neutron scattering

DOE PAGES

Yan, Yong; Qian, Shuo; Garrison, Ben; ...

2018-04-15

In this study, a nondestructive neutron scattering method to precisely measure the hydrogen content in high-temperature steam-oxidized Zircaloy-4 cladding was developed. Zircaloy-4 cladding was used to produce hydrided specimens with hydrogen content up to ≈500 wppm. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentrations were selected for the neutron study. The hydrided samples were then oxidized in steam up to ≈6.0wt. % at 1100°C. Optical microscopy shows that our hydriding procedure results in uniform distribution of circumferential hydrides across the wall thickness,more » and uniform oxide layers were formed on the sample surfaces by the steam oxidation. Small- and wide-angle neutron scattering were simultaneously performed to provide a quick (less than an hour per sample) measurement of the hydrogen content in various types of hydrided and oxidized Zircaloy-4. Our study demonstrates that the hydrogen in pre-oxidized Zircaloy-4 cladding can be measured very accurately by both small- and wide-angle neutron scattering. For steam-oxidized samples, the small-angle neutron scattering is contaminated with coherent scattering from additional structural features induced by the steam oxidation. However, the scattering intensity of the wide-angle neutron scattering increases proportionally with the hydrogen charged in the samples. The hydrogen content and wide-angle neutron scattering intensity are highly linearly correlated for the oxidized cladding samples examined in this work, and can be used to precisely determine the hydrogen content in steam-oxidized Zircaloy-4 samples. Hydrogen contents determined by neutron scattering of oxidation samples were also found to be consistent with the results of chemical analysis within acceptable margins for error.« less

Nondestructive hydrogen analysis of steam-oxidized Zircaloy-4 by wide-angle neutron scattering

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

Yan, Yong; Qian, Shuo; Garrison, Ben

In this study, a nondestructive neutron scattering method to precisely measure the hydrogen content in high-temperature steam-oxidized Zircaloy-4 cladding was developed. Zircaloy-4 cladding was used to produce hydrided specimens with hydrogen content up to ≈500 wppm. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentrations were selected for the neutron study. The hydrided samples were then oxidized in steam up to ≈6.0wt. % at 1100°C. Optical microscopy shows that our hydriding procedure results in uniform distribution of circumferential hydrides across the wall thickness,more » and uniform oxide layers were formed on the sample surfaces by the steam oxidation. Small- and wide-angle neutron scattering were simultaneously performed to provide a quick (less than an hour per sample) measurement of the hydrogen content in various types of hydrided and oxidized Zircaloy-4. Our study demonstrates that the hydrogen in pre-oxidized Zircaloy-4 cladding can be measured very accurately by both small- and wide-angle neutron scattering. For steam-oxidized samples, the small-angle neutron scattering is contaminated with coherent scattering from additional structural features induced by the steam oxidation. However, the scattering intensity of the wide-angle neutron scattering increases proportionally with the hydrogen charged in the samples. The hydrogen content and wide-angle neutron scattering intensity are highly linearly correlated for the oxidized cladding samples examined in this work, and can be used to precisely determine the hydrogen content in steam-oxidized Zircaloy-4 samples. Hydrogen contents determined by neutron scattering of oxidation samples were also found to be consistent with the results of chemical analysis within acceptable margins for error.« less

Layer Protecting the Surface of Zirconium Used in Nuclear Reactors.

PubMed

Ashcheulov, Petr; Skoda, Radek; Skarohlíd, Jan; Taylor, Andrew; Fendrych, Frantisek; Kratochvílová, Irena

2016-01-01

Zirconium alloys have very useful properties for nuclear facilities applications having low absorption cross-section of thermal electrons, high ductility, hardness and corrosion resistance. However, there is also a significant disadvantage: it reacts with water steam and during this (oxidative) reaction it releases hydrogen gas, which partly diffuses into the alloy forming zirconium hydrides. A new strategy for surface protection of zirconium alloys against undesirable oxidation in nuclear reactors by polycrystalline diamond film has been patented- Czech patent 305059: Layer protecting the surface of zirconium alloys used in nuclear reactors and PCT patent: Layer for protecting surface of zirconium alloys (Patent Number: WO2015039636-A1). The zirconium alloy surface was covered by polycrystalline diamond layer grown in plasma enhanced chemical vapor deposition apparatus with linear antenna delivery system. Substantial progress in the description and understanding of the polycrystalline diamond/ zirconium alloys interface and material properties under standard and nuclear reactors conditions (irradiation, hot steam oxidation experiments and heating-quenching cycles) was made. In addition, process technology for the deposition of protective polycrystalline diamond films onto the surface of zirconium alloys was optimized. Zircaloy2 nuclear fuel pins were covered by 300 nm thick protective polycrystalline diamond layer (PCD) using plasma enhanced chemical vapor deposition apparatus with linear antenna delivery system. The polycrystalline diamond layer protects the zirconium alloy surface against undesirable oxidation and consolidates its chemical stability while preserving its functionality. PCD covered Zircaloy2 and standard Zircaloy2 pins were for 30 min. oxidized in 1100°C hot steam. Under these conditions α phase of zirconium changes to β phase (more opened for oxygen/hydrogen diffusion). PCD anticorrosion protection of Zircaloy nuclear fuel assemblies can significantly prolong lifetime of Zirconium alloy in nuclear reactors even above Zirconium phase transition temperatures. Even after ion beam irradiation (10 dpa, 3 MeV Fe(2+)) the diamond film still shows satisfactory structural integrity with both sp(3) and sp(2) carbon phases. Zircaloy2 under the carbon-based protective layer after hot steam oxidation test differed from the original Zircaloy2 material composition only very slightly, proving that the diamond coating increases the material resistance to high temperature oxidation. Zirconium alloys nuclear fuel pins' surfaces were covered by compact and homogeneous polycrystalline diamond layers consisting of sp(3) and sp(2) carbon phases with a high crystalline diamond content and low roughness. Diamond withstands very high temperatures, has excellent thermal conductivity and low chemical reactivity, it does not degrade over time and (important for the nuclear fuel cladding) being pure carbon, it has perfect neutron cross-section properties. Moreover, polycrystalline diamond layers consisting of crystalline (sp(3)) and amorphous (sp(2)) carbon phases could have suitable thermal expansion. Zirconium alloys coated with polycrystalline diamond film are protected against undesirable changes and processes. Further, the polycrystalline diamond layer prevents the reaction between the alloy surface and water vapor. During such reaction, water molecules dissociate and initiate formation of zirconium dioxide and hydrogen, accompanied by the release of large amount of heat. Thus the protective layer prevents the formation of hydrogen and the release of reaction heat. Few relevant patents to the topic have been reviewed and cited.

Crystal plasticity modeling of irradiation growth in Zircaloy-2

DOE PAGES

Patra, Anirban; Tome, Carlos; Golubov, Stanislav I.

2017-05-10

A reaction-diffusion based mean field rate theory model is implemented in the viscoplastic self-consistent (VPSC) crystal plasticity framework to simulate irradiation growth in hcp Zr and its alloys. A novel scheme is proposed to model the evolution (both number density and radius) of irradiation-induced dislocation loops that can be informed directly from experimental data of dislocation density evolution during irradiation. This framework is used to predict the irradiation growth behavior of cold-worked Zircaloy-2 and trends compared to available experimental data. The role of internal stresses in inducing irradiation creep is discussed. Effects of grain size, texture, and external stress onmore » the coupled irradiation growth and creep behavior are also studied.« less

Crystal plasticity modeling of irradiation growth in Zircaloy-2

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

Patra, Anirban; Tome, Carlos; Golubov, Stanislav I.

A reaction-diffusion based mean field rate theory model is implemented in the viscoplastic self-consistent (VPSC) crystal plasticity framework to simulate irradiation growth in hcp Zr and its alloys. A novel scheme is proposed to model the evolution (both number density and radius) of irradiation-induced dislocation loops that can be informed directly from experimental data of dislocation density evolution during irradiation. This framework is used to predict the irradiation growth behavior of cold-worked Zircaloy-2 and trends compared to available experimental data. The role of internal stresses in inducing irradiation creep is discussed. Effects of grain size, texture, and external stress onmore » the coupled irradiation growth and creep behavior are also studied.« less

AN ATTEMPT TO LOCATE INTERMETALLIC PARTICLES IN ZIRCONIUM ALLOYS USING A BITTER FIGURE TECHNIQUE

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

Cox, B.; Harder, B.R.

1961-10-01

The compound ZrFe/sub 2/ is known to be ferromagnetic, and an attempt to locate particles of magnetic material in zircaloy-2 and dilute Zr- Fe alloys by a Bitter figure technlque is described. An Fe/sub 3/O/sub 4/ sol in water-soluble plastic was used to prepare Bitter figures of the alloy surfaces in the form of replicas, which were then examined in an electron microscope. No magnetic particles were located in either zircaloy-2 or a Zr-O.3% Fe alloy. Subsequent work on specimens of ZrFe/sub 2/ showed that the failure to detect it in the dilute alloys arose because the size of themore » intermetallic particles in the latter was smaller than the size of the magnetic domains. (auth)« less

Evaluation of steam corrosion and water quenching behavior of zirconium-silicide coated LWR fuel claddings

NASA Astrophysics Data System (ADS)

Yeom, Hwasung; Lockhart, Cody; Mariani, Robert; Xu, Peng; Corradini, Michael; Sridharan, Kumar

2018-02-01

This study investigates steam corrosion of bulk ZrSi2, pure Si, and zirconium-silicide coatings as well as water quenching behavior of ZrSi2 coatings to evaluate its feasibility as a potential accident-tolerant fuel cladding coating material in light water nuclear reactor. The ZrSi2 coating and Zr2Si-ZrSi2 coating were deposited on Zircaloy-4 flats, SiC flats, and cylindrical Zircaloy-4 rodlets using magnetron sputter deposition. Bulk ZrSi2 and pure Si samples showed weight loss after the corrosion test in pure steam at 400 °C and 10.3 MPa for 72 h. Silicon depletion on the ZrSi2 surface during the steam test was related to the surface recession observed in the silicon samples. ZrSi2 coating (∼3.9 μm) pre-oxidized in 700 °C air prevented substrate oxidation but thin porous ZrO2 formed on the coating. The only condition which achieved complete silicon immobilization in the oxide scale in aqueous environments was the formation of ZrSiO4 via ZrSi2 coating oxidation in 1400 °C air. In addition, ZrSi2 coatings were beneficial in enhancing quenching heat transfer - the minimum film boiling temperature increased by 6-8% in the three different environmental conditions tested. During repeated thermal cycles (water quenching from 700 °C to 85 °C for 20 s) performed as a part of quench tests, no spallation and cracking was observed and the coating prevented oxidation of the underlying Zircaloy-4 substrate.

Accident-tolerant oxide fuel and cladding

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

Mariani, Robert D.

Systems and methods for accident tolerant oxide fuel. One or more disks can be placed between fuel pellets comprising UO.sub.2, wherein such disks possess a higher thermal conductivity material than that of the UO.sub.2 to provide enhanced heat rejection thereof. Additionally, a cladding coating comprising zircaloy coated with a material that provides stability and high melting capability can be provided. The pellets can be configured as annular pellets having an annulus filled with the higher thermal conductivity material. The material coating the zircaloy can be, for example, Zr.sub.5Si.sub.4 or another silicide such as, for example, a Zr-Silicide that limits corrosion.more » The aforementioned higher thermal conductivity material can be, for example, Si, Zr.sub.xSi.sub.y, Zr, or Al.sub.2O.sub.3.« less

Application of thin layer activation technique for surface wear studies in Zr based materials using charged particle induced nuclear reactions

NASA Astrophysics Data System (ADS)

Chowdhury, D. P.; Pal, Sujit; Parthasarathy, R.; Mathur, P. K.; Kohli, A. K.; Limaye, P. K.

1998-09-01

Thin layer activation (TLA) technique has been developed in Zr based alloy materials, e.g., zircaloy II, using 40 MeV α-particles from Variable Energy Cyclotron Centre at Calcutta. A brief description of the methodology of TLA technique is presented to determine the surface wear. The sensitivity of the measurement of surface wear in zircaloy material is found to be 0.22±0.05 μm. The surface wear is determined by TLA technique in zircaloy material which is used in pressurised heavy water reactor and the values have been compared with that obtained by conventional technique for the analytical validation of the TLA technique.

Texture and hydride orientation relationship of Zircaloy-4 fuel clad tube during its fabrication for pressurized heavy water reactors

NASA Astrophysics Data System (ADS)

Vaibhaw, Kumar; Rao, S. V. R.; Jha, S. K.; Saibaba, N.; Jayaraj, R. N.

2008-12-01

Zircaloy-4 material is used for cladding tube in pressurized heavy water reactors (PHWRs) of 220 MWe and 540 MWe capacity in India. These tubes are fabricated by using various combinations of thermo-mechanical processes to achieve desired mechanical and corrosion properties. Cladding tube develops crystallographic texture during its fabrication, which has significant influence on its in-reactor performance. Due to radiolytic decomposition of water Zircaloy-4 picks-up hydrogen. This hydrogen in excess of its maximum solubility in reactor operating condition (˜300 °C), precipitates as zirconium hydrides causing embrittlement of cladding tube. Hydride orientation in the radial direction of the tube limits the service life and lowers the fuel burn-up in reactor. The orientation of the hydride primarily depends on texture developed during fabrication. A correlation between hydride orientation ( F n) with the texture in the tube during its fabrication has been developed using a second order polynomial. The present work is aimed at quantification and correlation of texture evolved in Zircaloy-4 cladding tube using Kearn's f-parameter during its fabrication process.

Effect of He implantation on the microstructure of zircaloy-4 studied using in situ TEM

NASA Astrophysics Data System (ADS)

Tunes, M. A.; Harrison, R. W.; Greaves, G.; Hinks, J. A.; Donnelly, S. E.

2017-09-01

Zirconium alloys are of great importance to the nuclear industry as they have been widely used as cladding materials in light-water reactors since the 1960s. This work examines the behaviour of these alloys under He ion implantation for the purposes of developing understanding of the fundamental processes behind their response to irradiation. Characterization of zircaloy-4 samples using TEM with in situ 6 keV He irradiation up to a fluence of 2.7 ×1017ions ·cm-2 in the temperature range of 298 to 1148 K has been performed. Ordered arrays of He bubbles were observed at 473 and 1148 K at a fluence of 1.7 ×1017ions ·cm-2 in αZr, the hexagonal compact (HCP) and in βZr, the body centred cubic (BCC) phases, respectively. In addition, the dissolution behaviour of cubic Zr hydrides under He irradiation has been investigated.

Study on the hydrogenation of Zircaloy-4

NASA Astrophysics Data System (ADS)

da Silva Dupim, Ivaldete; Moreira, João M. L.; Silva, Selma Luiza; Silva, Cecilia Chaves Guedes e.; Nunes, Oswaldo; Gomide, Ricardo Gonçalves

2012-08-01

In this article we investigate producing Zirconium powder from discarded Zircaloy-4 material through the hydride-dehydride method. We restrict our study to the first part of the method, namely the hydrogenation process. Differential thermal analyses of the hydrogenation process of the Zircaloy-4 show that no hydrogen absorption occurs at temperatures below 573 K and hydrogen gas pressure of 25 kPa. When the system temperature is raised to around 770 K, with the same gas pressure, the protecting oxide layer of the specimens can be overcome and they are quickly hydrogenated. The bulk of the reaction occurs in about 5 min with the precipitation of Zirconium hydrides in the Zr-δ and Zr-ɛ phases. Once the temperature passes 573 K, the incubation time to initiate the reaction is short (about 5 min). Tests in a tube furnace system with larger samples, hydrogen pressure varying from 30 to 180 kPa, and temperature from 700 to 833.15 K, show that the specimens are fully hydrogenated and can be easily pulverized. The results indicate that the hydrogenation of the Zircaloy-4 chips can be successfully undertaken at temperatures around 770 K and hydrogen gas pressure as low as 30 kPa.

Characterisation of metallic glass incorporated Zircaloy-2 weldments

NASA Astrophysics Data System (ADS)

Mishra, S.; Savalia, R. T.; Bhanumurthy, K.; Dey, G. K.; Banerjee, S.

1995-12-01

In this study the effect of incorporation of Zr based Fe and Ni bearing metallic glass in spot welds in Zircaloy components has been examined. A comparison of strength and microstructure of the welded joint with and without glass has been carried out. The welded joint with metallic glass has been found to be stronger than the one without metallic glass. The microstructure of the welded region with metallic glass has been found to comprise a large region having martensite. This large martensitic region has also been found to have considerable amount of excess solute (Fe, Ni). The higher strength of the weld with metallic glass seems to originate due to solid solution strengthening, small grain size and the presence of martensitic structure over a large region.

High Temperature Corrosion and Heat Transfer Studies of Zirconium-Silicide Coatings for Light Water Reactor Cladding Applications

NASA Astrophysics Data System (ADS)

Yeom, Hwasung

Experimental results investigating the feasibility of zirconium-silicide coating for accident tolerance of LWR fuel cladding coating was presented. The oxidation resistance of ZrSi2 appeared to be superior to bare Zircaloy-4 in high temperature air. It was shown that micro- and nanostructures consisting of alternating SiO2 and ZrO2 evolved during transient oxidation of ZrSi2, which was explained by spinodal phase decomposition of Zr-Si-O oxide. Coating optimization regarding oxidation resistance was performed mainly using magnetron sputter deposition method. ZrSi 2 coatings ( 3.9 microm) showed improvement of almost two orders of magnitude when compared to bare Zircaloy-4 after air-oxidation at 700 °C for 20-hours. Pre-oxidation of ZrSi2 coating at 700 °C for 5 h significantly mitigated oxygen diffusion in air-oxidation tests at 1000 °C for 1-hour and 1200 °C for 10-minutes. The ZrSi2 coating with the pre-oxidation was found to be the best condition to prevent oxide formation in Zircaloy-4 substrate in the steam condition even if the top surface of the coating was degraded by formation of zirconium-rich oxide layer. Only the ZrSiO4 phase, formed by exposing the ZrSi2 coating at 1400 °C in air, allowed for immobilization of silicon species in the oxide scale in the aqueous environments. A quench test facility was designed and built to study transient boiling heat transfer of modified Zircaloy-4 surfaces (e.g., roughened surfaces, oxidized surfaces, ZrSi2 coated surfaces) at various system conditions (e.g., elevated pressures and water subcooling). The minimum film boiling temperature increased with increasing system pressure and water subcooling, consistent with past literature. Quenching behavior was affected by the types of surface modification regardless of the environmental conditions. Quenching heat transfer was improved by the ZrSi 2 coating, a degree of surface oxidation (deltaox = 3 to 50 microm), and surface roughening (Ra 20 microm). A plausible hypothesis based on transient heat conduction models for liquid-solid contact in quenching process was proposed to explain the enhanced quenching performance. The theoretical model incorporated localized temperature behavior on superheated surface and elucidated bubble dynamics qualitatively, and predicts minimum film boiling temperature of oxidized Zirc-4 surfaces, which were in good agreement with experimental data.

Synchrotron X-ray diffraction investigations on strains in the oxide layer of an irradiated Zircaloy fuel cladding

NASA Astrophysics Data System (ADS)

Chollet, Mélanie; Valance, Stéphane; Abolhassani, Sousan; Stein, Gene; Grolimund, Daniel; Martin, Matthias; Bertsch, Johannes

2017-05-01

For the first time the microstructure of the oxide layer of a Zircaloy-2 cladding after 9 cycles of irradiation in a boiling water reactor has been analyzed with synchrotron micro-X-ray diffraction. Crystallographic strains of the monoclinic and to some extent of the tetragonal ZrO2 are depicted through the thick oxide layer. Thin layers of sub-oxide at the oxide-metal interface as found for autoclave-tested samples and described in the literature, have not been observed in this material maybe resulting from irradiation damage. Shifts of selected diffraction peaks of the monoclinic oxide show that the uniform strain produced during oxidation is orientated in the lattice and displays variations along the oxide layer. Diffraction peaks and their shifts from families of diffracting planes could be translated into a virtual tensor. This virtual tensor exhibits changes through the oxide layer passing by tensile or compressive components.

Ratcheting fatigue behavior of Zircaloy-2 at room temperature

NASA Astrophysics Data System (ADS)

Rajpurohit, R. S.; Sudhakar Rao, G.; Chattopadhyay, K.; Santhi Srinivas, N. C.; Singh, Vakil

2016-08-01

Nuclear core components of zirconium alloys experience asymmetric stress or strain cycling during service which leads to plastic strain accumulation and drastic reduction in fatigue life as well as dimensional instability of the component. Variables like loading rate, mean stress, and stress amplitude affect the influence of asymmetric loading. In the present investigation asymmetric stress controlled fatigue tests were conducted with mean stress from 80 to 150 MPa, stress amplitude from 270 to 340 MPa and stress rate from 30 to 750 MPa/s to study the process of plastic strain accumulation and its effect on fatigue life of Zircaloy-2 at room temperature. It was observed that with increase in mean stress and stress amplitude accumulation of ratcheting strain was increased and fatigue life was reduced. However, increase in stress rate led to improvement in fatigue life due to less accumulation of ratcheting strain.

Investigation of Zircaloy-2 oxidation model for SFP accident analysis

NASA Astrophysics Data System (ADS)

Nemoto, Yoshiyuki; Kaji, Yoshiyuki; Ogawa, Chihiro; Kondo, Keietsu; Nakashima, Kazuo; Kanazawa, Toru; Tojo, Masayuki

2017-05-01

The authors previously conducted thermogravimetric analyses on Zircaloy-2 in air. By using the thermogravimetric data, an oxidation model was constructed in this study so that it can be applied for the modeling of cladding degradation in spent fuel pool (SFP) severe accident condition. For its validation, oxidation tests of long cladding tube were conducted, and computational fluid dynamics analyses using the constructed oxidation model were proceeded to simulate the experiments. In the oxidation tests, high temperature thermal gradient along the cladding axis was applied and air flow rates in testing chamber were controlled to simulate hypothetical SFP accidents. The analytical outputs successfully reproduced the growth of oxide film and porous oxide layer on the claddings in oxidation tests, and validity of the oxidation model was proved. Influence of air flow rate for the oxidation behavior was thought negligible in the conditions investigated in this study.

THE DETERMINATION OF BORON IN ZIRCALOY

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

Freegarde, M.; Cartwright, J.

1962-03-01

An account is given of the development of a simple and reliable procedure for determining boron in Zircaloy at the parts per million level. The sample is dissolved in a mixture of bromine and methanol, and the boron is separated by distillation and determined as its rosocyanin complex with curcumin. The reproducibility of the method is characterized by a standard deviation of 0.03 ppm at the 0.3 ppm level. (auth)

Performance of iron-chromium-aluminum alloy surface coatings on Zircaloy 2 under high-temperature steam and normal BWR operating conditions

NASA Astrophysics Data System (ADS)

Zhong, Weicheng; Mouche, Peter A.; Han, Xiaochun; Heuser, Brent J.; Mandapaka, Kiran K.; Was, Gary S.

2016-03-01

Iron-chromium-aluminum (FeCrAl) coatings deposited on Zircaloy 2 (Zy2) and yttria-stabilized zirconia (YSZ) by magnetron sputtering have been tested with respect to oxidation weight gain in high-temperature steam. In addition, autoclave testing of FeCrAl-coated Zy2 coupons under pressure-temperature-dissolved oxygen coolant conditions representative of a boiling water reactor (BWR) environment has been performed. Four different FeCrAl compositions have been tested in 700 °C steam; compositions that promote alumina formation inhibited oxidation of the underlying Zy2. Parabolic growth kinetics of alumina on FeCrAl-coated Zy2 is quantified via elemental depth profiling. Autoclave testing under normal BWR operating conditions (288 °C, 9.5 MPa with normal water chemistry) up to 20 days demonstrates observable weight gain over uncoated Zy2 simultaneously exposed to the same environment. However, no FeCrAl film degradation was observed. The 900 °C eutectic in binary Fe-Zr is addressed with the FeCrAl-YSZ system.

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

Jackson, Timothy D; Hollenbach, Daniel F; Shedlock, Daniel

Radiography by Selective Detection (RSD), was investigated for its ability to determine the presence and types of defects in a UO{sub 2} fuel rod surrounded by zirconium cladding. Images created using a Monte Carlo model compared favorably with actual X-ray backscatter images from mock fuel rods. A fuel rod was modeled as a rectangular parallelepiped with zirconium cladding, and pencil beam X-ray sources of 160 kVp (79 keV avg) and 480 kVp (218 keV avg) were generated using the Monte Carlo N-Particle Transport Code to attempt to image void and palladium (Pd) defects in the interior and on the surfacemore » of the fuel pellet. It was found that the 160 kVp spectrum was unable to detect the presence of interior defects, whereas the 480 kVp spectrum detected them with both the standard and the RSD backscatter methods, though the RSD method was very inefficient. It was also found that both energy spectra were able to detect void and Pd defects on the surface using both imaging methods. Additionally, two mock fuel rods were imaged using a backscatter X-ray imaging system, one consisting of hafnium pellets in a Zircaloy-4 cladding and the other consisting of steel pellets in a Zircalloy-4 cladding which was then encased in a steel cladding (a double encapsulation configuration employed in irradiation and experiments). It was found that the system was capable of detecting individual HfO{sub 2} pellets in a Zircaloy-4 cladding and may be capable of detecting individual steel pellets in the double-encapsulated sample. It is expected that the system would also be capable of detecting individual UO{sub 2} pellets in a Zircaloy-4 cladding, though no UO{sub 2} fuel rod was available for imaging.« less

Effects of pretreatment processes for Zr electrorefining of oxidized Zircaloy-4 cladding tubes

NASA Astrophysics Data System (ADS)

Hwa Lee, Chang; Lee, Yoo Lee; Jeon, Min Ku; Choi, Yong Taek; Kang, Kweon Ho; Park, Geun Il

2014-06-01

The effect of pretreatment processes for the Zr electrorefining of oxidized Zircaloy-4 cladding tubes is examined in LiCl-KCl-ZrCl4 molten salts at 500 °C. The cyclic voltammetries reveal that the Zr dissolution kinetics is highly dependent on the thickness of a Zr oxide layer formed at 500 °C under air atmosphere. For the Zircaloy-4 tube covered with a 1 μm thick oxide layer, the Zr dissolution process is initiated from a non-stoichiometric Zr oxide surface through salt treatment at an open circuit potential in the molten salt electrolyte. The Zr dissolution of the samples in the middle range of oxide layer thickness appears to be more effectively derived by the salt treatment coupled with an anodic potential application at an oxidation potential of Zr. A modification of the process scheme offers an applicability of Zr electrorefining for the treatment of oxidized cladding hull wastes.

Corrosion behavior in high-temperature pressurized water of Zircaloy-4 joints brazed with Zr-Cu-based amorphous filler alloys

NASA Astrophysics Data System (ADS)

Lee, Jung Gu; Lee, Gyoung-Ja; Park, Jin-Ju; Lee, Min-Ku

2017-05-01

The compositional effects of ternary Zr-Cu-X (X: Al, Fe) amorphous filler alloys on galvanic corrosion susceptibility in high-temperature pressurized water were investigated for Zircaloy-4 brazed joints. Through an Al-induced microgalvanic reaction that deteriorated the overall nobility of the joint, application of the Zr-Cu-Al filler alloy caused galvanic coupling to develop readily between the Al-bearing joint and the Al-free base metal, finally leading to massive localized corrosion of the joint. Contrastingly, joints prepared with a Zr-Cu-Fe filler alloy showed excellent corrosion resistance comparable to that of the Zircaloy-4 base metal, since the Cu and Fe elements forming fine intermetallic particles with Zr did not influence the electrochemical stability of the resultant joints. The present results demonstrate that Fe is a more suitable alloying element than Al for brazing filler alloys subjected to high-temperature corrosive environments.

EPRI-NASA Cooperative Project on Stress Corrosion Cracking of Zircaloys. [nuclear fuel failures

NASA Technical Reports Server (NTRS)

Cubicciotti, D.; Jones, R. L.

1978-01-01

Examinations of the inside surface of irradiated fuel cladding from two reactors show the Zircaloy cladding is exposed to a number of aggressive substances, among them iodine, cadmium, and iron-contaminated cesium. Iodine-induced stress corrosion cracking (SCC) of well characterized samples of Zircaloy sheet and tubing was studied. Results indicate that a threshold stress must be exceeded for iodine SCC to occur. The existence of a threshold stress indicates that crack formation probably is the key step in iodine SCC. Investigation of the crack formation process showed that the cracks responsible for SCC failure nucleated at locations in the metal surface that contained higher than average concentrations of alloying elements and impurities. A four-stage model of iodine SCC is proposed based on the experimental results and the relevance of the observations to pellet cladding interaction failures is discussed.

High Resolution Neutron Radiography and Tomography of Hydrided Zircaloy-4 Cladding Materials

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

Smith, Tyler S; Bilheux, Hassina Z; Ray, Holly B

2015-01-01

Neutron radiography for hydrogen analysis was performed with several Zircaloy-4 cladding samples with controlled hydrogen concentrations up to 1100 ppm. Hydrogen charging was performed in a process tube that was heated to facilitate hydrogen absorption by the metal. A correlation between the hydrogen concentration in the hydrided tubes and the neutron intensity was established, by which hydrogen content can be determined precisely in a small area (55 m x 55 m). Radiography analysis was also performed to evaluate the heating rate and its correlation with the hydrogen distribution through hydrided materials. In addition to radiography analysis, tomography experiments were performedmore » on Zircaloy-4 tube samples to study the local hydrogen distribution. Through tomography analysis a 3D reconstruction of the tube was evaluated in which an uneven hydrogen distribution in the circumferential direction can be observed.« less

Implications of Zircaloy creep and growth to light water reactor performance

NASA Astrophysics Data System (ADS)

Franklin, David G.; Adamson, Ronald B.

1988-10-01

Deformation of zirconium alloy components in nuclear reactors has been a concern since the decision of Admiral Rickover to use them in the US Navy submarine reactors. With the exception of the first few light water reactors (LWRs) most of the core structural materials have been fabricated from either Zircaloy-2 or Zircaloy-4. Performance of these alloys has been extremely good, even though the effects of irradiation on deformation magnitudes and mechanisms were not fully appreciated until extensive service and in-reactor tests were accomplished. Since the reactor components are designed to operate at stress levels well below yield for normal conditions, the only significant deformation is time dependent. Although creep was anticipated, the enhancement by neutron irradiation and the stress-free, nearly constant-volume shape change known as irradiation growth were not known prior to materials testing in reactors under controlled conditions. Both of these phenomena have significant impact on performance and must be accounted for properly in design. Although irradiation creep and growth have resulted in only one significant performance problem (creep collapse of fuel cladding, which has been eliminated), deformation magnitudes and, particularly, differentials in strain magnitudes, are a continuing source of interest. Factors that affect dimensional stability due to both creep and growth include temperature, fluence, residual stress, texture, and microstructure. The first two are reactor variables and the others are related to component fabrication history. This paper includes a review of the applications of Zircaloy creep and growth to LWR fuel designs, a review of the impact of in-reactor creep and growth on fuel rod and fuel assembly performance, and comments on potential improvements. Since the reactor design, fuel design and the core environment in BWRs and PWRs are quite different, appropriate separation of the application of effects are made; of course, the basic phenomena are the same in both systems.

Crystal plasticity modeling of irradiation growth in Zircaloy-2

NASA Astrophysics Data System (ADS)

Patra, Anirban; Tomé, Carlos N.; Golubov, Stanislav I.

2017-08-01

A physically based reaction-diffusion model is implemented in the visco-plastic self-consistent (VPSC) crystal plasticity framework to simulate irradiation growth in hcp Zr and its alloys. The reaction-diffusion model accounts for the defects produced by the cascade of displaced atoms, their diffusion to lattice sinks and the contribution to crystallographic strain at the level of single crystals. The VPSC framework accounts for intergranular interactions and irradiation creep, and calculates the strain in the polycrystalline ensemble. A novel scheme is proposed to model the simultaneous evolution of both, number density and radius, of irradiation-induced dislocation loops directly from experimental data of dislocation density evolution during irradiation. This framework is used to predict the irradiation growth behaviour of cold-worked Zircaloy-2 and trends compared to available experimental data. The role of internal stresses in inducing irradiation creep is discussed. Effects of grain size, texture and external stress on the coupled irradiation growth and creep behaviour are also studied and compared with available experimental data.

Room temperature mechanical properties of electron beam welded zircaloy-4 sheet

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

Parga, C. J.; Rooyen, I. J.; Coryell, B. D.

Room temperature mechanical properties of electron beam welded and plain Zircaloy-4 sheet (1.6mm thick) have been measured and compared. Various welding parameters were utilized to join sheet material. Electron beam welded specimens and as-received sheet specimens show comparable mechanical properties. Zr-4 sheet displays anisotropy; tensile properties measured for transverse display higher elastic modulus, yield strength, reduction of area and slightly lower ductility than for the longitudinal (rolling direction). Higher welding power increases the alloy’s hardness, elastic modulus and yield strength, with a corresponding decrease in tensile strength and ductility. The hardness measured at weld is comparable to the parent metalmore » hardness. Hardness at heat-affected-zone is slightly higher. Electron microscopic examination shows distinct microstructure morphology and grain size at the weld zone, HAZ and parent metal. A correlation between welding parameters, mechanical properties and microstructural features was established for electron beam welded Zircaloy-4 sheet material.« less

Room temperature mechanical properties of electron beam welded zircaloy-4 sheet

DOE PAGES

Parga, C. J.; Rooyen, I. J.; Coryell, B. D.; ...

2017-11-04

Room temperature mechanical properties of electron beam welded and plain Zircaloy-4 sheet (1.6mm thick) have been measured and compared. Various welding parameters were utilized to join sheet material. Electron beam welded specimens and as-received sheet specimens show comparable mechanical properties. Zr-4 sheet displays anisotropy; tensile properties measured for transverse display higher elastic modulus, yield strength, reduction of area and slightly lower ductility than for the longitudinal (rolling direction). Higher welding power increases the alloy’s hardness, elastic modulus and yield strength, with a corresponding decrease in tensile strength and ductility. The hardness measured at weld is comparable to the parent metalmore » hardness. Hardness at heat-affected-zone is slightly higher. Electron microscopic examination shows distinct microstructure morphology and grain size at the weld zone, HAZ and parent metal. A correlation between welding parameters, mechanical properties and microstructural features was established for electron beam welded Zircaloy-4 sheet material.« less

Review of PWR fuel rod waterside corrosion behavior

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

Garzarolli, F.; Jorde, D.; Manzel, R.

Waterside corrosion of Zircaloy has generally not been a problem under normal PWR operating conditions, although some instances of accelerated corrosion have been reported. However, an incentive exists to extend the average fuel rod discharge burnups to about 50,000 MWd/MTU. To minimize corrosion at these extended burnups, the factors which influence Zircaloy corrosion need to be better understood. A data base of Zircaloy corrosion behavior under PWR operating conditions has been established. The data are compiled previously published reports as well as from new Kraftwerk Union examinations. A non-destructive eddy-current technique is used to measure the oxide layer thickness onmore » fuel rods. Comparisons of measuremnts made using this eddy-current technique with those made by usual metallographic methods indicate good agreement. The data were evaluated by defining a fitting factor F which describes the increase in corrosion rate observed in-reactor over that observed from measurements of ex-reactor corrosion coupons.« less

Bending testing and characterization of surrogate nuclear fuel rods made of Zircaloy-4 cladding and aluminum oxide pellets

NASA Astrophysics Data System (ADS)

Wang, Hong; Wang, Jy-An John

2016-10-01

Behavior of surrogate nuclear fuel rods made of Zircaloy-4 (Zry-4) cladding with alumina pellets under reversed cyclic bending was studied. Tests were performed under load or moment control at 5 Hz. The surrogate rods fractured under moment amplitudes greater than 10.16 Nm with fatigue lives between 2.4 × 103 and 2.2 × 106 cycles. Fatigue response of Zry-4 cladding was characterized by using flexural rigidity. Degradation of flexural rigidity was shown to depend on the moment and the prefatigue condition of specimens. Pellet-to-pellet interface (PPI), pellet-to-cladding interface (PCI), and pellet condition affect surrogate rod failure. Both debonding of PPI/PCI and pellet fracturing contribute to surrogate rod bending fatigue. The effect of sensor spacing on curvature measurement using three-point deflections was studied; the method based on effective gauge length is effective in sensor spacing correction. The database developed and the understanding gained in this study can serve as input to analysis of SNF (spent nuclear fuel) vibration integrity.

The effect of plastic strain on the evolution of crystallographic texture in Zircaloy-2

NASA Astrophysics Data System (ADS)

Ballinger, R. G.; Lucas, G. E.; Pelloux, R. M.

1984-09-01

The evolution of crystallographic texture during plastic deformation was investigated in Zircaloy-2 using X-ray and metallographic techniques. Inverse pole figures, the resolved fraction of basal poles, and the volume fraction of twinned material, were determined as a function of plastic strain for several strain paths and initial textures at 298 K and 623 K. Incremental transverse platic strain ratios ( R) were mesured as a function of plastic strain. Texture rotation occurs early in the deformation process, after as little as 1.5% plastic strain. For compressive plastic strains, the resolved fraction of basal poles increases in the direction parallel to the strain axis. For tensile plastic strains, the resolved fraction of basal poles decreases in the direction parallel to the strain axis. The rate of change of the resolved fraction of basal poles with plastic strain is a function of the initial resolved fraction of basal poles. The texture rotation can be explained by considering the operation of the principal tensile twinning systems, {101¯2}<1¯011>.

75 FR 80546 - Virginia Electric and Power Company; Surry Power Station Unit Nos. 1 and 2; Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-22

... used to predict the rates of energy release, hydrogen concentration, and cladding oxidation from the... associated hydrogen pickup) for Optimized ZIRLO TM at any given burnup would be less than both zircaloy-4 and... between cladding hydrogen content (due to in-service corrosion) and post-quench ductility. \\2\\ ADAMS...

In situ high temperature oxidation analysis of Zircaloy-4 using acoustic emission coupled with thermogravimetry

NASA Astrophysics Data System (ADS)

Omar, Al Haj; Véronique, Peres; Eric, Serris; François, Grosjean; Jean, Kittel; François, Ropital; Michel, Cournil

2015-06-01

Zircaloy-4 oxidation behavior at high temperature (900 °C), which can be reached in case of severe accidental situations in nuclear pressurised water reactor, was studied using acoustic emission analysis coupled with thermogravimetry. Two different atmospheres were used to study the oxidation of Zircaloy-4: (a) helium and pure oxygen, (b) helium and oxygen combined with slight addition of air. The experiments with 20% of oxygen confirm the dependence on oxygen anions diffusion in the oxide scale. Under a mixture of oxygen and air in helium, an acceleration of the corrosion was observed due to the detrimental effect of nitrogen. The kinetic rate increased significantly after a kinetic transition (breakaway). This acceleration was accompanied by an acoustic emission activity. Most of the acoustic emission bursts were recorded after the kinetic transition (post-transition) or during the cooling of the sample. The characteristic features of the acoustic emission signals appear to be correlated with the different populations of cracks and their occurrence in the ZrO2 layer or in the α-Zr(O) layer. Acoustic events were recorded during the isothermal dwell time at high temperature under air. They were associated with large cracks in the zirconia porous layer. Acoustic events were also recorded during cooling after oxidation tests both under air or oxygen. For the latter, cracks were observed in the oxygen enriched zirconium metal phase and not in the dense zirconia layer after 5 h of oxidation.

75 FR 76051 - Northern States Power Company-Minnesota, Prairie Island Nuclear Generating Plant, Units 1 and 2...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-12-07

..., 2010 (Agencywide Documents Access and Management System Accession Nos. ML093280883 and ML101480083... systems for light-water nuclear power reactors,'' and appendix K to 10 CFR part 50, ``ECCS Evaluation... core cooling system (ECCS) for reactors fueled with zircaloy or ZIRLO\\TM\\ cladding. In addition...

Diffusion and phase change characterization by mass spectrometry

NASA Technical Reports Server (NTRS)

Koslin, M. E.; White, F. A.

1979-01-01

The high temperature diffusion of trace elements in metals and alloys was investigated. Measurements were made by high sensitivity mass spectrometry in which individual atoms were detected, and quantitative data was obtained for zircaloy-2, 304 stainless steel, and tantalum. Additionally, a mass spectrometer was also an analytical tool for determining an allotropic phase change for stainless steel at 955 C, and a phase transition region between 772 C and 1072 C existing for zircaloy-2. Diffusion rates were measured in thin (0.001" (0.0025 cm) and 0.0005" (0.0013 cm)) ribbons which were designed as high temperature thermal ion sources, with the alkali metals as naturally occurring impurities. In the temperature and pressure regime where diffusion measurements were made, the solute atoms evaporated from the ribbon filaments when the impurities diffused to the surface, with a fraction of these impurity atoms ionized according to the Langmuir-Saha relation. The techniques developed can be applied to many other alloys important to space vehicles and supersonic transports; and, with appropriate modifications, to the diffusion of impurities in composites.

Hydride Microstructure at the Metal-Oxide Interface of Zircaloy-4 from H.B. Robinson Nuclear Reactor

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

Cinbiz, Mahmut N; Edmondson, Philip D; Terrani, Kurt A

2017-01-01

This study investigates the hydride rim microstructure at the metal-oxide interface of Zircaloy-4 cladding segment removed from H.B. Robinson Nuclear Reactor by utilizing high resolution electron microscopy techniques with energy dispersive x-ray spectroscopy at Oak Ridge National Laboratory under the NSUF Rapid Turnout Experiment program. A complex stacking and orientation of hydride platelets has been observed below the sub-oxide layer. Furthermore, radial hydride platelets have been observed. EDS signals of both Fe and Cr has been reduced within hydrides whereas EDS signal of Sn is unaffected.

Effects of anisotropy and irradiation on the deformation behavior of Zircaloy 2. Final report

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

Pelloux, R.M.; Ballinger, R.; Lucas, G.

1979-01-01

An experimental program investigated the effects of texture anisotropy and irradiation on the mechanical behavior of Zircaloy-2. Short time and time dependent mechanical behavior were considered. Irradiation effects were simulated through the use of 4.75 MeV protons. The temperature ranges investigated were 298/sup 0/K and 573 to 673/sup 0/K. Both cold worked-stress relieved and annealed material were used in this experimental program. Short time yield behavior of different crystallographic textures was determined by uniaxial and plane strain tests in the temperature range 298/sup 0/K and 573 to 673/sup 0/K. Monotonic flow loci were constructed for each texture. Yield behavior ismore » a strong function of the crystallographic texture number f at all temperatures investigated. The rotation of texture with increasing plastic strain was investigated as a function of initial texture at 298/sup 0/K and 623/sup 0/K. The rate of texture rotation df/epsilon/sub p/ was found to be a unique function of the initial texture for plastic strains less than 0.08. Time dependent mechanical behavior was investigated in the range 573 to 673/sup 0/K using constant load creep and stress relaxation tests. The tensile creep strength is proportional to the resolved fraction of basal poles in the test direction. In variable stress and temperature tests, the time-hardening rule was found to be inapplicable. The strain-hardening rule was applied with success to data obtained at temperatures less than or equal to 648/sup 0/K. Irradiation creep tests were conducted in vacuum at 598/sup 0/K and 102 to 241 MPa on 80..mu..m thick Zircaloy-2 foil specimens in both the recrystallized and cold worked-stress relieved condition. In the irradiation creep tests irradiation hardening and enhanced irradiation creep were observed. Radiation hardening effects were significant in annealed material but were attenuated in cold worked-stress relieved material.« less

76 FR 68511 - STP Nuclear Operating Company; South Texas Project, Units 1 and 2; Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2011-11-04

... reactor located in Matagorda County in Texas. 2.0 Request/Action Pursuant to Title 10 of the Code of... from the metal/water reaction. The Baker-Just equation assumes the use of zircaloy or ZIRLO \\TM\\, which... underlying purpose of 10 CFR part 50, appendix K, Section I.A.5, ``Metal-Water Reaction Rate,'' is to ensure...

Demonstration of fuel resistant to pellet-cladding interaction. Phase I. Final report

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

Rosenbaum, H.S.

1979-03-01

This program has as its ultimate objective the demonstration of an advanced fuel design that is resistant to the failure mechanism known as fuel pellet-cladding interaction (PCI). Two fuel concepts are being developed for possible demonstration within this program: (a) Cu-barrier fuel, and (b) Zr-liner fuel. These advanced fuels (known collectively as barrier fuels) have special fuel cladding designed to protect the Zircaloy cladding tube from the harmful effects of localized stress, and reactive fission products during reactor service. This is the final report for PHASE 1 of this program. Support tests have shown that the barrier fuel resists PCImore » far better than does the conventional Zircaloy-clad fuel. Power ramp tests thus far have shown good PCI resistance for Cu-barrier fuel at burnup > 12 MWd/kg-U and for Zr-liner fuel > 16 MWd/kg-U. The program calls for continued testing to still higher burnup levels in PHASE 2.« less

MODELLING OF FUEL BEHAVIOUR DURING LOSS-OF-COOLANT ACCIDENTS USING THE BISON CODE

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

Pastore, G.; Novascone, S. R.; Williamson, R. L.

2015-09-01

This work presents recent developments to extend the BISON code to enable fuel performance analysis during LOCAs. This newly developed capability accounts for the main physical phenomena involved, as well as the interactions among them and with the global fuel rod thermo-mechanical analysis. Specifically, new multiphysics models are incorporated in the code to describe (1) transient fission gas behaviour, (2) rapid steam-cladding oxidation, (3) Zircaloy solid-solid phase transition, (4) hydrogen generation and transport through the cladding, and (5) Zircaloy high-temperature non-linear mechanical behaviour and failure. Basic model characteristics are described, and a demonstration BISON analysis of a LWR fuel rodmore » undergoing a LOCA accident is presented. Also, as a first step of validation, the code with the new capability is applied to the simulation of experiments investigating cladding behaviour under LOCA conditions. The comparison of the results with the available experimental data of cladding failure due to burst is presented.« less

HRTEM and chemical study of an ion-irradiated chromium/zircaloy-4 interface

NASA Astrophysics Data System (ADS)

Wu, A.; Ribis, J.; Brachet, J.-C.; Clouet, E.; Leprêtre, F.; Bordas, E.; Arnal, B.

2018-06-01

Chromium-coated zirconium alloys are being studied as Enhanced Accident Tolerant Fuel Cladding for Light Water Reactors (LWRs). Those materials are especially studied to improve the oxidation resistance of LWRs current fuel claddings in nominal and at High Temperature (HT) for hypothetical accidental conditions such as LOss of Coolant Accident. Beyond their HT behavior, it is essential to assess the materials behavior under irradiation. A first generation chromium/Zircaloy-4 interface was thus irradiated with 20 MeV Kr8+ ions at 400 °C up to 10 dpa. High-Resolution Transmission Electron Microscopy and chemical analysis (EDS) were conducted at the Cr/Zr interface. The atomic structure of the interface reveals the presence of Zr(Fe, Cr)2 Laves phase, displaying both C14 and C15 structure. After irradiation, only the C14 structure was observed and atomic row matching was preserved across the different interfaces, thus ensuring a good adhesion of the coating after irradiation.

Stress corrosion cracking of Zircaloys in unirradiated and irradiated CsI

NASA Astrophysics Data System (ADS)

Cox, B.; Surette, B. A.; Wood, J. C.

1986-03-01

Unirradiated split-ring specimens of Zircaloy fuel cladding, coated with CsI, cracked when stressed at elevated temperatures. The specimens have been reexamined fractographically and metallographically in order to confirm that the cause of cracking was stress corrosion (SCC) and not delayed hydride cracking (DHC). Further specimens have been cracked at 350°C by a solution of CsI in a fused mixture of nitrates of rubidium, cesium, strontium and barium, by a similar mechanism. CsI dissolved in a fused molybdate melt was not stable at 400°C, and rapidly evolved iodine, leaving a melt that was incapable of causing SCC. Irradiation of stressed split-ring specimens of Zircaloy fuel cladding in a γ-irradiator of 10 6 R/h and in the U-5 loop in the NRU reactor at an estimated 10 9 R/h caused SCC when the specimens were packed in dry CsI powder. Care had to be taken to dry the CsI, otherwise cracking occurred by a DHC mechanism from hydrogen absorbed from residual moisture in the CsI. Fractography showed that the crack surfaces obtained with dry CsI were typical of iodine-induced SCC rather than cesium-induced metal vapour embrittlement. Thus, if a transport process is provided for the iodide to obtain access to the zirconium surface, CsI is capable of causing SCC of Zircaloy. This transport process might be ionic diffusion in a fission product oxide melt in the fuel-clad gap, however, radiolysis of CsI to form a volatile iodine species in a radiation field is the more probable explanation of PCI failures.

Quantitative analysis of deuterium in zircaloy using double-pulse laser-induced breakdown spectrometry (LIBS) and helium gas plasma without a sample chamber.

PubMed

Suyanto, H; Lie, Z S; Niki, H; Kagawa, K; Fukumoto, K; Rinda, Hedwig; Abdulmadjid, S N; Marpaung, A M; Pardede, M; Suliyanti, M M; Hidayah, A N; Jobiliong, E; Lie, T J; Tjia, M O; Kurniawan, K H

2012-03-06

A crucial safety measure to be strictly observed in the operation of heavy-water nuclear power plants is the mandatory regular inspection of the concentration of deuterium penetrated into the zircaloy fuel vessels. The existing standard method requires a tedious, destructive, and costly sample preparation process involving the removal of the remaining fuel in the vessel and melting away part of the zircaloy pipe. An alternative method of orthogonal dual-pulse laser-induced breakdown spectrometry (LIBS) is proposed by employing flowing atmospheric helium gas without the use of a sample chamber. The special setup of ps and ns laser systems, operated for the separate ablation of the sample target and the generation of helium gas plasma, respectively, with properly controlled relative timing, has succeeded in producing the desired sharp D I 656.10 nm emission line with effective suppression of the interfering H I 656.28 nm emission by operating the ps ablation laser at very low output energy of 26 mJ and 1 μs ahead of the helium plasma generation. Under this optimal experimental condition, a linear calibration line is attained with practically zero intercept and a 20 μg/g detection limit for D analysis of zircaloy sample while creating a crater only 10 μm in diameter. Therefore, this method promises its potential application for the practical, in situ, and virtually nondestructive quantitative microarea analysis of D, thereby supporting the more-efficient operation and maintenance of heavy-water nuclear power plants. Furthermore, it will also meet the anticipated needs of future nuclear fusion power plants, as well as other important fields of application in the foreseeable future.

In-reactor oxidation of zircaloy-4 under low water vapor pressures

NASA Astrophysics Data System (ADS)

Luscher, Walter G.; Senor, David J.; Clayton, Kevin K.; Longhurst, Glen R.

2015-01-01

Complementary in- and ex-reactor oxidation tests have been performed to evaluate the oxidation and hydrogen absorption performance of Zircaloy-4 (Zr-4) under relatively low partial pressures (300 and 1000 Pa) of water vapor at specified test temperatures (330 and 370 °C). Data from these tests will be used to support the fabrication of components intended for isotope-producing targets and provide information regarding the temperature and pressure dependence of oxidation and hydrogen absorption of Zr-4 over the specified range of test conditions. Comparisons between in- and ex-reactor test results were performed to evaluate the influence of irradiation.

Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

2017-01-01

This report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy is dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along is found to be slightly higher than that along , with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins.

Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations

PubMed Central

Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

2017-01-01

This report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy is dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along is found to be slightly higher than that along , with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins. PMID:28106154

Anisotropic hydrogen diffusion in α-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations

DOE PAGES

Zhang, Yongfeng; Jiang, Chao; Bai, Xianming

2017-01-20

Here, this report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in α-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in α-Zr and Zircaloy ismore » dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along < c > is found to be slightly higher than that along < a >, with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in α-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins.« less

a Study on the Fretting Fatigue Life of Zircaloy Alloys

NASA Astrophysics Data System (ADS)

Kwon, Jae-Do; Park, Dae-Kyu; Woo, Seung-Wan; Chai, Young-Suck

Studies on the strength and fatigue life of machines and structures have been conducted in accordance with the development of modern industries. In particular, fine and repetitive cyclic damage occurring in contact regions has been known to have an impact on fretting fatigue fractures. The main component of zircaloy alloy is Zr, and it possesses good mechanical characteristics at high temperatures. This alloy is used in the fuel rod material of nuclear power plants because of its excellent resistance. In this paper, the effect of the fretting damage on the fatigue behavior of the zircaloy alloy is studied. Further, various types of mechanical tests such as tension and plain fatigue tests are performed. Fretting fatigue tests are performed with a flat-flat contact configuration using a bridge-type contact pad and plate-type specimen. Through these experiments, it is found that the fretting fatigue strength decreases by about 80% as compared to the plain fatigue strength. Oblique cracks are observed in the initial stage of the fretting fatigue, in which damaged areas are found. These results can be used as the basic data for the structural integrity evaluation of corrosion-resisting alloys considering the fretting damages.

Recovery and recrystalization kinetics of cold-worked Zircaloy-4 plate and tubing (LWBR Development Program)

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

Katz, O.M.

1968-02-01

Empirical kinetic equations were derived to describe the recovery region between 550 and 1020/sup 0/F for times to 4000 hours for 15 to 78% cold-worked Zircaloy-4 plate and tubing. The properties studied were electrical resistivity and X-ray line sharpening. Recrystallization kinetics were described with sigmoidal curves derived from X-ray intensity and microhardness data. Light, replica, and transmission electron microscopy and selected-area electron diffraction were used to postulate recovery and recrystallization mechanisms. From a structural aspect, the annealing process in cold-worked Zircaloy-4 is visualized as a dislocation climb and annihilation process to the limit allowed by the size of the deformationmore » subcells, a reorientation of the subgrain material into a recrystallization texture, a growth of reoriented cells located in the most highly worked bands, and a consumption of less favorably strained and/or oriented cells by the high-angle boundaries of the reoriented cells. Comparison of 15 and 73% cold-worked tubing showed the activation energy to be less (21 versus 60 kcal/mol) and the subcell size greater (8000A versus 1000A) for the 15% cold-worked material. (NSA 22: 21698)« less

Azimuthally anisotropic hydride lens structures in Zircaloy 4 nuclear fuel cladding: High-resolution neutron radiography imaging and BISON finite element analysis

NASA Astrophysics Data System (ADS)

Lin, Jun-Li; Zhong, Weicheng; Bilheux, Hassina Z.; Heuser, Brent J.

2017-12-01

High-resolution neutron radiography has been used to image bulk circumferential hydride lens particles in unirradiated Zircaloy 4 tubing cross section specimens. Zircaloy 4 is a common light water nuclear reactor (LWR) fuel cladding; hydrogen pickup, hydride formation, and the concomitant effect on the mechanical response are important for LWR applications. Ring cross section specimens with three hydrogen concentrations (460, 950, and 2830 parts per million by weight) and an as-received reference specimen were imaged. Azimuthally anisotropic hydride lens particles were observed at 950 and 2830 wppm. The BISON finite element analysis nuclear fuel performance code was used to model the system elastic response induced by hydride volumetric dilatation. The compressive hoop stress within the lens structure becomes azimuthally anisotropic at high hydrogen concentrations or high hydride phase fraction. This compressive stress anisotropy matches the observed lens anisotropy, implicating the effect of stress on hydride formation as the cause of the observed lens azimuthal asymmetry. The cause and effect relation between compressive stress and hydride lens anisotropy represents an indirect validation of a key BISON output, the evolved hoop stress associated with hydride formation.

Physical and Mechanical Metallurgy of Zirconium Alloys for Nuclear Applications: A Multi-Scale Computational Study

NASA Astrophysics Data System (ADS)

Glazoff, Michael Vasily

In the post-Fukushima world, thermal and structural stability of materials under extreme conditions is an important issue for the safety of nuclear reactors. Because the nuclear industry will continue using zirconium (Zr) cladding for the foreseeable future, it becomes critical to gain a fundamental understanding of several interconnected problems. First, what are the thermodynamic and kinetic factors affecting oxidation and hydrogen pick-up by these materials at normal, off-normal conditions, and in long-term storage? Secondly, what protective coatings could be used in order to gain valuable time at off-normal conditions (temperature exceeds ~1200°C (2200°F)? Thirdly, the kinetics of the coating's oxidation must be understood. Lastly, one needs automated inspection algorithms allowing identifying cladding's defects. This work attempts to explore the problem from a computational perspective, utilizing first principles atomistic simulations, computational thermodynamics, plasticity theory, and morphological algorithms of image processing for defect identification. It consists of the four parts dealing with these four problem areas preceded by the introduction. In the 1st part, computational thermodynamics and ab initio calculations were used to shed light upon the different stages of zircaloy oxidation and hydrogen pickup, and microstructure optimization to increase thermal stability. The 2 nd part describes the kinetic theory of oxidation of the several materials considered to be perspective coatings for Zr alloys: SiC and ZrSiO4. The 3rd part deals with understanding the respective roles of the two different plasticity mechanisms in Zr nuclear alloys: twinning (at low T) and crystallographic slip (higher T's). For that goal, an advanced plasticity model was proposed. In the 4th part projectional algorithms for defect identification in zircaloy coatings are described. Conclusions and recommendations are presented in the 5th part. This integrative approach's value is in developing multi-faceted understanding of complex processes taking place in nuclear fuel rods. It helped identify several problems pertaining to the safe operations with nuclear fuel: limits of temperature that should be strictly obeyed in storage to retard zircaloy hydriding; understanding the benefits and limitations of coatings; developing in-depth understanding of Zr plasticity; developing original algorithms for defect identification in SiC-braided zircaloy. The obtained results will be useful for the nuclear industry.

Light-water-reactor safety research program. Quarterly progress report, July--September 1975

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

Not Available

1975-01-01

Progress is summarized in the following research and development areas: (1) loss-of-coolant accident research; heat transfer and fluid dynamics; (2) transient fuel response and fission-product release; and (3) mechanical properties of Zircaloy containing oxygen. Also included is an appendix on Kinetics of Fission Gas and Volatile Fission-product Behavior under Transient Conditions in LWR Fuel.

Fundamental metallurgical aspects of axial splitting in zircaloy cladding

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

Chung, H. M.

Fundamental metallurgical aspects of axial splitting in irradiated Zircaloy cladding have been investigated by microstructural characterization and analytical modeling, with emphasis on application of the results to understand high-burnup fuel failure under RIA situations. Optical microscopy, SEM, and TEM were conducted on BWR and PWR fuel cladding tubes that were irradiated to fluence levels of 3.3 x 10{sup 21} n cm{sup {minus}2} to 5.9 x 10{sup 21} n cm{sup {minus}2} (E > 1 MeV) and tested in hot cell at 292--325 C in Ar. The morphology, distribution, and habit planes of macroscopic and microscopic hydrides in as-irradiated and posttest claddingmore » were determined by stereo-TEM. The type and magnitude of the residual stress produced in association with oxide-layer growth and dense hydride precipitation, and several synergistic factors that strongly influence axial-splitting behavior were analyzed. The results of the microstructural characterization and stress analyses were then correlated with axial-splitting behavior of high-burnup PWR cladding reported for simulated-RIA conditions. The effects of key test procedures and their implications for the interpretation of RIA test results are discussed.« less

Research and Engineering Operation, Irradiation Processing Department monthly record report, May 1965

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

Ambrose, T.W.

1965-06-04

Process and development activities reported include: depleted uranium irradiations, thoria irradiation, and hot die sizing. Reactor engineering activities include: brittle fracture of 190-C tanks, increased graphite temperature limits for the F reactor, VSR channel caulking, K reactor downcomer flow, zircaloy hydriding, and ribbed zircaloy process tubes. Reactor physics activities include: thoria irradiations, E-D irradiations, boiling protection with the high speed scanner, and in-core flux monitoring. Radiological engineering activities include: radiation control, classification, radiation occurrences, effluent activity data, and well car shielding. Process standards are listed, along with audits, and fuel failure experience. Operational physics and process physics studies are presented.more » Lastly, testing activities are detailed.« less

Cladding burst behavior of Fe-based alloys under LOCA

DOE PAGES

Terrani, Kurt A.; Dryepondt, Sebastien N.; Pint, Bruce A.; ...

2015-12-17

Burst behavior of austenitic and ferritic Fe-based alloy tubes has been examined under a simulated large break loss of coolant accident. Specifically, type 304 stainless steel (304SS) and oxidation resistant FeCrAl tubes were studied alongside Zircaloy-2 and Zircaloy-4 that are considered reference fuel cladding materials. Following the burst test, characterization of the cladding materials was carried out to gain insights regarding the integral burst behavior. Given the widespread availability of a comprehensive set of thermo-mechanical data at elevated temperatures for 304SS, a modeling framework was implemented to simulate the various processes that affect burst behavior in this Fe-based alloy. Themore » most important conclusion is that cladding ballooning due to creep is negligible for Fe-based alloys. Thus, unlike Zr-based alloys, cladding cross-sectional area remains largely unchanged up to the point of burst. Furthermore, for a given rod internal pressure, the temperature onset of burst in Fe-based alloys appears to be simply a function of the alloy's ultimate tensile strength, particularly at high rod internal pressures.« less

Possible consequences of operation with KIVN fuel elements in K Zircaloy process tubes

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

Carlson, P.A.

1963-08-06

From considerations of the results of experimental simulations of non-axial placement of fuel elements in process tubes and in-reactor experience, it is concluded that the ultimate outcome of a charging error which results in operation with one or more unsupported fuel elements in a K Zircaloy-2 process tube would be multiple fuel failure and failure of the process tube. The outcome of the accident is determined by the speed with which the fuel failure is detected and the reactor is shut down. The release of fission products would be expected to be no greater than that which has occurred followingmore » severe fuel failure incidents. The highest probability for fission product release occurs during the discharge of failed fuel elements, when a small fraction of the exposed uranium of the fuel element may be oxidized when exposed to air before the element falls into the water-filled discharge chute. The confinement and fog spray facilities were installed to reduce the amount of fission products which might escape from the reactor building after such an event.« less

Light-Water-Reactor safety research program. Quarterly progress report, January--March 1977

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

None

The report summarizes the Argonne National Laboratory work performed during January, February, and March 1977 on water-reactor-safety problems. The following research and development areas are covered: (1) loss-of-coolant accident research: heat transfer and fluid dynamics; (2) transient fuel response and fission-product release program; (3) mechanical properties of zircaloy containing oxygen; and (4) steam-explosion studies.

Characterization of deformation mechanisms in zirconium alloys: effect of temperature and irradiation

NASA Astrophysics Data System (ADS)

Long, Fei

Zirconium alloys have been widely used in the CANDU (CANada Deuterium Uranium) reactor as core structural materials. Alloy such as Zircaloy-2 has been used for calandria tubes; fuel cladding; the pressure tube is manufactured from alloy Zr-2.5Nb. During in-reactor service, these alloys are exposed to a high flux of fast neutron at elevated temperatures. It is important to understand the effect of temperature and irradiation on the deformation mechanism of zirconium alloys. Aiming to provide experimental guidance for future modeling predictions on the properties of zirconium alloys this thesis describes the result of an investigation of the change of slip and twinning modes in Zircaloy-2 and Zr-2.5Nb as a function of temperature and irradiation. The aim is to provide scientific fundamentals and experimental evidences for future industry modeling in processing technique design, and in-reactor property change prediction of zirconium components. In situ neutron diffraction mechanical tests carried out on alloy Zircaloy-2 at three temperatures: 100¢ªC, 300¢ªC, and 500¢ªC, and described in Chapter 3. The evolution of the lattice strain of individual grain families in the loading and Poisson's directions during deformation, which probes the operation of slip and twinning modes at different stress levels, are described. By using the same type of in situ neutron diffraction technique, tests on Zr-2.5Nb pressure tube material samples, in either the fast-neutron irradiated or un-irradiated condition, are reported in Chapter 4. In Chapter 5, the measurement of dislocation density by means of line profile analysis of neutron diffraction patterns, as well as TEM observations of the dislocation microstructural evolution, is described. In Chapter 6 a hot-rolled Zr-2.5Nb with a larger grain size compared with the pressure tubing was used to study the development of dislocation microstructures with increasing plastic strain. In Chapter 7, in situ loading of heavy ion irradiated hot-rolled Zr-2.5Nb alloy is described, providing evidence for the interaction between moving dislocations and irradiation induced loops. Chapter 8 gives the effect on the dislocation structure of different levels of compressive strains along two directions in the hot-rolled Zr-2.5Nb alloy. By using high resolution neutron diffraction and TEM observations, the evolution of type and dislocation densities, as well as changes of dislocation microstructure with plastic strain were characterized.

Fuel Performance Calculations for FeCrAl Cladding in BWRs

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

George, Nathan; Sweet, Ryan; Maldonado, G. Ivan

2015-01-01

This study expands upon previous neutronics analyses of the reactivity impact of alternate cladding concepts in boiling water reactor (BWR) cores and directs focus toward contrasting fuel performance characteristics of FeCrAl cladding against those of traditional Zircaloy. Using neutronics results from a modern version of the 3D nodal simulator NESTLE, linear power histories were generated and supplied to the BISON-CASL code for fuel performance evaluations. BISON-CASL (formerly Peregrine) expands on material libraries implemented in the BISON fuel performance code and the MOOSE framework by providing proprietary material data. By creating material libraries for Zircaloy and FeCrAl cladding, the thermomechanical behaviormore » of the fuel rod (e.g., strains, centerline fuel temperature, and time to gap closure) were investigated and contrasted.« less

Thermal hydraulic design and decay heat removal of a solid target for a spallation neutron source

NASA Astrophysics Data System (ADS)

Takenaka, N.; Nio, D.; Kiyanagi, Y.; Mishima, K.; Kawai, M.; Furusaka, M.

2005-08-01

Thermal hydraulic design and thermal stress calculations were conducted for a water-cooled solid target irradiated by a MW-class proton beam for a spallation neutron source. Plate type and rod bundle type targets were examined. The thickness of the plate and the diameter of the rod were determined based on the maximum and the wall surface temperature. The thermal stress distributions were calculated by a finite element method (FEM). The neutronics performance of the target is roughly proportional to its average density. The averaged densities of the designed targets were calculated for tungsten plates, tantalum clad tungsten plates, tungsten rods sheathed by tantalum and Zircaloy and they were compared with mercury density. It was shown that the averaged density was highest for the tungsten plates and was high for the tantalum cladding tungsten plates, the tungsten rods sheathed by tantalum and Zircaloy in order. They were higher than or equal to that of mercury for the 1 2 MW proton beams. Tungsten target without the cladding or the sheath is not practical due to corrosion by water under irradiation condition. Therefore, the tantalum cladding tungsten plate already made successfully by HIP and the sheathed tungsten rod are the candidate of high performance solid targets. The decay heat of each target was calculated. It was low enough low compared to that of ISIS for the target without tantalum but was about four times as high as that of ISIS when the thickness of the tantalum cladding was 0.5 mm. Heat removal methods of the decay heat with tantalum were examined. It was shown that a special cooling system was required for the target exchange when tantalum was used for the target. It was concluded that the tungsten rod target sheathed with stainless steel or Zircaloy was the most reliable from the safety considerations and had similar neutronics performance to that of mercury.

Pourbaix Diagrams at Elevated Temperatures A Study of Zinc and Tin

NASA Astrophysics Data System (ADS)

Palazhchenko, Olga

Metals in industrial settings such as power plants are often subjected to high temperature and pressure aqueous environments, where failure to control corrosion compromises worker and environment safety. For instance, zircaloy (1.2-1.7 wt.% Sn) fuel rods are exposed to aqueous 250-310 °C coolant in CANDU reactors. The Pourbaix (EH-pH) diagram is a plot of electrochemical potential versus pH, which shows the domains of various metal species and by inference, corrosion susceptibility. Elevated temperature data for tin +II and tin +IV species were obtained using solid-aqueous phase equilibria with the respective oxides, in a batch vessel with in-situ pH measurement. Solubilities, determined via spectroscopic techniques, were used to calculate equilibrium constants and the Gibbs energies of Sn complexes for E-pH diagram construction. The SnOH3+ and Sn(OH )-5 species were incorporated, for the first time, into the 298.15 K and 358.15 K diagrams, with novel Go values determined at 358.15 K. Key words: Pourbaix diagrams, EH-pH, elevated temperatures, solubility, equilibrium, metal oxides, hydrolysis, redox potential, pH, thermochemical data, tin, zinc, zircaloy, corrosion, passivity.

A study on the reaction of Zircaloy-4 tube with hydrogen/steam mixture

NASA Astrophysics Data System (ADS)

Lee, Ji-Min; Kook, Dong-Hak; Cho, Il-Je; Kim, Yong-Soo

2017-08-01

In order to fundamentally understand the secondary hydriding mechanism of zirconium alloy cladding, the reaction of commercial Zircaloy-4 tubes with hydrogen and steam mixture was studied using a thermo-gravimetric analyser with two variables, H2/H2O ratio and temperature. Phenomenological analysis revealed that in the steam starvation condition, i.e., when the H2/H2O ratio is greater than 104, hydriding is the dominant reaction and the weight gain increases linearly after a short incubation time. On the other hand, when the gas ratio is 5 × 102 or 103, both hydriding and oxidation reactions take place simultaneously, leading to three distinct regimes: primary hydriding, enhanced oxidation, and massive hydriding. Microstructural changes of oxide demonstrate that when the weight gain exceeds a certain critical value, massive hydriding takes place due to the significant localized crack development within the oxide, which possibly simulates the secondary hydriding failure in a defective fuel operation. This study reveals that the steam starvation condition above the critical H2/H2O ratio is only a necessary condition for the secondary hydriding failure and, as a sufficient condition, oxide needs to grow sufficiently to reach the critical thickness that produces substantial crack development. In other words, in a real defective fuel operation incident, the secondary failure is initiated only when both steam starvation and oxide degradation conditions are simultaneously met. Therefore, it is concluded that the indispensable time for the critical oxide growth primarily determines the triggering time of massive hydriding failure.

Nuclear Energy Advanced Modeling and Simulation (NEAMS) Accident Tolerant Fuels High Impact Problem: Coordinate Multiscale FeCrAl Modeling

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

Gamble, K. A.; Hales, J. D.; Zhang, Y.

Since the events at the Fukushima-Daiichi nuclear power plant in March 2011 significant research has unfolded at national laboratories, universities and other institutions into alternative materials that have potential enhanced ac- cident tolerance when compared to traditional UO2 fuel zircaloy clad fuel rods. One of the potential replacement claddings are iron-chromium-alunimum (FeCrAl) alloys due to their increased oxidation resistance [1–4] and higher strength [1, 2]. While the oxidation characteristics of FeCrAl are a benefit for accident tolerance, the thermal neu- tron absorption cross section of FeCrAl is about ten times that of Zircaloy. This neutronic penalty necessitates thinner cladding. Thismore » allows for slightly larger pellets to give the same cold gap width in the rod. However, the slight increase in pellet diameter is not sufficient to compensate for the neutronic penalty and enriching the fuel beyond the current 5% limit appears to be necessary [5]. Current estimates indicate that this neutronic penalty will impose an increase in fuel cost of 15-35% [1, 2]. In addition to the neutronic disadvantage, it is anticipated that tritium release to the coolant will be larger because the permeability of hydrogen in FeCrAl is about 100 times higher than in Zircaloy [6]. Also, radiation-induced hardening and embrittlement of FeCrAl need to be fully characterized experimentally [7]. Due to the aggressive development schedule for inserting some of the potential materials into lead test assemblies or rods by 2022 [8] multiscale multiphysics modeling approaches have been used to provide insight into these the use of FeCrAl as a cladding material. The purpose of this letter report is to highlight the multiscale modeling effort for iron-chromium-alunimum (FeCrAl) cladding alloys as part of the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program through its Accident Tolerant Fuel (ATF) High Impact Problem (HIP). The approach taken throughout the HIP is to utilize lower length scale approaches (e.g., density functional theory, cluster dynamics, rate theory, phase field, and Visco-Plastic- Self-Consistent (VPSC)) to develop more physically informed models at the engineering scale for use in the BISON [9] fuel performance code.« less

Physical properties of molten core materials: Zr-Ni and Zr-Cr alloys measured by electrostatic levitation

NASA Astrophysics Data System (ADS)

Ohishi, Yuji; Kondo, Toshiki; Ishikawa, Takehiko; Okada, Junpei T.; Watanabe, Yuki; Muta, Hiroaki; Kurosaki, Ken; Yamanaka, Shinsuke

2017-03-01

It is important to understand the behaviors of molten core materials to investigate the progression of a core meltdown accident. In the early stages of bundle degradation, low-melting-temperature liquid phases are expected to form via the eutectic reaction between Zircaloy and stainless steel. The main component of Zircaloy is Zr and those of stainless steel are Fe, Ni, and Cr. Our group has previously reported physical property data such as viscosity, density, and surface tension for Zr-Fe liquid alloys using an electrostatic levitation technique. In this study, we report the viscosity, density, and surface tension of Zr-Ni and Zr-Cr liquid alloys (Zr1-xNix (x = 0.12 and 0.24) and Zr0.77Cr0.23) using the electrostatic levitation technique.

Characterization of LWRS Hybrid SiC-CMC-Zircaloy-4 Fuel Cladding after Gamma Irradiation

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

Isabella J van Rooyen

2012-09-01

The purpose of the gamma irradiation tests conducted at the Idaho National Laboratory (INL) was to obtain a better understanding of chemical interactions and potential changes in microstructural properties of a mock-up hybrid nuclear fuel cladding rodlet design (unfueled) in a simulated PWR water environment under irradiation conditions. The hybrid fuel rodlet design is being investigated under the Light Water Reactor Sustainability (LWRS) program for further development and testing of one of the possible advanced LWR nuclear fuel cladding designs. The gamma irradiation tests were performed in preparation for neutron irradiation tests planned for a silicon carbide (SiC) ceramic matrixmore » composite (CMC) zircaloy-4 (Zr-4) hybrid fuel rodlet that may be tested in the INL Advanced Test Reactor (ATR) if the design is selected for further development and testing« less

Effect of Isothermal Hold on the Microstructural Evolution of the Stainless Steel 304L/Zircaloy-4 Interface

NASA Astrophysics Data System (ADS)

Lebaili, A.; Taouinet, M.; Nibou, D.; Lebaili, S.; Hodaj, F.

2017-07-01

The transition from solid-state bonding of the stainless steel 304L/Zircaloy-4 diffusion couple to a partial liquid-phase bonding is important for the bonding process at temperatures ranging from 950 to 1050 °C. In this study, the temperature at which a melting process occurs at the interface after 45 min of isothermal holdings is determined experimentally. This melting process leads to a drastic change in the thickness of the reaction products zone (RPZ) as well as on its microstructure. Diffusion couples were characterized by SEM-EDS, and quantitative chemical analyses of different phases are performed by EPMA. The RPZ consists of three layers: the (α-Fe-Cr) phase layer and two layers consisting of Zr(Fe,Cr)2 (ɛ), Zr2(Fe,Ni) and (α-Zr) phases. The thickness of these layers strongly depends on the holding temperature. The analysis allowed the description of the physicochemical phenomena occurring during isothermal holding as well as during cooling. The solidification paths are determined at 1000, 1020 and 1050 °C. Hardness tests are performed on the bonded samples in order to qualify the mechanical properties of different phases of the RPZ. This study leads to a better understanding of the complex phenomena intervening in the joining process which is very useful for applications in industrial scale.

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

Lombardo, N.J.; Marseille, T.J.; White, M.D.

TRUMP-BD (Boil Down) is an extension of the TRUMP (Edwards 1972) computer program for the analysis of nuclear fuel assemblies under severe accident conditions. This extension allows prediction of the heat transfer rates, metal-water oxidation rates, fission product release rates, steam generation and consumption rates, and temperature distributions for nuclear fuel assemblies under core uncovery conditions. The heat transfer processes include conduction in solid structures, convection across fluid-solid boundaries, and radiation between interacting surfaces. Metal-water reaction kinetics are modeled with empirical relationships to predict the oxidation rates of steam-exposed Zircaloy and uranium metal. The metal-water oxidation models are parabolic inmore » form with an Arrhenius temperature dependence. Uranium oxidation begins when fuel cladding failure occurs; Zircaloy oxidation occurs continuously at temperatures above 13000{degree}F when metal and steam are available. From the metal-water reactions, the hydrogen generation rate, total hydrogen release, and temporal and spatial distribution of oxide formations are computed. Consumption of steam from the oxidation reactions and the effect of hydrogen on the coolant properties is modeled for independent coolant flow channels. Fission product release from exposed uranium metal Zircaloy-clad fuel is modeled using empirical time and temperature relationships that consider the release to be subject to oxidation and volitization/diffusion ( bake-out'') release mechanisms. Release of the volatile species of iodine (I), tellurium (Te), cesium (Ce), ruthenium (Ru), strontium (Sr), zirconium (Zr), cerium (Cr), and barium (Ba) from uranium metal fuel may be modeled.« less

METALLURGY OF ZIRCALOY-2. PART II. THE EFFECTS OF FABRICATION VARIABLES ON THE PREFERRED ORIENTATION AND ANISOTROPY OF STRAIN BEHAVIOR

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

Rittenhouse, P.L.; Picklesimer, M.L.

1961-02-01

The preferred orientation and anisotropy of strain behavior of Zircaloy- 2 were studied as functions of fabrication variables. An inverse-pole-figure technique was used for the preferred orientation determinations. Evaluation of the effects of the fabrication variables on the anisotropy of strain behavior was accomplished by a contractile strainaxial strain analysis. An analysis of strain behavior in the normal direction was developed on the basis of theory of plastic flow of anisotropic metals. A simple intuitively derivable relation was found to exist between the strainstrain analysis and the preferred orientation data. Correlations of the strain-strain data with true-stress-truestrain diagrams and mechanicalmore » properties were attempted. The preferred orientation of Zircaloy-2 produced by the Oak Ridge National Laboratory-Homogeneous Reactor Project (ORNL- HRP) metallurgy fabrication schedule (ingot breakdown at 1500 to 1900 deg F, major reduction at 1800 to 1900 deg F or 1350 to 1450 deg F, a heat treatment of 30 min at 1800 at 1550 deg F followed by a water quench or rapid air cool to below 1200 deg F, a final reduction of 25 to 40% at 1000 deg F. and a 3O-min anneal at 1400 to 1425 deg F) was weak compared to that of most of the other schedules investigated. Elimination of the beta heat treatment (1800 to 1850 deg F for 30 min) between the major reduction and final reduction steps resulted in a material with a high degree of preferred orienation and with a state of pseudoisotropy in ihe rolling plane. A unique and quite high degree of preferred orientaion was developed when the ORNL-HRP metallurgy fabrication procedure was used, but the ingot axis was in the transverse rather than the rolling direction of the finished plate permitting more contractile sirain to occur in the normal direction than in either the rolling or transverse directions. The strain-strain analyses of the materials were consistent with the conclusions reached by the preferred orientation analyses. The effects of cross rolling on the anisotropy of strain behavior of Zircaloy-2 were found to depend on the type of cross rolling (unidirectional or rotational), the temperature of cross rolling, and the stage of fabrication at which the cross rolling was done. Unidirectional cross rolling at 1000 deg F after beta heat treatment caused only a slight increase in anisotropy of strain behavior over that for straight-rolled material, but roiational cross rolling at 1000 deg F after beta heat treatment resulted in a material with a state of isotropy of strain behavior only in the rolling plane. Rotational cross rolling before beta heat treatment, for one material at 1450 deg F and for another from 1900 deg F, produced different states or degrees of anisotropy of strain behavior. Because of flow constraints which exist in sheettype tensile specimens with width-to-thickness ratios > 1.0, it is imperative that round tensile specimens be used in the contractile strain-axial strain analysis. Since the principal axes of anisotropy are generally not the major sheet directions, they must be found by the preferred orientation analysis. (auth)« less

In situ synchrotron X-ray diffraction study of hydrides in Zircaloy-4 during thermomechanical cycling

DOE PAGES

Cinbiz, Mahmut N.; Koss, Donald A.; Motta, Arthur T.; ...

2017-02-20

The d-spacing evolution of both in-plane and out-of-plane hydrides has been studied using in situ synchrotron radiation X-ray diffraction during thermo-mechanical cycling of cold-worked stress-relieved Zircaloy-4. The structure of the hydride precipitates is such that the δ{111} d-spacing of the planes aligned with the hydride platelet face is greater than the d-spacing of the 111 planes aligned with the platelet edges. Upon heating from room temperature, the δ{111} planes aligned with hydride plate edges exhibit bi-linear thermally-induced expansion. In contrast, the d-spacing of the (111) plane aligned with the hydride plate face initially contracts upon heating. Furthermore, these experimental resultsmore » can be understood in terms of a reversal of stress state associated with precipitating or dissolving hydride platelets within the α-zirconium matrix.« less

Intergrannular strain evolution in a zircaloy-4 alloy with Widmanstatten microstructure

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

Clausen, Bjorn; Vogel, Sven C; Garlea, Eena

2009-01-01

A Zircaloy-4 alloy with Widmanstatten-Basketweave microstructure and random texture has been used to study the deformation systems responsible for the polycrystalline plasticity at the grain level. The evolution of internal strain and bulk texture is investigated using neutron diffraction and an elasto-plastic self-consistent (EPSC) modeling scheme. The macroscopic stress-strain behavior and intergranular (hkil-specific) strain development, parallel and perpendicular to the loading direction, were measured in-situ during uniaxial tensile loading. Then, the EPSC model was employed to simulate the experimental results. This modeling scheme accounts for the thermal anisotropy; elastic-plastic properties of the constituent grains; and activation, reorientation, and stress relaxationmore » associated with twinning. The agreement between the experiment and the model will be discussed as well as the critical resolved shear stresses (CRSS) and the hardening coefficients obtained from the model.« less

Study of the mechanical behavior of the hydride blister/rim structure in Zircaloy-4 using in-situ synchrotron X-ray diffraction

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

Lin, Jun-li; Han, Xiaochun; Heuser, Brent J.

2016-04-01

High-energy synchrotron X-ray diffraction was utilized to study the mechanical response of the f.c.c delta hydride phase, the intermetallic precipitation with hexagonal C14 lave phase and the alpha-Zr phase in the Zircaloy-4 materials with a hydride rim/blister structure near one surface of the material during in-situ uniaxial tension experiment at 200 degrees C. The f.c.c delta was the only hydride phase observed in the rim/blister structure. The conventional Rietveld refinement was applied to measure the macro-strain equivalent response of the three phases. Two regions were delineated in the applied load versus lattice strain measurement: a linear elastic strain region andmore » region that exhibited load partitioning. Load partitioning was quantified by von Mises analysis. The three phases were observed to have similar elastic modulus at 200 degrees C.« less

Analysis of hardening behavior of sheet metals by a new simple shear test method taking into account the Bauschinger effect

NASA Astrophysics Data System (ADS)

Bang, Sungsik; Rickhey, Felix; Kim, Minsoo; Lee, Hyungyil; Kim, Naksoo

2013-12-01

In this study we establish a process to predict hardening behavior considering the Bauschinger effect for zircaloy-4 sheets. When a metal is compressed after tension in forming, the yield strength decreases. For this reason, the Bauschinger effect should be considered in FE simulations of spring-back. We suggested a suitable specimen size and a method for determining the optimum tightening torque for simple shear tests. Shear stress-strain curves are obtained for five materials. We developed a method to convert the shear load-displacement curve to the effective stress-strain curve with FEA. We simulated the simple shear forward/reverse test using the combined isotropic/kinematic hardening model. We also investigated the change of the load-displacement curve by varying the hardening coefficients. We determined the hardening coefficients so that they follow the hardening behavior of zircaloy-4 in experiments.

Characterization of Hydrogen Embrittled Zircaloy-4 by Using a Van de Graaff Particle Accelerator

NASA Astrophysics Data System (ADS)

Budd, John

2013-04-01

On-site, dry cask storage was originally by the intended to be a short-term solution for holding spent nuclear fuel. Due to the lack of a permanent storage facility, the nuclear power industry seeks to assess the effective lifetime of the casks. One issue which could compromise cask integrity is Hydrogen embrittlement. This phenomenon occurs in the Zircaloy-4 fuel-rod cladding and is caused by the formation of Zirconium hydrides. Over time, thermal stresses caused by the heat from reactions of the stored nuclear fuel could result in significant breaches of the cladding. Our group at Texas A&M University- Kingsville is conducting experiments to aid in determining when such breaches will occur. We will irradiate samples of the alloy with protons of energies up to 400 keV using a Van de Graaff particle accelerator. Once irradiated, their properties will be characterized using scanning electron microscopy and Vickers hardness tests.

Safety margins in zircaloy oxidation and embrittlement criteria for emergency core cooling system acceptance

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

Williford, R.E.

1986-09-01

Current emergency core cooling system acceptance criteria for light water reactors specify that, under loss-of-coolant accident (LOCA) conditions, the Baker-Just (BJ) correlation must be used to calculate Zircaloy-steam oxidation, calculated peak cladding temperatures (PCT) must not exceed 1204/sup 0/C, and calculated oxidation must not exceed 17% equivalent cladding reacted (ECR). An appropriately defined minimum margin of safety was estimated for each of these criteria. The currently required BJ oxidation correlation provides margins only over the 1100 to 1500/sup 0/C temperature range at the 95% confidence level. The PCT margins for thermal shock and handling failures are adequate at oxidation temperaturesmore » above 1204/sup 0/C for up to 210 and 160 s, respectively, at the 95% confidence level. The ECR thermal shock and handling margins at the 50 and 95% confidence levels, respectively, range between 2 and 7% ECR for the BJ correlation, but vanish at temperatures above 1100 to 1160/sup 0/C for the best-estimate Cathcart-Pawel correlation. However, use of the Cathcart Pawel correlation for ''design basis'' LOCA calculations can be justified at the 85 to 88% confidence level if cooling rate effects can be neglected.« less

Recycle of Zirconium from Used Nuclear Fuel Cladding: A Major Element of Waste Reduction

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

Collins, Emory D; DelCul, Guillermo D; Terekhov, Dmitri

2011-01-01

Feasibility tests were initiated to determine if the zirconium in commercial used nuclear fuel (UNF) cladding can be recovered in sufficient purity to permit re-use, and if the recovery process can be operated economically. Initial tests are being performed with unirradiated, non-radioactive samples of various types of Zircaloy materials that are used in UNF cladding to develop the recovery process and determine the degree of purification that can be obtained. Early results indicate that quantitative recovery can be accomplished and product contamination with alloy constituents can be controlled sufficiently to meet purification requirements. Future tests with actual radioactive UNF claddingmore » are planned. The objective of current research is to determine the feasibility of recovery and recycle of zirconium from used fuel cladding wastes. Zircaloy cladding, which contains 98+% of hafnium-free zirconium, is the second largest mass, on average {approx}25 wt %, of the components in used U.S. light-water-reactor fuel assemblies. Therefore, recovery and recycle of the zirconium would enable a large reduction in geologic waste disposal for advanced fuel cycles. Current practice is to compact or grout the cladding waste and store it for subsequent disposal in a geologic repository. This paper describes results of initial tests being performed with unirradiated, non-radioactive samples of various types of Zircaloy materials that are used in UNF cladding to develop the recovery process and determine the degree of purification that can be obtained. Future tests with actual radioactive UNF cladding are planned.« less

Chemical and microstructural characterization of a 9 cycle Zircaloy-2 cladding using EPMA and FIB tomography

NASA Astrophysics Data System (ADS)

Baris, A.; Restani, R.; Grabherr, R.; Chiu, Y.-L.; Evans, H. E.; Ammon, K.; Limbäck, M.; Abolhassani, S.

2018-06-01

A high burn-up Zircaloy-2 cladding is characterised in order to correlate its microstructure and composition to the change of oxidation and hydrogen uptake behaviour during long term service in the reactor. After 9 cycle of service, the chemical analysis of the cladding segment shows that most secondary phase particles (SPPs) have dissolved into the matrix. Fe and Ni are distributed homogenously in the metal matrix. Cr-containing clusters, remnants of the original Zr(Fe, Cr)2 type precipitates, are still present. Hydrides are observed abundantly in the metal side close to the metal-oxide interface. These hydrides have lower Fe and Ni concentration than that in the metal matrix. The three-dimensional (3D) reconstruction of the oxide and the metal-oxide interface obtained by Focused Ion Beam (FIB) tomography shows how the oxide microstructure has evolved with the number of cycles. The composition and microstructural changes in the oxide and the metal can be correlated to the oxidation kinetics and the H-uptake. It is observed that there is an increase in the oxidation kinetics and in the H-uptake between the third and the fifth cycles, as well as during the last two cycles. At the same time the volume fraction of cracks in the oxide significantly increased. Many fine cracks and pores exist in the oxide formed in the last cycle. Furthermore, the EPMA results confirm that this oxide formed at the last cycle reflects the composition of the metal at the metal-oxide interface after the long residence time in the reactor.

Solid-phase zirconium and fluoride species in alkaline zircaloy cladding waste at Hanford.

PubMed

Reynolds, Jacob G; Huber, Heinz J; Cooke, Gary A; Pestovich, John A

2014-08-15

The United States Department of Energy Hanford Site, near Richland, Washington, USA, processed plutonium between 1944 and 1987. Fifty-six million gallons of waste of various origins remain, including waste from removing zircaloy fuel cladding using the so-called Zirflex process. The speciation of zirconium and fluoride in this waste is important because of the corrosivity and reactivity of fluoride as well as the (potentially) high density of Zr-phases. This study evaluates the solid-phase speciation of zirconium and fluoride using X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). Two waste samples were analyzed: one waste sample that is relatively pure zirconium cladding waste from tank 241-AW-105 and another that is a blend of zirconium cladding wastes and other high-level wastes from tank 241-C-104. Villiaumite (NaF) was found to be the dominant fluoride species in the cladding waste and natrophosphate (Na7F[PO4]2 · 19H2O) was the dominant species in the blended waste. Most zirconium was present as a sub-micron amorphous Na-Zr-O phase in the cladding waste and a Na-Al-Zr-O phase in the blended waste. Some zirconium was present in both tanks as either rounded or elongated crystalline needles of Na-bearing ZrO2 that are up to 200 μm in length. These results provide waste process planners the speciation data needed to develop disposal processes for this waste. Copyright © 2014 Elsevier B.V. All rights reserved.

METHOD FOR ANNEALING AND ROLLING ZIRCONIUM-BASE ALLOYS

DOEpatents

Picklesimer, M.L.

1959-07-14

A fabrication procedure is presented for alpha-stabilized zirconium-base alloys, and in particular Zircaloy-2. The alloy is initially worked at a temperature outside the alpha-plus-beta range (810 to 970 deg ), held at a temperature above 970 deg C for 30 minutes and cooled rapidly. The alloy is then cold-worked to reduce the size at least 20% and annealed at a temperature from 700 to 810 deg C. This procedure serves both to prevent the formation of stringers and to provide a randomly oriented crystal structure.

Understanding thermally activated plastic deformation behavior of Zircaloy-4

NASA Astrophysics Data System (ADS)

Kumar, N.; Alomari, A.; Murty, K. L.

2018-06-01

Understanding micromechanics of plastic deformation of existing materials is essential for improving their properties further and/or developing advanced materials for much more severe load bearing applications. The objective of the present work was to understand micromechanics of plastic deformation of Zircaloy-4, a zirconium-based alloy used as fuel cladding and channel (in BWRs) material in nuclear reactors. The Zircaloy-4 in recrystallized (at 973 K for 4 h) condition was subjected to uniaxial tensile testing at a constant cross-head velocity at temperatures in the range 293 K-1073 K and repeated stress relaxation tests at 293 K, 573 K, and 773 K. The minimum in the total elongation was indicative of dynamic strain aging phenomenon in this alloy in the intermediate temperature regime. The yield stress of the alloy was separated into effective and athermal components and the transition from thermally activated dislocation glide to athermal regime took place at around 673 K with the athermal stress estimated to be 115 MPa. The activation volume was found to be in the range of 40 b3 to 160 b3. The activation volume values and the data analyses using the solid-solution models in literature indicated dislocation-solute interaction to be a potential deformation mechanism in thermally activated regime. The activation energy calculated at 573 K was very close to that found for diffusivity of oxygen in α-Zr that was suggestive of dislocations-oxygen interaction during plastic deformation. This type of information may be helpful in alloy design in selecting different elements to control the deformation behavior of the material and impart desired mechanical properties in those materials for specific applications.

Fabrication and testing of U–7Mo monolithic plate fuel with Zircaloy cladding

DOE PAGES

Pasqualini, E. E.; Robinson, A. B.; Porter, D. L.; ...

2016-07-15

The Materials Management and Minimization program is developing fuel designs to replace highly enriched fuel with fuels of low enrichment. In the most challenging cases, U–(7–10wt%)Mo monolithic plate fuel are proposed. The chosen design includes aluminum-alloy cladding, which provides some challenges in fabrication and fuel/cladding interaction in service. We investigated zircaloy cladding, specifically Zry–4as an alternative cladding, and development of a fabrication method was performed by researchers with the Comisión Nacionalde Energia Atómica (CNEA) in Argentina, resulting in test fuel plates (Zry–4 clad U–7Mo) which were subsequently tested in the Advanced Test Reactor in Idaho. Because Zry–4 and U–(7–10)Mo havemore » similar high-temperature mechanical properties, fabrication was simplified in that the fuel foil and cladding could be co-rolled and bonded. The challenge was to prevent a thermal-expansion mismatch which could destroy the fuel/cladding bond before complete bonding was achieved; the solution was to prevent the composites from cooling significantly between roll passes. Our final product performed very well in-reactor, showing good bonding, very little fuel/cladding interaction, either from fabrication or in-reactor testing, and little swelling, especially no detectable heterogeneous bubble formation at the fuel/cladding interface tested to a fission density of up to 2.54E+21« less

Fabrication and testing of U–7Mo monolithic plate fuel with Zircaloy cladding

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

Pasqualini, E. E.; Robinson, A. B.; Porter, D. L.

The Materials Management and Minimization program is developing fuel designs to replace highly enriched fuel with fuels of low enrichment. In the most challenging cases, U–(7–10wt%)Mo monolithic plate fuel are proposed. The chosen design includes aluminum-alloy cladding, which provides some challenges in fabrication and fuel/cladding interaction in service. We investigated zircaloy cladding, specifically Zry–4as an alternative cladding, and development of a fabrication method was performed by researchers with the Comisión Nacionalde Energia Atómica (CNEA) in Argentina, resulting in test fuel plates (Zry–4 clad U–7Mo) which were subsequently tested in the Advanced Test Reactor in Idaho. Because Zry–4 and U–(7–10)Mo havemore » similar high-temperature mechanical properties, fabrication was simplified in that the fuel foil and cladding could be co-rolled and bonded. The challenge was to prevent a thermal-expansion mismatch which could destroy the fuel/cladding bond before complete bonding was achieved; the solution was to prevent the composites from cooling significantly between roll passes. Our final product performed very well in-reactor, showing good bonding, very little fuel/cladding interaction, either from fabrication or in-reactor testing, and little swelling, especially no detectable heterogeneous bubble formation at the fuel/cladding interface tested to a fission density of up to 2.54E+21« less

Multispectral pyrometry for surface temperature measurement of oxidized Zircaloy claddings

NASA Astrophysics Data System (ADS)

Bouvry, B.; Cheymol, G.; Ramiandrisoa, L.; Javaudin, B.; Gallou, C.; Maskrot, H.; Horny, N.; Duvaut, T.; Destouches, C.; Ferry, L.; Gonnier, C.

2017-06-01

Non-contact temperature measurement in a nuclear reactor is still a huge challenge because of the numerous constraints to consider, such as the high temperature, the steam atmosphere, and irradiation. A device is currently developed at CEA to study the nuclear fuel claddings behavior during a Loss-of-Coolant Accident. As a first step of development, we designed and tested an optical pyrometry procedure to measure the surface temperature of nuclear fuel claddings without any contact, under air, in the temperature range 700-850 °C. The temperature of Zircaloy-4 cladding samples was retrieved at various temperature levels. We used Multispectral Radiation Thermometry with the hypothesis of a constant emissivity profile in the spectral ranges 1-1.3 μm and 1.45-1.6 μm. To allow for comparisons, a reference temperature was provided by a thermocouple welded on the cladding surface. Because of thermal losses induced by the presence of the thermocouple, a heat transfer simulation was also performed to estimate the bias. We found a good agreement between the pyrometry measurement and the temperature reference, validating the constant emissivity profile hypothesis used in the MRT estimation. The expanded measurement uncertainty (k = 2) of the temperature obtained by the pyrometry method was ±4 °C, for temperatures between 700 and 850 °C. Emissivity values, between 0.86 and 0.91 were obtained.

An elasto-plastic fracture mechanics based model for assessment of hydride embrittlement in zircaloy cladding tubes

NASA Astrophysics Data System (ADS)

Nilsson, Karl-Fredrik; Jakšić, Nikola; Vokál, Vratko

2010-01-01

This paper describes a finite element based fracture mechanics model to assess how hydrides affect the integrity of zircaloy cladding tubes. The hydrides are assumed to fracture at a low load whereas the propagation of the fractured hydrides in the matrix material and failure of the tube is controlled by non-linear fracture mechanics and plastic collapse of the ligaments between the hydrides. The paper quantifies the relative importance of hydride geometrical parameters such as size, orientation and location of individual hydrides and interaction between adjacent hydrides. The paper also presents analyses for some different and representative multi-hydride configurations. The model is adaptable to general and complex crack configurations and can therefore be used to assess realistic hydride configurations. The mechanism of cladding failure is by plastic collapse of ligaments between interacting fractured hydrides. The results show that the integrity can be drastically reduced when several radial hydrides form continuous patterns.

Hydrogen motion in Zircaloy-4 cladding during a LOCA transient

NASA Astrophysics Data System (ADS)

Elodie, T.; Jean, D.; Séverine, G.; M-Christine, B.; Michel, C.; Berger, P.; Martine, B.; Antoine, A.

2016-04-01

Hydrogen and oxygen are key elements influencing the embrittlement of zirconium-based nuclear fuel cladding during the quench phase following a Loss Of Coolant Accident (LOCA). The understanding of the mechanisms influencing the motion of these two chemical elements in the metal is required to fully describe the material embrittlement. High temperature steam oxidation tests were performed on pre-hydrided Zircaloy-4 samples with hydrogen contents ranging between 11 and 400 wppm prior to LOCA transient. Thanks to the use of both Electron Probe Micro-Analysis (EPMA) and Elastic Recoil Detection Analysis (μ-ERDA), the chemical elements partitioning has been systematically quantified inside the prior-β phase. Image analysis and metallographic examinations were combined to provide an average oxygen profile as well as hydrogen profile within the cladding thickness after LOCA transient. The measured hydrogen profile is far from homogeneous. Experimental distributions are compared to those predicted numerically using calculations derived from a finite difference thermo-diffusion code (DIFFOX) developed at IRSN.

Investigation of morphological, structural, and mechanical characteristics of Zircaloy-4 irradiated with 3.5 MeV hydrogen ions beam

NASA Astrophysics Data System (ADS)

Rafique, Mohsin; Butt, M. Z.; Ahmad, Sajjad

2017-09-01

Zircaloy-4 specimens were irradiated with 3.5 MeV hydrogen ions (dose range: 1  ×  1013 H+1 cm-2 to 1  ×  1015 H+1 cm-2) using a Pelletron accelerator. FESEM studies reveal formation of hydrogen micro-bubbles, bubbles induced blisters of irregular shapes, and development of cracks on the specimen surface, as in the case of pure zirconium. However, for the highest irradiation dose of 1  ×  1015 H+1 cm-2, agglomeration of flower-shape blisters is observed. XRD analysis shows that the most preferentially oriented crystallographic plane is (0 0 4) with texture coefficient values 1.832-2.308 depending on the ions dose. Its diffraction peak intensity first decreases with the increase in ions dose up to 5  ×  1013 H+1 cm-2 and later increases up to 1  ×  1015 H+1 cm-2. Opposite is found in case of diffraction peak width. Crystallite size and lattice strain determined by Williamson-Hall analysis display a linear relationship between the two with positive slope. Mechanical strength, namely yield stress (YS), ultimate tensile strength (UTS), and fracture stress (FS), increases sharply with ions dose up to 5  ×  1013 H+1 cm-2. For 1  ×  1014 H+1 cm-2 dose there is a sudden drop of stress to a lowest value and then a slow steady increase in stress up to the highest dose 1  ×  1015 H+1 cm-2. Same pattern is followed by uniform elongation and total elongation. All three stress parameters YS, UTS, and FS follow Inverse Hall-Petch relation.

Microstructural Modeling of Dynamic Intergranular and Transgranular Fracture Modes in Zircaloys

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

Mohammed, I.; Zikry, M.A.; Ziaei, S.

2017-04-01

In this time period, we have continued to focus on (i) refining the thermo-mechanical fracture model for zirconium (Zr) alloys subjected to large deformations and high temperatures that accounts for the cracking of ZrH and ZrH2 hydrides, (ii) formulating a framework to account intergranular fracture due to iodine diffusion and pit formation in grain-boundaries (GBs). Our future objectives are focused on extending to a combined population of ZrH and ZrH2 populations and understanding how thermo-mechanical behavior affects hydride reorientation and cracking. We will also refine the intergranular failure mechanisms for grain boundaries with pits.

Neutronic analysis of candidate accident-tolerant cladding concepts in pressurized water reactors

DOE PAGES

George, Nathan Michael; Terrani, Kurt A.; Powers, Jeffrey J.; ...

2014-09-29

A study analyzed the neutronics of alternate cladding materials in a pressurized water reactor (PWR) environment. Austenitic type 310 (310SS) and 304 stainless steels, ferritic Fe-20Cr-5Al (FeCrAl) and APMT™ alloys, and silicon carbide (SiC)-based materials were considered and compared with Zircaloy-4. SCALE 6.1 was used to analyze the associated neutronics penalty/advantage, changes in reactivity coefficients, and spectral variations once a transition in the cladding was made. In the cases examined, materials containing higher absorbing isotopes invoked a reduction in reactivity due to an increase in neutron absorption in the cladding. Higher absorbing materials produced a harder neutron spectrum in themore » fuel pellet, leading to a slight increase in plutonium production. A parametric study determined the geometric conditions required to match cycle length requirements for each alternate cladding material in a PWR. A method for estimating the end of cycle reactivity was implemented to compare each model to that of standard Zircaloy-4 cladding. By using a thinner cladding of 350 μm and keeping a constant outer diameter, austenitic stainless steels require an increase of no more than 0.5 wt% enriched 235U to match fuel cycle requirements, while the required increase for FeCrAl was about 0.1%. When modeling SiC (with slightly lower thermal absorption properties than that of Zircaloy), a standard cladding thickness could be implemented with marginally less enriched uranium (~0.1%). Moderator temperature and void coefficients were calculated throughout the depletion cycle. Nearly identical reactivity responses were found when coolant temperature and void properties were perturbed for each cladding material. By splitting the pellet into 10 equal areal sections, relative fission power as a function of radius was found to be similar for each cladding material. FeCrAl and 310SS cladding have a slightly higher fission power near the pellet’s periphery due to the harder neutron spectrum in the system, causing more 239Pu breeding. An economic assessment calculated the change in fuel pellet production costs for use of each cladding. Furthermore, implementing FeCrAl alloys would increase fuel pellet production costs about 15% because of increased 235U enrichment and the additional UO 2 pellet volume enabled by using thinner cladding.« less

Engineered Zircaloy Cladding Modifications for Improved Accident Tolerance of LWR Nuclear Fuel

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

Heuser, Brent; Stubbins, James; Kozlowski, Tomasz

The DOE NEUP sponsored IRP on accident tolerant fuel (ATF) entitled Engineered Zircaloy Cladding Modifications for Improved Accident Tolerance of LWR Nuclear Fuel involved three academic institutions, Idaho National Laboratory (INL), and ATI Materials (ATI). Detailed descriptions of the work at the University of Illinois (UIUC, prime), the University of Florida (UF), the University of Michigan (UMich), and INL are included in this document as separate sections. This summary provides a synopsis of the work performed across the IRP team. Two ATF solution pathways were initially proposed, coatings on monolithic Zr-based LWR cladding material and selfhealing modifications of Zr-based alloys.more » The coating pathway was extensively investigated, both experimentally and in computations. Experimental activities related to ATF coatings were centered at UIUC, UF, and UMich and involved coating development and testing, and ion irradiation. Neutronic and thermal hydraulic aspects of ATF coatings were the focus of computational work at UIUC and UMich, while materials science aspects were the focus of computational work at UF and INL. ATI provided monolithic Zircaloy 2 and 4 material and a binary Zr-Y alloy material. The selfhealing pathway was investigated with advanced computations only. Beryllium was identified as a valid self-healing additive early in this work. However, all attempts to fabricate a Zr-Be alloy failed. Several avenues of fabrication were explored. ATI ultimately declined our fabrication request over health concerns associated with Be (we note that Be was not part of the original work scope and the ATI SOW). Likewise, Ames Laboratory declined our fabrication request, citing known litigation dating to the 1980s and 1990s involving the U.S. Federal government and U.S. National Laboratory employees involving the use of Be. Materion (formerly, Brush Wellman) also declined our fabrication request, citing the difficulty in working with a highly reactive Zr and Be. International fabrication options were explored in Europe and Asia, but this proved to be impractical, if not impossible. Consequently, experimental investigation of the Zr-Be binary system was dropped and exploration binary Zr-Y binary system was initiated. The motivation behind the Zr-Y system is the known thermodynamic stability of yttria over zirconia.« less

Fabrication and testing of U-7Mo monolithic plate fuel with Zircaloy cladding

NASA Astrophysics Data System (ADS)

Pasqualini, E. E.; Robinson, A. B.; Porter, D. L.; Wachs, D. M.; Finlay, M. R.

2016-10-01

Nuclear fuel designs are being developed to replace highly enriched fuel used in research and test reactors with fuels of low enrichment. In the most challenging cases, U-(7-10 wt%)Mo monolithic plate fuels are proposed. One of the considered designs includes aluminum-alloy cladding, which provides some challenges in fabrication and fuel/cladding interaction during service. Zircaloy cladding, specifically Zry-4, was investigated as an alternative cladding, and development of a fabrication method was performed by researchers with the Comisión Nacionalde Energia Atómica (CNEA) in Argentina, resulting in test fuel plates (Zry-4 clad U-7Mo) which were subsequently tested in the Advanced Test Reactor in Idaho. Because Zry-4 and U-(7-10)Mo have similar high-temperature mechanical properties, fabrication was simplified in that the fuel foil and cladding could be co-rolled and bonded. The challenge was to prevent a thermal-expansion mismatch, which could destroy the fuel/cladding bond before complete bonding was achieved; the solution was to prevent the composites from cooling significantly during or between roll passes. The final product performed very well in-reactor, showing good bonding, very little fuel/cladding interaction-either from fabrication or in-reactor testing-and little swelling, especially no detectable heterogeneous bubble formation at the fuel/cladding interface tested to a fission density of up to 2.7E+21 (average) fissions/cm3, 3.8E+21 (peak).

Assessment of safety margins in zircaloy oxidation and embrittlement criteria for ECCS acceptance

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

Williford, R.E.

1986-04-01

Current Emergency Core Cooling System (ECCS) Acceptance Criteria for light-water reactors include certain requirements pertaining to calculations of core performance during a Loss of Coolant Accident (LOCA). The Baker-Just correlation must be used to calculate Zircaloy-steam oxidation, calculated peak cladding temperatures (PCT) must not exceed 1204/sup 0/C, and calculated oxidation must not exceed 17% equivalent cladding reacted (17% ECR). The minimum margin of safety was estimated for each of these criteria, based on research performed in the last decade. Margins were defined as the amounts of conservatism over and above the expected extreme values computed from the data base atmore » specified confidence levels. The currently required Baker-Just oxidation correlation provides margins only over the 1100/sup 0/C to 1500/sup 0/C temperature range at the 95% confidence level. The PCT margins for thermal shock and handling failures are adequate at oxidation temperatures above 1204/sup 0/C for 210 and 160 seconds, respectively, at the 95% confidence level. ECR thermal shock and handling margins at the 50% and 95% confidence levels, respectively, range between 2% and 7% ECR for the Baker-Just correlation, but vanish at temperatures between 1100/sup 0/C and 1160/sup 0/C for the best-estimate Cathcart-Pawel correlation. Use of the Cathcart-Pawel correlation for LOCA calculations can be justified at the 85% to 88% confidence level if cooling rate effects can be neglected. 75 refs., 21 figs.« less

PROCESS FOR DISSOLVING BINARY URANIUM-ZIRCONIUM OR ZIRCONIUM-BASE ALLOYS

DOEpatents

Jonke, A.A.; Barghusen, J.J.; Levitz, N.M.

1962-08-14

A process of dissolving uranium-- zirconium and zircaloy alloys, e.g. jackets of fuel elements, with an anhydrous hydrogen fluoride containing from 10 to 32% by weight of hydrogen chloride at between 400 and 450 deg C., preferably while in contact with a fluidized inert powder, such as calcium fluoride is described. (AEC)

Estimation of ring tensile properties of steam oxidized Zircaloy-4 fuel cladding under simulated LOCA condition

NASA Astrophysics Data System (ADS)

Shriwastaw, R. S.; Sawarn, Tapan K.; Banerjee, Suparna; Rath, B. N.; Dubey, J. S.; Kumar, Sunil; Singh, J. L.; Bhasin, Vivek

2017-09-01

The present study involves the estimation of ring tensile properties of Indian Pressurised Heavy Water Reactor (IPHWR) fuel cladding made of Zircaloy-4, subjected to experiments under a simulated loss-of-coolant-accident (LOCA) condition. Isothermal steam oxidation experiments were conducted on clad tube specimens at temperatures ranging from 900 to 1200 °C at an interval of 50 °C for different soaking periods with subsequent quenching in water at ambient temperature. The specimens, which survived quenching, were then subjected to ambient temperature ring tension test (RTT). The microstructure was correlated with the mechanical properties. The yield strength (YS) and ultimate tensile strength (UTS) increased initially with rise in oxidation temperature and time duration but then decreased with further increase in oxidation. Ductility is adversely affected with rising oxidation temperature and longer holding time. A higher fraction of load bearing phase and lower oxygen content in it ensures higher residual ductility. Cladding shows almost zero ductility behavior in RIT when load bearing phase fraction is less than 0.72 and its average oxygen concentration is greater than 0.58 wt%.

Experimental and statistical study on fracture boundary of non-irradiated Zircaloy-4 cladding tube under LOCA conditions

NASA Astrophysics Data System (ADS)

Narukawa, Takafumi; Yamaguchi, Akira; Jang, Sunghyon; Amaya, Masaki

2018-02-01

For estimating fracture probability of fuel cladding tube under loss-of-coolant accident conditions of light-water-reactors, laboratory-scale integral thermal shock tests were conducted on non-irradiated Zircaloy-4 cladding tube specimens. Then, the obtained binary data with respect to fracture or non-fracture of the cladding tube specimen were analyzed statistically. A method to obtain the fracture probability curve as a function of equivalent cladding reacted (ECR) was proposed using Bayesian inference for generalized linear models: probit, logit, and log-probit models. Then, model selection was performed in terms of physical characteristics and information criteria, a widely applicable information criterion and a widely applicable Bayesian information criterion. As a result, it was clarified that the log-probit model was the best among the three models to estimate the fracture probability in terms of the degree of prediction accuracy for both next data to be obtained and the true model. Using the log-probit model, it was shown that 20% ECR corresponded to a 5% probability level with a 95% confidence of fracture of the cladding tube specimens.

Design study of the geometry of the blanking tool to predict the burr formation of Zircaloy-4 sheet

NASA Astrophysics Data System (ADS)

Ha, Jisun; Lee, Hyungyil; Kim, Dongchul; Kim, Naksoo

2013-12-01

In this work, we investigated factors that influence burr formation for zircaloy-4 sheet used for spacer grids of nuclear fuel roads. Factors we considered are geometric factors of punch. We changed clearance and velocity in order to consider the failure parameters, and we changed shearing angle and corner radius of L-shaped punch in order to consider geometric factors of punch. First, we carried out blanking test with failure parameter of GTN model using L-shaped punch. The tendency of failure parameters and geometric factors that affect burr formation by analyzing sheared edges is investigated. Consequently, geometric factor's influencing on the burr formation is also high as failure parameters. Then, the sheared edges and burr formation with failure parameters and geometric factors is investigated using FE analysis model. As a result of analyzing sheared edges with the variables, we checked geometric factors more affect burr formation than failure parameters. To check the reliability of the FE model, the blanking force and the sheared edges obtained from experiments are compared with the computations considering heat transfer.

Bending testing and characterization of surrogate nuclear fuel rods made of Zircaloy-4 cladding and aluminum oxide pellets

DOE PAGES

Wang, Hong; Wang, Jy-An John

2016-07-20

We studied behavior of surrogate nuclear fuel rods made of Zircaloy-4 (Zry-4) cladding with alumina pellets under reversed cyclic bending. Tests were performed under load or moment control at 5 Hz, and an empirical correlation was established between rod fatigue life and amplitude of the applied moment. Fatigue response of Zry-4 cladding was further characterized by using flexural rigidity. Degradation of flexural rigidity was shown to depend on the moment applied and the prefatigue condition of specimens. Pellet-to-pellet interface (PPI), pellet-to-cladding interface (PCI), and pellet condition all affect surrogate rod failure. Bonding/debonding of PPI/PCI and pellet fracturing contribute to surrogatemore » rod bending fatigue. Also, the effect of sensor spacing on curvature measurement using three-point deflections was studied; the method based on effective specimen gauge length is effective in sensor spacing correction. Finally, we developed the database and gained understanding in this study such that it will serve as input to analysis of SNF vibration integrity.« less

Fuel cladding behavior under rapid loading conditions

NASA Astrophysics Data System (ADS)

Yueh, K.; Karlsson, J.; Stjärnsäter, J.; Schrire, D.; Ledergerber, G.; Munoz-Reja, C.; Hallstadius, L.

2016-02-01

A modified burst test (MBT) was used in an extensive test program to characterize fuel cladding failure behavior under rapid loading conditions. The MBT differs from a normal burst test with the use of a driver tube to simulate the expansion of a fuel pellet, thereby producing a partial strain driven deformation condition similar to that of a fuel pellet expansion in a reactivity insertion accident (RIA). A piston/cylinder assembly was used to pressurize the driver tube. By controlling the speed and distance the piston travels the loading rate and degree of sample deformation could be controlled. The use of a driver tube with a machined gauge section localizes deformation and allows for continuous monitoring of the test sample diameter change at the location of maximum hoop strain, during each test. Cladding samples from five irradiated fuel rods were tested between 296 and 553 K and loading rates from 1.5 to 3.5/s. The test rods included variations of Zircaloy-2 with different liners and ZIRLO, ranging in burn-up from 41 to 74 GWd/MTU. The test results show cladding ductility is strongly temperature and loading rate dependent. Zircaloy-2 cladding ductility degradation due to operational hydrogen pickup started to recover at approximately 358 K for test condition used in the study. This recovery temperature is strongly loading rate dependent. At 373 K, ductility recovery was small for loading rates less than 8 ms equivalent RIA pulse width, but longer than 8 ms the ductility recovery increased exponentially with increasing pulse width, consistent with literature observations of loading rate dependent brittle-to-ductile (BTD) transition temperature. The cladding ductility was also observed to be strongly loading rate/pulse width dependent for BWR cladding below the BTD temperature and Pressurized Water Reactor (PWR) cladding at both 296 and 553 K.

Remote Field Eddy Curent Signal Modeling for the Gap Measurement of Neighboring Tubes

NASA Astrophysics Data System (ADS)

Jung, H. K.; Lee, D. H.; Lee, Y. S.

2005-04-01

The fuel channels in the Canadian Deuterium Uranium (CANDU) reactor consist of the coaxial pressure tube (PT) and the calandria tube (CT). The Liquid injection nozzle (LIN) is cross aligned with the fuel channel to control the reactor by injecting poison. For a safe operation, the gap between the LIN and CT should be maintained in order to prevent a contact of the neighboring tubes. The remote field eddy current (RFEC) method was applied to measure the gap between a nonmagnetic Zircaloy-2 liquid injection nozzle (LIN) and a Zircaloy-2 calandria tube. Under the condition of inserting the RFEC probe into the coaxial tubes and of crossing a LIN above or under the CT, the modeling of a LIN signal is needed to check the possibility of a gap measurement. The Volume Integral Code S/W which covers the axi-symmetric 3D configuration has been very rarely applied to obtain a LIN signal. This problem was solved by assuming a LIN as a flaw which can be described as a complete 3D object. This simulated LIN signal was verified by performing the laboratory experiment. The gap between the LIN and CT can be correlated with the amplitude of the LIN signals in the voltage plane. Typical noises in the fuel channel were the relative constriction, the change in the pressure tube diameter (fill-factor), thickness variation, and so on. These noise signals were simulated by using the modeling and were analyzed by considering their dependency on the phase angle and amplitude of the voltage plane in order to separate the gap signal from them. It could be concluded that the voltage plane analysis of the simulated RFEC signals were effective for obtaining the gap measurement of the neighboring tube.

PRESSURIZED WATER REACTOR PROGRAM TECHNICAL PROGRESS REPORT FOR THE PERIOD MAY 5, 1955 TO JUNE 16, 1955

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

None

The current PWR plant and core parameters are listed. Resign requirements are briefly summarized for a radiation monitoring system, a fuel handling water system, a coolant purification system, an electrical power distribution system, and component shielding. Results of studies on thermal bowing and stressing of UO/sub 2/ are reported. A graph is presented of reactor power vs. reactor flow for various hot channel conditions. Development of U-- Mo and U-Nb alloys has been stopped because of the recent selection of UO/sub 2/ fuel material for the PWR core and blanket. The fabrication characteristics of UO/sub 2/ powders are being studied.more » Seamless Zircaloy-2 tubing has been tested to determine elastic limits, bursting pressures, and corrosion resistance. Fabrication techniques and tests for corrosion and defects in Zircaloy-clad U-Mo and UO/sub 2/ fuel rods are described. The preparation of UO/sub 2/ by various methods is being studied to determine which method produces a material most suitable for PWR fuel elements. The stability of UO/sub 2/ compacts in high temperature water and steam is being determined. Surface area and density measurements have been performed on samples of UO/sub 2/ powder prepared by various methods. Revelopment work on U-- Mo and U--Nb alloys has included studies of the effect on corrosion behavior of additions to the test water, additions to the alloys, homogenization of the alloys, annealing times, cladding, and fabrication techniques. Data are presented on relaxation in spring materials after exposure to a corrosive environment. Results are reported from loop and autoclave tests on fission product and crud deposition. Results of irradiation and corrosion testing of clad and unclad U--Mo and U-Nh alloys are described. The UO/sub 2/ irradiation program has included studies of dimensional changes, release of fission gases, and activity in the water surrounding the samples. A review of the methods of calculating reactor physics parameters has been completed, and the established procedures have been applied to determination of PWR reference design parameters. Critical experiments and primary loop shielding analyses are described. (D.E.B.)« less

One-way implodable tag capsule with hemispherical beaded end cap for LWR fuel manufacturing

DOEpatents

Gross, K.; Lambert, J.

1999-04-06

A capsule is disclosed containing a tag gas in a zircaloy body portion having a hemispherical top curved toward the bottom of the body portion. The hemispherical top has a rupturable portion upon exposure to elevated gas pressure and the capsule is positioned within a fuel element in a nuclear reactor. 3 figs.

Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

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

Parker, Stephen S.; White, Josh; Hosemann, Peter

High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. We measured the oxidation kinetic constant (k) as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3–5 orders of magnitude lower across the experimental temperature range. Our results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

DOE PAGES

Parker, Stephen S.; White, Josh; Hosemann, Peter; ...

2017-11-03

High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. We measured the oxidation kinetic constant (k) as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3–5 orders of magnitude lower across the experimental temperature range. Our results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

NASA Astrophysics Data System (ADS)

Parker, Stephen S.; White, Josh; Hosemann, Peter; Nelson, Andrew

2018-02-01

High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. The oxidation kinetic constant ( k) was measured as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3-5 orders of magnitude lower across the experimental temperature range. The results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

Studies of electrochemical oxidation of Zircaloy nuclear reactor fuel cladding using time-of-flight-energy elastic recoil detection analysis

NASA Astrophysics Data System (ADS)

Whitlow, H. J.; Zhang, Y.; Wang, Y.; Winzell, T.; Simic, N.; Ahlberg, E.; Limbäck, M.; Wikmark, G.

2000-03-01

The trend towards increased fuel burn-up and higher operating temperatures in order to achieve more economic operation of nuclear power plants places demands on a better understanding of oxidative corrosion of Zircaloy (Zry) fuel rod cladding. As part of a programme to study these processes we have applied time-of-flight-energy elastic recoil detection (ToF-E ERD), electrochemical impedance measurements and scanning electron microscopy to quantitatively characterise thin-oxide films corresponding to the pre-transition oxidation regime. Oxide films of different nominal thickness in the 9-300 nm range were grown on a series of rolled Zr and Zry-2 plates by anodisation in dilute H 2SO 4 with applied voltages. The dielectric thickness of the oxide layer was determined from the electrochemical impedance measurements and the surface topography characterised by scanning electron microscopy. ToF-E ERD with a 60 MeV 127I 11+ ion beam was used to determine the oxygen content and chemical composition of the oxide layer. In the Zr samples, the oxygen content (O atom cm -2) that was determined by ERD was closely similar to the O content derived from impedance measurements from the dielectric film. The absolute agreement was well within the uncertainty associated with the stopping powers. Moreover, the measured composition of the thick oxide layers corresponded to ZrO 2 for the films thicker than 65 nm where the oxide layer was resolved in the ERD depth profile. Zry-2 samples exhibited a similar behaviour for small thickness ( ⩽130 nm) but had an enhanced O content at larger thicknesses that could be associated either with enhanced rough surface topography or porous oxide formation that was correlated with the presence of Second Phase Particles (SPP) in Zry-2. The concentration of SPP elements (Fe, Cr, Ni) in relation to Zr was the same in the outer 9×10 17 atom cm -2 of oxide as in the same thickness of metal. The results also revealed the presence of about 1 at.% 32S in the oxides on the Zr and Zry-2 samples which presumably originates from the electrolyte.

In situ characterization of Zircaloy-4 oxidation at 500 °C in dry air

NASA Astrophysics Data System (ADS)

Vermoyal, J. J.; Dessemond, L.; Hammou, A.; Frichet, A.

2001-10-01

The in situ oxidation of Zircaloy-4 at 500 °C in dry air was investigated by thermogravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS). The coating of the alloy by a platinum film as electrode material was observed as not to modify the oxidation kinetic properties. After an initial cubic rate law, a transition to a quasi-linear curve occurs. The independence of the oxidation behavior to the Pt coupling is compatible with oxygen diffusion as the rate-determining step. During the pre-transition step, the rest potential of the cell Pt/oxide/Zy-4, the color of the oxide and the modulus of the single EIS signature indicate the high non-stoichiometry of the oxide. The kinetic transition was proposed to be correlated to the degradation of the film into a partially porous layer. This alteration of the oxide is associated to the appearance of a 1.2 V constant rest potential and the modification of the impedance diagrams in two high modulus contributions. The Cole-Cole representation has been used to demonstrate that the time variation of impedance spectra is related to the oxide growth. An equivalent circuit including two RC loops in series, whose capacitances are frequency dispersed, was proposed to be related to the film structure. Fitted data show that the thickness of the assumed protective layer of the film, close to the metal-oxide interface, is time independent in agreement with a constant oxidation rate. Finally, electrical properties of this inner layer were found to be quite different in pre- and post-transition stage.

The role of hydrogen in zirconium alloy corrosion

NASA Astrophysics Data System (ADS)

Ensor, B.; Lucente, A. M.; Frederick, M. J.; Sutliff, J.; Motta, A. T.

2017-12-01

Hydrogen enters zirconium metal as a result of the corrosion process and forms hydrides when present in quantities above the solubility limit at a given temperature. Zircaloy-4 coupons of different thicknesses (0.4 mm-2.3 mm) but identical chemistry and processing were corroded in autoclave at 360 °C for various times up to 2800 days. Coupons were periodically removed and weighed to determine weight gain, which allows follow of the corrosion kinetics. Coupon thickness differences resulted in different volumetric concentrations of hydrogen, as quantified using hot vacuum extraction. The thinnest coupons, having the highest concentration of hydrogen, demonstrated acceleration in their corrosion kinetics and shorter transition times when compared to thicker coupons. Furthermore, it was seen that the post-transition corrosion rate was increased with increasing hydrogen concentration. Corrosion rates increased only after the terminal solid solubility (TSS) was exceeded for hydrogen in Zircaloy-4 at 360 °C. Therefore, it is hypothesized that the corrosion acceleration is caused by the formation of hydrides. Scanning electron microscope (SEM) examinations of fractured oxide layers demonstrate the oxide morphology changed with hydrogen content, with more equiaxed oxide grains in the high hydrogen samples than in those with lower hydrogen content. Additionally, locations of advanced oxide growth were correlated with locations of hydrides in the metal. A hypothesis is proposed to explain the accelerated corrosion due to the presence of the hydrides, namely that the metal, locally, is less able to accommodate oxide growth stresses and this leads to earlier loss of oxide protectiveness in the form of more frequent oxide kinetic transitions.

On the corrosion behavior of zircaloy-4 in spent fuel pools under accidental conditions

NASA Astrophysics Data System (ADS)

Lavigne, O.; Shoji, T.; Sakaguchi, K.

2012-07-01

After zircaloy cladding tubes have been subjected to irradiation in the reactor core, they are stored temporarily in spent fuel pools. In case of an accident, the integrity of the pool may be affected and the composition of the coolant may change drastically. This was the case in Fukushima Daiichi in March 2011. Successive incidents have led to an increase in the pH of the coolant and to chloride contamination. Moreover, water radiolysis may occur owing to the remnant radioactivity of the spent fuel. In this study, we propose to evaluate the corrosion behavior of oxidized Zr-4 (in autoclave at 288 °C for 32 days) in function of the pH and the presence of chloride and radical forms. The generation of radicals is achieved by the sonolysis of the solution. It appears that the increase in pH and the presence of radicals lead to an increase in current densities. However, the current densities remain quite low (depending on the conditions, between 1 and 10 μA cm-2). The critical parameter is the presence of chloride ions. The chloride ions widely decrease the passive range of the oxidized samples (the pitting potential is measured around +0.6 V (vs. SCE)). Moreover, if the oxide layer is scratched or damaged (which is likely under accidental conditions), the pitting potential of the oxidized sample reaches the pitting potential of the non-oxidized sample (around +0.16 V (vs. SCE)), leaving a shorter stable passive range for the Zr-4 cladding tubes.

TEM study on the initial oxidation of Zircaloy-4 thin foil specimens heated in a low vacuum air condition at 280-300 °C

NASA Astrophysics Data System (ADS)

Wang, Zhen; Zhou, Bang-xin; Zhu, Wei; Wen, Bang; Yao, Mei-yi; Li, Qiang; Wu, Lu; Zhang, Jin-long; Fang, Zhong-qiang

2017-04-01

As one of the important structural materials in nuclear industry, the corrosion resistance of zirconium alloy limits their in-pile application. Therefore, it is necessary to investigate the corrosion mechanism of zirconium alloys. The zirconium-oxygen reaction at the O/M interface is one of the factors that affect the oxidation process. There are few reports in this regard. Ideally, the reaction process at the O/M interface has certain relevance with the initiation oxidation of zirconium, which provided a new way to investigate the reaction process by observing the initiation oxidation behaviours. To investigate the oxidation behaviours of zirconium alloy at the initial stage, in this paper, zircaloy-4 TEM thin foil specimens in 3 mm diameter were studied by TEM observation after heating in air condition with a vacuum of 3 Pa at 280 °C, 290 °C and 300 °C for 30 min exposures. The results show that, ZrO2 begin to nucleate at a size of 3-5 nm at a high Zr/O ratio of 10.4 and oxide layer formed while Zr/O was 4.6. As a result of stress caused by the P.B ratio of Zr, slip bands formed and a bcc structure sub-oxide b-ZrOx (a = 0.51 nm) grew up along with the slip bands was observed. At both sides of b-ZrOx, two hcp structure sub-oxides having the same a-axis lattice parameter and different c-axis lattice parameter were detected.

PLUTONIUM-ZIRCONIUM ALLOYS

DOEpatents

Schonfeld, F.W.; Waber, J.T.

1960-08-30

A series of nuclear reactor fuel alloys consisting of from about 5 to about 50 at.% zirconium (or higher zirconium alloys such as Zircaloy), balance plutonium, and having the structural composition of a plutonium are described. Zirconium is a satisfactory diluent because it alloys readily with plutonium and has desirable nuclear properties. Additional advantages are corrosion resistance, excellent fabrication propenties, an isotropie structure, and initial softness.

Air oxidation of Zircaloy-4 in the 600-1000 °C temperature range: Modeling for ASTEC code application

NASA Astrophysics Data System (ADS)

Coindreau, O.; Duriez, C.; Ederli, S.

2010-10-01

Progress in the treatment of air oxidation of zirconium in severe accident (SA) codes are required for a reliable analysis of severe accidents involving air ingress. Air oxidation of zirconium can actually lead to accelerated core degradation and increased fission product release, especially for the highly-radiotoxic ruthenium. This paper presents a model to simulate air oxidation kinetics of Zircaloy-4 in the 600-1000 °C temperature range. It is based on available experimental data, including separate-effect experiments performed at IRSN and at Forschungszentrum Karlsruhe. The kinetic transition, named "breakaway", from a diffusion-controlled regime to an accelerated oxidation is taken into account in the modeling via a critical mass gain parameter. The progressive propagation of the locally initiated breakaway is modeled by a linear increase in oxidation rate with time. Finally, when breakaway propagation is completed, the oxidation rate stabilizes and the kinetics is modeled by a linear law. This new modeling is integrated in the severe accident code ASTEC, jointly developed by IRSN and GRS. Model predictions and experimental data from thermogravimetric results show good agreement for different air flow rates and for slow temperature transient conditions.

Equations of state for crystalline zirconium iodide: The role of dispersion

NASA Astrophysics Data System (ADS)

Rossi, Matthew L.; Taylor, Christopher D.

2013-02-01

We present the first-principle equations of state of several zirconium iodides, ZrI2, ZrI3, and ZrI4, computed using density functional theory methods that apply various methods for introducing the dispersion correction. Iodides formed due to reaction of molecular or atomic iodine with zirconium and zircaloys are of particular interest due to their application to the cladding material used in the fabrication of nuclear fuel rods. Stress corrosion cracking (SCC), associated with fission product chemistry with the clad material, is a major concern in the life cycle of nuclear fuels, as many of the observed rod failures have occurred due to pellet-cladding chemical interactions (PCCI) [A. Atrens, G. Dannhäuser, G. Bäro, Stress-corrosion-cracking of zircaloy-4 cladding tubes, Journal of Nuclear Materials 126 (1984) 91-102; P. Rudling, R. Adamson, B. Cox, F. Garzarolli, A. Strasser, High burn-up fuel issues, Nuclear Engineering and Technology 40 (2008) 1-8]. A proper understanding of the physical properties of the corrosion products is, therefore, required for the development of a comprehensive SCC model. In this particular work, we emphasize that, while existing modeling techniques include methods to compute crystal structures and associated properties, it is important to capture intermolecular forces not traditionally included, such as van der Waals (dispersion) correction. Furthermore, crystal structures with stoichiometries favoring a high I:Zr ratio are found to be particularly sensitive, such that traditional density functional theory approaches that do not incorporate dispersion incorrectly predict significantly larger volumes of the lattice. This latter point is related to the diffuse nature of the iodide electron cloud.

DEVELOPMENT OF PLASTICITY MODEL USING NON ASSOCIATED FLOW RULE FOR HCP MATERIALS INCLUDING ZIRCONIUM FOR NUCLEAR APPLICATIONS

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

Michael V. Glazoff; Jeong-Whan Yoon

2013-08-01

In this report (prepared in collaboration with Prof. Jeong Whan Yoon, Deakin University, Melbourne, Australia) a research effort was made to develop a non associated flow rule for zirconium. Since Zr is a hexagonally close packed (hcp) material, it is impossible to describe its plastic response under arbitrary loading conditions with any associated flow rule (e.g. von Mises). As a result of strong tension compression asymmetry of the yield stress and anisotropy, zirconium displays plastic behavior that requires a more sophisticated approach. Consequently, a new general asymmetric yield function has been developed which accommodates mathematically the four directional anisotropies alongmore » 0 degrees, 45 degrees, 90 degrees, and biaxial, under tension and compression. Stress anisotropy has been completely decoupled from the r value by using non associated flow plasticity, where yield function and plastic potential have been treated separately to take care of stress and r value directionalities, respectively. This theoretical development has been verified using Zr alloys at room temperature as an example as these materials have very strong SD (Strength Differential) effect. The proposed yield function reasonably well models the evolution of yield surfaces for a zirconium clock rolled plate during in plane and through thickness compression. It has been found that this function can predict both tension and compression asymmetry mathematically without any numerical tolerance and shows the significant improvement compared to any reported functions. Finally, in the end of the report, a program of further research is outlined aimed at constructing tensorial relationships for the temperature and fluence dependent creep surfaces for Zr, Zircaloy 2, and Zircaloy 4.« less

An investigation of FeCrAl cladding behavior under normal operating and loss of coolant conditions

DOE PAGES

Gamble, Kyle A.; Barani, Tommaso; Pizzocri, David; ...

2017-04-30

Iron-chromium-aluminum (FeCrAl) alloys are candidates to be used as nuclear fuel cladding for increased accident tolerance. An analysis of the response of FeCrAl under normal operating and loss of coolant conditions has been performed using fuel performance modeling. In particular, recent information on FeCrAl material properties and phenomena from separate effects tests has been implemented in the BISON fuel performance code and analyses of integral fuel rod behavior with FeCrAl cladding have been performed. BISON simulations included both light water reactor normal operation and loss-of-coolant accidental transients. In order to model fuel rod behavior during accidents, a cladding failure criterionmore » is desirable. For FeCrAl alloys, a failure criterion is developed using recent burst experiments under loss of coolant like conditions. The added material models are utilized to perform comparative studies with Zircaloy-4 under normal operating conditions and oxidizing and non-oxidizing out-of-pile loss of coolant conditions. The results indicate that for all conditions studied, FeCrAl behaves similarly to Zircaloy-4 with the exception of improved oxidation performance. Here, further experiments are required to confirm these observations.« less

Considerable knock-on displacement of metal atoms under a low energy electron beam.

PubMed

Gu, Hengfei; Li, Geping; Liu, Chengze; Yuan, Fusen; Han, Fuzhou; Zhang, Lifeng; Wu, Songquan

2017-03-15

Under electron beam irradiation, knock-on atomic displacement is commonly thought to occur only when the incident electron energy is above the incident-energy threshold of the material in question. However, we report that when exposed to intense electrons at room temperature at a low incident energy of 30 keV, which is far below the theoretically predicted incident-energy threshold of zirconium, Zircaloy-4 (Zr-1.50Sn-0.25Fe-0.15Cr (wt.%)) surfaces can undergo considerable displacement damage. We demonstrate that electron beam irradiation of the bulk Zircaloy-4 surface resulted in a striking radiation effect that nanoscale precipitates within the surface layer gradually emerged and became clearly visible with increasing the irradiation time. Our transmission electron microscope (TEM) observations further reveal that electron beam irradiation of the thin-film Zircaly-4 surface caused the sputtering of surface α-Zr atoms, the nanoscale atomic restructuring in the α-Zr matrix, and the amorphization of precipitates. These results are the first direct evidences suggesting that displacement of metal atoms can be induced by a low incident electron energy below threshold. The presented way to irradiate may be extended to other materials aiming at producing appealing properties for applications in fields of nanotechnology, surface technology, and others.

An investigation of FeCrAl cladding behavior under normal operating and loss of coolant conditions

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

Gamble, Kyle A.; Barani, Tommaso; Pizzocri, David

Iron-chromium-aluminum (FeCrAl) alloys are candidates to be used as nuclear fuel cladding for increased accident tolerance. An analysis of the response of FeCrAl under normal operating and loss of coolant conditions has been performed using fuel performance modeling. In particular, recent information on FeCrAl material properties and phenomena from separate effects tests has been implemented in the BISON fuel performance code and analyses of integral fuel rod behavior with FeCrAl cladding have been performed. BISON simulations included both light water reactor normal operation and loss-of-coolant accidental transients. In order to model fuel rod behavior during accidents, a cladding failure criterionmore » is desirable. For FeCrAl alloys, a failure criterion is developed using recent burst experiments under loss of coolant like conditions. The added material models are utilized to perform comparative studies with Zircaloy-4 under normal operating conditions and oxidizing and non-oxidizing out-of-pile loss of coolant conditions. The results indicate that for all conditions studied, FeCrAl behaves similarly to Zircaloy-4 with the exception of improved oxidation performance. Here, further experiments are required to confirm these observations.« less

ORNL Interim Progress Report on Hydride Reorientation CIRFT Tests

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

Wang, Jy-An John; Yan, Yong; Wang, Hong

A systematic study of H. B. Robinson (HBR) high burnup spent nuclear fuel (SNF) vibration integrity was performed in Phase I project under simulated transportation environments, using the Cyclic Integrated Reversible-Bending Fatigue Tester (CIRFT) hot cell testing technology developed at Oak Ridge National Laboratory in 2013–14. The data analysis on the as-irradiated HBR SNF rods demonstrated that the load amplitude is the dominant factor that controls the fatigue life of bending rods. However, previous studies have shown that the hydrogen content and hydride morphology has an important effect on zirconium alloy mechanical properties. To address the effect of radial hydridesmore » in SNF rods, in Phase II a test procedure was developed to simulate the effects of elevated temperatures, pressures, and stresses during transfer-drying operations. Pressurized and sealed fuel segments were heated to the target temperature for a preset hold time and slow-cooled at a controlled rate. The procedure was applied to both non-irradiated/prehydrided and high-burnup Zircaloy-4 fueled cladding segments using the Nuclear Regulatory Commission-recommended 400°C maximum temperature limit at various cooling rates. Before testing high-burnup cladding, four out-of-cell tests were conducted to optimize the hydride reorientation (R) test condition with pre-hydride Zircaloy-4 cladding, which has the same geometry as the high burnup fuel samples. Test HR-HBR#1 was conducted at the maximum hoop stress of 145 MPa, at a 400°C maximum temperature and a 5°C/h cooling rate. On the other hand, thermal cycling was performed for tests HR-HBR#2, HR-HBR#3, and HR-HBR#4 to generate more radial hydrides. It is clear that thermal cycling increases the ratio of the radial hydride to circumferential hydrides. The internal pressure also has a significant effect on the radial hydride morphology. This report describes a procedure and experimental results of the four out-of-cell hydride reorientation tests of hydrided Zircaloy-4 cladding, which served as a guideline to prepare in-cell hydride reorientation samples with high burnup HBR fuel segments. This report also provides the Phase II CIRFT test data for the hydride reorientation irradiated samples. The variations in fatigue life are provided in terms of moment, equivalent stress, curvature, and equivalent strain for the tested SNFs. The CIRFT results appear to indicate that hydride reoriented treatment (HRT) have a negative effect on fatigue life, in addition to hydride reorientation effect. For HR4 specimen that had no pressurization procedure applied, the thermal annealing treatment alone showed a negative impact on the fatigue life compared to the HBR rod.« less

An investigation of the oxidation behaviour of zirconium alloys using isotopic tracers and high resolution SIMS

NASA Astrophysics Data System (ADS)

Yardley, Sean S.; Moore, Katie L.; Ni, Na; Wei, Jang Fei; Lyon, Stuart; Preuss, Michael; Lozano-Perez, Sergio; Grovenor, Chris R. M.

2013-11-01

High resolution secondary ion mass spectrometry (SIMS) analysis has been used to study the oxidation mechanisms when commercial low tin ZIRLO™Low tin ZIRLO™ is a trademark of Westinghouse Electric Company LLC in the United States and may be registered in other countries throughout the world. Unauthorized use is strictly prohibited.1 and Zircaloy 4 materials are exposed to corroding environments containing both 18O and 2H isotopes. Clear evidence has been shown for different characteristic distributions of 18O before and after the kinetic transitions, and this behaviour has been correlated with the development of porosity in the oxide which allows the corroding medium to penetrate locally to the metal/oxide interface.

Preliminary assessment of accident-tolerant fuels on LWR performance during normal operation and under DB and BDB accident conditions

NASA Astrophysics Data System (ADS)

Ott, L. J.; Robb, K. R.; Wang, D.

2014-05-01

Following the severe accidents at the Japanese Fukushima Daiichi Nuclear Power Station in 2011, the US Department of Energy initiated research and development on the enhancement of the accident tolerance of light water reactors by the development of fuels/cladding that, in comparison with the standard UO2/Zircaloy (Zr) system, can tolerate loss of active cooling in the core for a considerably longer time period while maintaining or improving the fuel performance during normal operations. Analyses are presented that illustrate the impact of these new candidate fuel/cladding materials on the fuel performance at normal operating conditions and on the reactor system under DB and BDB accident conditions.

Etude du comportement et de la modélisation viscoplastique du zircaloy 4recristallisé sous chargements monotones et cycliques uni et multiaxes

NASA Astrophysics Data System (ADS)

Delobelle, P.; Robinet, P.

1994-08-01

The results of experiment performed on a recrystallized zircaloy 4 alloy in the intermediate temperature domain 20 leqslant T leqslant 400 ^{circ}C are presented. To characterize the anisotropy, especially at 350 ^{circ}C, the tests were made under both monotonic and cyclic uni- and bidirectional loadings, i.e. tension-compression, tension-torsion and tension-internal pressure tests. The different anisotropy coefficients and especially R^p = \\varepsilon^p_{θθ} /\\varepsilon^ p _ {{^-_-}{^-_-} } seem to be temperature independent. An important feature of the behavior of this alloy in the neighbourhood of 300 ^{circ}C is attributed to the dislocations-point defects interactions (dynamic strain aging), phenomena often observed in the solid solutions. For the 2D cyclic non proportional loadings it is shown that a weak supplementary hardening appears, which is a function of the degree of the phase lag. We propose to particularize and to apply a unified viscoplastic model with internal variables to the considered alloy, as the model as already been developed and identified elsewhere for other isotropic materials. From a general point of view the introduction of the anisotropy in the model is made by four tensors of rank 4 ; [ M] is assigned to the flow directions, [ N] to the linear parts of the kinematical hardening variables and [ Q] , [ R] respectively to the dynamic and static recoveries of these tensorial variables. This phenomenological formulation leads to a correct representation of the set of the experimental results presented at 350 ^{circ}C, which provides an a posteriori confirmation of the formalism used. On étudie, entre 20 et 400 ^{circ}C, à l'aide d'essais sous chargements multiaxiaux monotones et cycliques (traction, torsion et pression interne) les propriétés viscoplastiques anisotropes de tube de zircaloy 4 recristallisé. A la température de 350 ^{circ}C, l'anisotropie a été quantifiée de façon détaillée. Les quelques résultats obtenus à la température ambiante ainsi que l'indépendance du rapport R^p = \\varepsilon^p_{θθ}/\\varepsilon^ p_{{^-_-}{^-_-} } avec la température laissent supposer que l'ensemble des coefficients d'anisotropie ne dépendent pas de la température. Par contre, la fluidité de cet alliage présente un minimum très marqué au voisinage de 300 ^{circ}C. Ce comportement est imputable au vieillissement dynamique fréquemment observé dans les solutions solides d'insertion. Lors d'un chargement cyclique hors phase (traction-torsion déphasée à 90^{circ}) ce matériau présente un léger durcissement supplémentaire. On propose l'extension au cas du zircaloy 4 de la formulation d'un modèle viscoplastique unifié développé et identifié par ailleurs sur d'autres matériaux initialement isotropes. D'une manière générale, l'introduction de l'anisotropie dans ce modèle s'effectue par l'intermédiaire de quatre tenseurs d'ordre 4 affectant les directions d'écoulement [ M] , les parties linéaires des écrouissages cinématiques [ N] , ainsi que les restaurations dynamiques [ Q] et statiques [ R] de ces mêmes variables d'écrouissage. L'identification de ce modèle est discutée et réalisée à 350 ^{circ}C. On montre l'adéquation du formalisme à appréhender l'ensemble des caractéristiques mécaniques de cet alliage.

Crack growth through the thickness of thin-sheet Hydrided Zircaloy-4

NASA Astrophysics Data System (ADS)

Raynaud, Patrick A. C.

In recent years, the limits on fuel burnup have been increased to allow an increase in the amount of energy produced by a nuclear fuel assembly thus reducing waste volume and allowing greater capacity factors. As a result, it is paramount to ensure safety after longer reactor exposure times in the case of design-basis accidents, such as reactivity-initiated accidents (RIA). Previously proposed failure criteria do not directly address the particular cladding failure mechanism during a RIA, in which crack initiation in brittle outer-layers is immediately followed by crack growth through the thickness of the thin-wall tubing. In such a case, the fracture toughness of hydrided thin-wall cladding material must be known for the conditions of through-thickness crack growth in order to predict the failure of high-burnup cladding. The fracture toughness of hydrided Zircaloy-4 in the form of thin-sheet has been examined for the condition of through-thickness crack growth as a function of hydride content and distribution at 25°C, 300°C, and 375°C. To achieve this goal, an experimental procedure was developed in which a linear hydride blister formed across the width of a four-point bend specimen was used to inject a sharp crack that was subsequently extended by fatigue pre-cracking. The electrical potential drop method was used to monitor the crack length during fracture toughness testing, thus allowing for correlation of the load-displacement record with the crack length. Elastic-plastic fracture mechanics were used to interpret the experimental test results in terms of fracture toughness, and J-R crack growth resistance curves were generated. Finite element modeling was performed to adapt the classic theories of fracture mechanics applicable to thick-plate specimens to the case of through-thickness crack growth in thin-sheet materials, and to account for non-uniform crack fronts. Finally, the hydride microstructure was characterized in the vicinity of the crack tip by means of digital image processing, so as to understand the influence of the hydride microstructure on fracture toughness, at the various test temperatures. Crack growth occurred through a microstructure which varied within the thickness of the thin-sheet Zircaloy-4 such that the hydrogen concentration and the radial hydride content decreased with increasing distance from the hydride blister. At 25°C, the fracture toughness was sensitive to the changes in hydride microstructure, such that the toughness KJi decreased from 39 MPa√m to 24 MPa√m with increasing hydrogen content and increasing the fraction of radial hydrides. The hydride particles present in the Zircaloy-4 substrate fractured ahead of the crack tip, and crack growth occurred by linking the crack-tip with the next hydride-induced primary void ahead of it. Unstable crack growth was observed at 25°C prior to any stable crack growth in the specimens where the hydrogen content was the highest. At 375°C as well as in most cases at 300°C, the hydride particles were resistant to cracking and the resistance to crack-growth initiation was very high. As a result, for this bend test procedure, crack extension was solely due to crack-tip blunting instead of crack growth in all tests at 375°C and in most cases at 300°C. The lower bound for fracture toughness at these temperatures, the parameter KJPmax, had values of K JPmax˜54MPa√m at both 300°C and 375°C. For cases where stable crack growth occurred at 300°C, the fracture toughness was K Ji˜58MPa√m and the tearing modulus was twice as high as that at 25°C. It is believed that the failure of hydrided Zircaloy-4 thin-wall cladding can be predicted using fracture mechanics analyses when failure occurs by crack growth. This failure mechanism was observed to occur in all cases at 25°C and in some cases at 300°C. However, at more elevated temperatures, such as 375°C, failure will likely occur by a mechanism other than crack growth, possibly by an imperfection-induced shear instability.

Stress corrosion crack initiation of Zircaloy-4 cladding tubes in an iodine vapor environment during creep, relaxation, and constant strain rate tests

NASA Astrophysics Data System (ADS)

Jezequel, T.; Auzoux, Q.; Le Boulch, D.; Bono, M.; Andrieu, E.; Blanc, C.; Chabretou, V.; Mozzani, N.; Rautenberg, M.

2018-02-01

During accidental power transient conditions with Pellet Cladding Interaction (PCI), the synergistic effect of the stress and strain imposed on the cladding by thermal expansion of the fuel, and corrosion by iodine released as a fission product, may lead to cladding failure by Stress Corrosion Cracking (SCC). In this study, internal pressure tests were conducted on unirradiated cold-worked stress-relieved Zircaloy-4 cladding tubes in an iodine vapor environment. The goal was to investigate the influence of loading type (constant pressure tests, constant circumferential strain rate tests, or constant circumferential strain tests) and test temperature (320, 350, or 380 °C) on iodine-induced stress corrosion cracking (I-SCC). The experimental results obtained with different loading types were consistent with each other. The apparent threshold hoop stress for I-SCC was found to be independent of the test temperature. SEM micrographs of the tested samples showed many pits distributed over the inner surface, which tended to coalesce into large pits in which a microcrack could initiate. A model for the time-to-failure of a cladding tube was developed using finite element simulations of the viscoplastic mechanical behavior of the material and a modified Kachanov's damage growth model. The times-to-failure predicted by this model are consistent with the experimental data.

Fast, quantitative, and nondestructive evaluation of hydrided LWR fuel cladding by small angle incoherent neutron scattering of hydrogen

DOE PAGES

Yan, Y.; Qian, S.; Littrell, K.; ...

2015-02-13

A non-destructive neutron scattering method to precisely measure the uptake of hydrogen and the distribution of hydride precipitates in light water reactor (LWR) fuel cladding was developed. Zircaloy-4 cladding used in commercial LWRs was used to produce hydrided specimens. The hydriding apparatus consists of a closed stainless steel vessel that contains Zr alloy specimens and hydrogen gas. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method, by which the samples with desired hydrogen concentration were selected for the neutron study. Optical microscopy shows that our hydriding procedure results in uniform distributionmore » of circumferential hydrides across the wall. Small angle neutron incoherent scattering was performed in the High Flux Isotope Reactor at Oak Ridge National Laboratory. This study demonstrates that the hydrogen in commercial Zircaloy-4 cladding can be measured very accurately in minutes by this nondestructive method over a wide range of hydrogen concentrations from a very small amount ( 20 ppm) to over 1000 ppm. The hydrogen distribution in a tube sample was obtained by scaling the neutron scattering rate with a factor determined by a calibration process using standard, destructive direct chemical analysis methods on the specimens. This scale factor will be used in future tests with unknown hydrogen concentrations, thus providing a nondestructive method for absolute hydrogen concentration determination.« less

Examination of Hybrid Metal Coatings for Mitigation of Fission Product Release and Corrosion Protection of LWR SiC/SiC

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

Ang, Caen K.; Burns, Joseph R.; Terrani, Kurt A.

2016-09-01

There is a need to increase the safety margins of current and future light water reactors (LWRs) due to the unfortunate events at Fukushima Daiichi Nuclear Plant. Safety is crucial to restore public confidence in nuclear energy, acknowledged as an economical, high-­density energy solution to climate change. The development of accident-­tolerant fuel (ATF) concepts is crucial to this endeavor. The objective of ATF is to delay the consequences of accident progression, being inset in high temperature steam and maintaining high thermomechanical strength for radionuclide retention. The use of advanced SiCf-­SiC composite as a substitute for zircaloy-­based cladding is being considered.more » However, at normal operations, SiC is vulnerable to the reactor coolant and may corrode at an unacceptable rate. As a ceramic-­matrix composite material, it is likely to undergo microcracking operation, which may compromise the ability to contain gaseous fission products. A proposed solution to both issues is the application of mitigation coatings for use in normal operations. At Oak Ridge National Laboratory (ORNL), three coating technologies have been investigated with industry collaborators and vendors. These are electrochemical deposition, cathodic arc physical vapor deposition (PVD hereafter) and vacuum plasma spray (VPS). The objective of this document is to summarize these processing technologies, the resultant as-­processed microstructures and properties of the coatings. In all processes, substrate constraint resulted in substantial tensile stresses within the coating layer. Each technology must mitigate this tensile stress. Electrochemical coatings use chromium as the coolant facing material, and are deposited on a nickel or carbon “bond coat”. This is economical but suffers microcracking in the chromium layer. PVD-­based coatings use chromium and titanium in both metallic form and nitrides, and can be deposited defense-­in-­depth as multilayers. This vapor method eliminated tensile stress during processing and coatings were up to ~30 μm thick without microcracking. VPS produced coatings based on Zircaloy-2, which has a proven reactor-­compatibility. The tensile stresses appearred to be partially mitigated by annealing. Analysis showed that VPS coatings required further optimizations to prevent adverse reactions with the substrate and need a minimum thickness of ~50 μm. In addition, development of coatings are constrained by neutronic depletion analysis, which clearly indicated enrichment as an issue if the coating is too thick. Based on the present work, the cathodic arc PVD technology was considered ready for the extensive testing and evaluation on cladding materials due to their ability to mitigate the excessive tensile stresses and the reasonable coating quality achieved. The VPS Zircaloy-­2 coating technology required additional development toward mitigation of issues related to the substrate reaction and porosity. In the future, PVD and VPS will have be scaled upon successful development and demonstration. Electrochemical coatings, which are proven scalability, currently require development to mitigate issues related to the tensile stress after deposition.« less

Compatibility studies on Mo-coating systems for nuclear fuel cladding applications

NASA Astrophysics Data System (ADS)

Koh, Huan Chin; Hosemann, Peter; Glaeser, Andreas M.; Cionea, Cristian

2017-12-01

To improve the safety factor of nuclear power plants in accident scenarios, molybdenum (Mo), with its high-temperature strength, is proposed as a potential fuel-cladding candidate. However, Mo undergoes rapid oxidation and sublimation at elevated temperatures in oxygen-rich environments. Thus, it is necessary to coat Mo with a protective layer. The diffusional interactions in two systems, namely, Zircaloy-2 (Zr2) on a Mo tube, and iron-chromium-aluminum (FeCrAl) on a Mo rod, were studied by aging coated Mo substrates in high vacuum at temperatures ranging from 650 °C to 1000° for 1000 h. The specimens were characterized using scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS) and nanoindentation. In both systems, pores in the coating increased in size and number with increasing temperature over time, and cracks were also observed; intermetallic phases formed between the Mo and its coatings.

Evaluation of Tritium Content and Release from Pressurized Water Reactor Fuel Cladding

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

Robinson, Sharon M.; Chattin, Marc Rhea; Giaquinto, Joseph

2015-09-01

It is expected that tritium pretreatment will be required in future reprocessing plants to prevent the release of tritium to the environment (except for long-cooled fuels). To design and operate future reprocessing plants in a safe and environmentally compliant manner, the amount and form of tritium in the used nuclear fuel (UNF) must be understood and quantified. Tritium in light water reactor (LWR) fuel is dispersed between the fuel matrix and the fuel cladding, and some tritium may be in the plenum, probably as tritium labelled water (THO) or T 2O. In a standard processing flowsheet, tritium management would bemore » accomplished by treatment of liquid streams within the plant. Pretreating the fuel prior to dissolution to release the tritium into a single off-gas stream could simplify tritium management, so the removal of tritium in the liquid streams throughout the plant may not be required. The fraction of tritium remaining in the cladding may be reduced as a result of tritium pretreatment. Since Zircaloy® cladding makes up roughly 25% by mass of UNF in the United States, processes are being considered to reduce the volume of reprocessing waste for Zircaloy® clad fuel by recovering the zirconium from the cladding for reuse. These recycle processes could release the tritium in the cladding. For Zircaloy-clad fuels from light water reactors, the tritium produced from ternary fission and other sources is expected to be divided between the fuel, where it is generated, and the cladding. It has been previously documented that a fraction of the tritium produced in uranium oxide fuel from LWRs can migrate and become trapped in the cladding. Estimates of the percentage of tritium in the cladding typically range from 0–96%. There is relatively limited data on how the tritium content of the cladding varies with burnup and fuel history (temperature, power, etc.) and how pretreatment impacts its release. To gain a better understanding of how tritium in cladding will behave during processing, scoping tests are being performed to determine the tritium content in the cladding pre- and post-tritium pretreatment. Samples of Surry-2 and H.B. Robinson pressurized water reactor cladding were heated to 1100–1200°C to oxidize the zirconium and release all of the tritium in the cladding sample. Cladding samples were also heated within the temperature range of 480–600ºC expected for standard air tritium pretreatment systems, and to a slightly higher temperature (700ºC) to determine the impact of tritium pretreatment on tritium release from the cladding. The tritium content of the Surry-2 and H.B. Robinson cladding was measured to be ~234 and ~500 µCi/g, respectively. Heating the Surry-2 cladding at 500°C for 24 h removed ~0.2% of the tritium from the cladding, and heating at 700°C for 24 h removed ~9%. Heating the H.B. Robinson cladding at 700°C for 24 h removed ~11% of the tritium. When samples of the Surry-2 and H.B. Robinson claddings were heated at 700°C for 96 h, essentially all of the tritium in the cladding was removed. However, only ~3% of the tritium was removed when a sample of Surry-2 cladding was heated at 600°C for 96 h. These data indicate that the amount of tritium released from tritium pretreatment systems will be dependent on both the operating temperature and length of time in the system. Under certain conditions, a significant fraction of the tritium could remain bound in the cladding and would need to be considered in operations involving cladding recycle.« less

Surrogate fuel assembly multi-axis shaker tests to simulate normal conditions of rail and truck transport

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

McConnell, Paul E.; Koenig, Greg John; Uncapher, William Leonard

2016-05-01

This report describes the third set of tests (the “DCLa shaker tests”) of an instrumented surrogate PWR fuel assembly. The purpose of this set of tests was to measure strains and accelerations on Zircaloy-4 fuel rods when the PWR assembly was subjected to rail and truck loadings simulating normal conditions of transport when affixed to a multi-axis shaker. This is the first set of tests of the assembly simulating rail normal conditions of transport.

Surrogate fuel assembly multi-axis shaker tests to simulate normal conditions of rail and truck transport

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

McConnell, Paul E.; Koenig, Greg John; Uncapher, William Leonard

2016-05-12

This report describes the third set of tests (the “DCL a shaker tests”) of an instrumented surrogate PWR fuel assembly. The purpose of this set of tests was to measure strains and accelerations on Zircaloy-4 fuel rods when the PWR assembly was subjected to rail and truck loadings simulating normal conditions of transport when affixed to a multi-axis shaker. This is the first set of tests of the assembly simulating rail normal conditions of transport.

Mechanical and thermal properties of bulk ZrB2

NASA Astrophysics Data System (ADS)

Nakamori, Fumihiro; Ohishi, Yuji; Muta, Hiroaki; Kurosaki, Ken; Fukumoto, Ken-ichi; Yamanaka, Shinsuke

2015-12-01

ZrB2 appears to have formed in the fuel debris at the Fukushima Daiichi nuclear disaster site, through the reaction between Zircaloy cladding materials and the control rod material B4C. Since ZrB2 has a high melting point of 3518 K, the ceramic has been widely studied as a heat-resistant material. Although various studies on the thermochemical and thermophysical properties have been performed for ZrB2, significant differences exist in the data, possibly due to impurities or the porosity within the studied samples. In the present study, we have prepared a ZrB2 bulk sample with 93.1% theoretical density by sintering ZrB2 powder. On this sample, we have comprehensively examined the thermal and mechanical properties of ZrB2 by the measurement of specific heat, ultrasonic sound velocities, thermal diffusivity, and thermal expansion. Vickers hardness and fracture toughness were also measured and found to be 13-23 GPa and 1.8-2.8 MPa m0.5, respectively. The relationships between these properties were carefully examined in the present study.

Effect of negative bias on TiAlSiN coating deposited on nitrided Zircaloy-4

NASA Astrophysics Data System (ADS)

Jun, Zhou; Zhendong, Feng; Xiangfang, Fan; Yanhong, Liu; Huanlin, Li

2018-01-01

TiAlSiN coatings were deposited on the nitrided Zircaloy-4 by multi-arc ion plating at -100 V, -200 V and -300 V. In this study, the high temperature oxidation behavior of coatings was tested by a box-type resistance furnace in air for 3 h at 800 °C; the macro-morphology of coatings was observed and analyzed by a zoom-stereo microscope; the micro-morphology of coatings was analyzed by a scanning electron microscopy (SEM), and the chemical elements of samples were analyzed by an energy dispersive spectroscopy(EDS); the adhesion strength of the coating to the substrate was measured by an automatic scratch tester; and the phases of coatings were analyzed by an X-ray diffractometer(XRD). Results show that the coating deposited at -100 V shows better high temperature oxidation resistance behavior, at the same time, Al elements contained in the coating is of the highest amount, meanwhile, the adhesion strength of the coating to the substrate is the highest, which is 33N. As the bias increases, high temperature oxidation resistance behavior of the coating weakens first and then increases, the amount of large particles on the surface of the coating increases first and then decreases whereas the density of the coating decreases first and then increases, and adhesion strength of the coating to the substrate increases first and then weakens. The coating's quality is relatively poor when the bias is -200 V.

Nuclear Energy Advanced Modeling and Simulation (NEAMS) Accident Tolerant Fuels High Impact Problem: Coordinate Multiscale U 3Si 2 Modeling

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

Gamble, K. A.; Hales, J. D.; Miao, Y.

Since the events at the Fukushima-Daiichi nuclear power plant in March 2011 significant research has unfolded at national laboratories, universities and other institutions into alternative materials that have potential enhanced accident tolerance when compared to traditional \\uo~fuel zircaloy clad fuel rods. One of the potential replacement fuels is uranium silicide (\\usi) for its higher thermal conductivity and uranium density. The lower melting temperature is of potential concern during postulated accident conditions. Another disadvantage for \\usi~ is the lack of experimental data under power reactor conditions. Due to the aggressive development schedule for inserting some of the potential materials into leadmore » test assemblies or rods by 2022~\\cite{bragg-sitton_2014} multiscale multiphysics modeling approaches have been used to provide insight into these materials. \\\\ \

Pre-irradiation testing and analysis to support the LWRS Hybrid SiC-CMC-Zircaloy-04 unfueled rodlet irradiation

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

Isabella J van Rooyen

2012-09-01

Nuclear fuel performance is a significant driver of nuclear power plant operational performance, safety, economics and waste disposal requirements. The Advanced Light Water Reactor (LWR) Nuclear Fuel Development Pathway focuses on improving the scientific knowledge basis to enable the development of high-performance, high burn-up fuels with improved safety and cladding integrity and improved nuclear fuel cycle economics. To achieve significant improvements, fundamental changes are required in the areas of nuclear fuel composition, cladding integrity, and fuel/cladding interaction.

Pre-irradiation testing and analysis to support the LWRS Hybrid SiC-CMC-Zircaloy-04 unfueled rodlet irradiation

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

Isabella J van Rooyen

2013-01-01

Nuclear fuel performance is a significant driver of nuclear power plant operational performance, safety, economics and waste disposal requirements. The Advanced Light Water Reactor (LWR) Nuclear Fuel Development Pathway focuses on improving the scientific knowledge basis to enable the development of high-performance, high burn-up fuels with improved safety and cladding integrity and improved nuclear fuel cycle economics. To achieve significant improvements, fundamental changes are required in the areas of nuclear fuel composition, cladding integrity, and fuel/cladding interaction.

Corrosion evaluation of N reactor pressure tube 1756

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

Larrick, A.P.

1967-10-26

N Reactor Zircaloy-2 pressure tube No. 1756 and its associated ASTM A234 steel nozzles were examined for corrosion and hydrogen content after approximately 300 days exposure in-reactor. Visual examination showed tight, adherent, dull black oxides in the pressure tube except for scratching in the bottom due to sliding of fuel and fuel spacers through the tube during charge- discharge operations. Several fretted areas up to $sup 3$/$sub 8$ inch wide by $sup 1$/$sub 2$ inch long by up to 13 mils deep were observed at the downstream end--these pits were caused by vibration of the fuel spacers against the pressuremore » tube. Hydrogen levels were fairly constant along the tube length with an average of about 19 +- 6 ppm except at one location. At approximately 30 inches from the front end of the tube a sharp peak to a maximum of 58 ppm hydrogen occurred. The reason for the peak is unknown. (auth)« less

Microstructure studies of interdiffusion behavior of U 3Si 2/Zircaloy-4 at 800 and 1000 °C

DOE PAGES

He, Lingfeng; Harp, Jason M.; Hoggan, Rita E.; ...

2017-01-22

Fuel swelling during normal reactor operations could lead to unfavorable chemical interactions when in contact with its cladding. As new fuel types are developed, it is crucial to understand the interaction behavior between fuel and its cladding. Diffusion experiments between U 3Si 2 and Zricaloy-4 (Zry-4) were conducted at 800 and 1000°C up to 100 hours. The microstructure of pristine U 3Si 2 and U 3Si 2/Zry-4 interdiffusion products were examined using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) equipped with an energy dispersive X-ray spectroscopy (EDS) system. The primary interdiffusion product observed at 800°C is ZrSi 2,more » with secondary phases of U-Zr in the Zry-4, and Fe-Cr-W-Zr-Si phases at Zry-4/ZrSi 2 interface and Fe-Cr-U-Si phases at ZrSi 2/U-Si interface. As a result, the primary interdiffusion products at 1000°C were Zr 2Si, U-Zr-Fe-Ni, U, U-Zr, and a low melting point phase U 6Fe.« less

Fully Ceramic Microencapsulated Fuel Development for LWR Applications

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

Snead, Lance Lewis; Besmann, Theodore M; Terrani, Kurt A

2012-01-01

The concept, fabrication, and key feasibility issues of a new fuel form based on the microencapsulated (TRISO-type) fuel which has been specifically engineered for LWR application and compacted within a SiC matrix will be presented. This fuel, the so-called fully ceramic microencapsulated fuel is currently undergoing development as an accident tolerant fuel for potential UO2 replacement in commercial LWRs. While the ability of this fuel to facilitate normal LWR cycle performance is an ongoing effort within the program, this will not be a focus of this paper. Rather, key feasibility and performance aspects of the fuel will be presented includingmore » the ability to fabricate a LWR-specific TRISO, the need for and route to a high thermal conductivity and fully dense matrix that contains neutron poisons, and the performance of that matrix under irradiation and the interaction of the fuel with commercial zircaloy clad.« less

Irradiation effects on thermal properties of LWR hydride fuel

NASA Astrophysics Data System (ADS)

Terrani, Kurt; Balooch, Mehdi; Carpenter, David; Kohse, Gordon; Keiser, Dennis; Meyer, Mitchell; Olander, Donald

2017-04-01

Three hydride mini-fuel rods were fabricated and irradiated at the MIT nuclear reactor with a maximum burnup of 0.31% FIMA or ∼5 MWd/kgU equivalent oxide fuel burnup. Fuel rods consisted of uranium-zirconium hydride (U (30 wt%)ZrH1.6) pellets clad inside a LWR Zircaloy-2 tubing. The gap between the fuel and the cladding was filled with lead-bismuth eutectic alloy to eliminate the gas gap and the large temperature drop across it. Each mini-fuel rod was instrumented with two thermocouples with tips that are axially located halfway through the fuel centerline and cladding surface. In-pile temperature measurements enabled calculation of thermal conductivity in this fuel as a function of temperature and burnup. In-pile thermal conductivity at the beginning of test agreed well with out-of-pile measurements on unirradiated fuel and decreased rapidly with burnup.

Evaluation of a Zirconium Recycle Scrubber System

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

Spencer, Barry B.; Bruffey, Stephanie H.

2017-04-01

A hot-cell demonstration of the zirconium recycle process is planned as part of the Materials Recovery and Waste Forms Development (MRWFD) campaign. The process treats Zircaloy® cladding recovered from used nuclear fuel with chlorine gas to recover the zirconium as volatile ZrCl4. This releases radioactive tritium trapped in the alloy, converting it to volatile tritium chloride (TCl). To meet regulatory requirements governing radioactive emissions from nuclear fuel treatment operations, the capture and retention of a portion of this TCl may be required prior to discharge of the off-gas stream to the environment. In addition to demonstrating tritium removal from amore » synthetic zirconium recycle off-gas stream, the recovery and quantification of tritium may refine estimates of the amount of tritium present in the Zircaloy cladding of used nuclear fuel. To support these objectives, a bubbler-type scrubber was fabricated to remove the TCl from the zirconium recycle off-gas stream. The scrubber was fabricated from glass and polymer components that are resistant to chlorine and hydrochloric acid solutions. Because of concerns that the scrubber efficiency is not quantitative, tests were performed using DCl as a stand-in to experimentally measure the scrubbing efficiency of this unit. Scrubbing efficiency was ~108% ± 3% with water as the scrubber solution. Variations were noted when 1 M NaOH scrub solution was used, values ranged from 64% to 130%. The reason for the variations is not known. It is recommended that the equipment be operated with water as the scrubbing solution. Scrubbing efficiency is estimated at 100%.« less

Modelling of the Gadolinium Fuel Test IFA-681 using the BISON Code

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

Pastore, Giovanni; Hales, Jason Dean; Novascone, Stephen Rhead

2016-05-01

In this work, application of Idaho National Laboratory’s fuel performance code BISON to modelling of fuel rods from the Halden IFA-681 gadolinium fuel test is presented. First, an overview is given of BISON models, focusing on UO2/UO2-Gd2O3 fuel and Zircaloy cladding. Then, BISON analyses of selected fuel rods from the IFA-681 test are performed. For the first time in a BISON application to integral fuel rod simulations, the analysis is informed by detailed neutronics calculations in order to accurately capture the radial power profile throughout the fuel, which is strongly affected by the complex evolution of absorber Gd isotopes. Inmore » particular, radial power profiles calculated at IFE–Halden Reactor Project with the HELIOS code are used. The work has been carried out in the frame of the collaboration between Idaho National Laboratory and Halden Reactor Project. Some slide have been added as an Appendix to present the newly developed PolyPole-1 algorithm for modeling of intra-granular fission gas release.« less

Hydrogen pickup mechanism of zirconium alloys

NASA Astrophysics Data System (ADS)

Couet, Adrien

Although the optimization of zirconium based alloys has led to significant improvements in hydrogen pickup and corrosion resistance, the mechanisms by which such alloy improvements occur are still not well understood. In an effort to understand such mechanisms, a systematic study of the alloy effect on hydrogen pickup is conducted, using advanced characterization techniques to rationalize precise measurements of hydrogen pickup. The hydrogen pick-up fraction is accurately measured for a specially designed set of commercial and model alloys to investigate the effects of alloying elements, microstructure and corrosion kinetics on hydrogen uptake. Two different techniques to measure hydrogen concentrations were used: a destructive technique, Vacuum Hot Extraction, and a non-destructive one, Cold Neutron Prompt Gamma Activation Analysis. The results indicate that hydrogen pickup varies not only from alloy to alloy but also during the corrosion process for a given alloy. For instance Zircaloy type alloys show high hydrogen pickup fraction and sub-parabolic oxidation kinetics whereas ZrNb alloys show lower hydrogen pickup fraction and close to parabolic oxidation kinetics. Hypothesis is made that hydrogen pickup result from the need to balance charge during the corrosion reaction, such that the pickup of hydrogen is directly related to (and indivisible of) the corrosion mechanism and decreases when the rate of electron transport or oxide electronic conductivity sigmao xe through the protective oxide increases. According to this hypothesis, alloying elements (either in solid solution or in precipitates) embedded in the oxide as well as space charge variations in the oxide would impact the hydrogen pick-up fraction by modifying sigmaox e, which drives oxidation and hydriding kinetics. Dedicated experiments and modelling were performed to assess and validate these hypotheses. In-situ electrochemical impedance spectroscopy (EIS) experiments were performed on Zircaloy-4 tubes to directly measure the evolution of sigma oxe as function of exposure time. The results show that sigmao xe decreases as function of exposure time and that its variations are directly correlated to the instantaneous hydrogen pickup fraction variations. The electron transport through the oxide layer is thus altered as the oxide grows, reasons for which are yet to be exactly determined. Preliminary results also show that sigma oxe of ZrNb alloys would be much higher compared with Zircaloy-4. Thus, it is confirmed that sigmaox e is a key parameter in the hydrogen and oxidation mechanism. Because the mechanism whereby alloying elements are incorporated into the oxide layer is critical to changing sigmao xe, the evolution of the oxidation state of two common alloying elements, Fe and Nb, when incorporated into the growing oxide layers is investigated using X-Ray Absorption Near-Edge Spectroscopy (XANES) using micro-beam synchrotron radiation on cross sectional oxide samples. The results show that the oxidation of both Fe and Nb is delayed in the oxide layer compared to that of Zr, and that this oxidation delay is related to the variations of the instantaneous hydrogen pick-up fraction with exposure time. The evolution of Nb oxidation as function of oxide depth is also compatible with space charge compensation in the oxide and with an increase in sigmaox e of ZrNb alloys compared to Zircaloys. Finally, various successively complex models from the well-known Wagner oxidation theory to the more complex effect of space charge on oxidation kinetics have been developed. The general purpose of the modeling effort is to provide a rationale for the sub-parabolic oxidation kinetics and demonstrate the correlation with hydrogen pickup fraction. It is directly demonstrated that parabolic oxidation kinetics is associated with high sigmao xe and low space charges in the oxide whereas sub-parabolic oxidation kinetics is associated with lower sigmaox e and higher space charge in the oxide. All these observations helped us to propose a general corrosion mechanism of zirconium alloys involving both oxidation and hydrogen pickup mechanism to better understand and predict the effect of alloying additions on the behavior of zirconium alloys.

Development and Validation of Accident Models for FeCrAl Cladding

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

Gamble, Kyle Allan Lawrence; Hales, Jason Dean

2016-08-01

The purpose of this milestone report is to present the work completed in regards to material model development for FeCrAl cladding and highlight the results of applying these models to Loss of Coolant Accidents (LOCA) and Station Blackouts (SBO). With the limited experimental data available (essentially only the data used to create the models) true validation is not possible. In the absence of another alternative, qualitative comparisons during postulated accident scenarios between FeCrAl and Zircaloy-4 cladded rods have been completed demonstrating the superior performance of FeCrAl.

Thermodynamic modelling of the C-U and B-U binary systems

NASA Astrophysics Data System (ADS)

Chevalier, P. Y.; Fischer, E.

2001-02-01

The thermodynamic modelling of the carbon-uranium (C-U) and boron-uranium (B-U) binary systems is being performed in the framework of the development of a thermodynamic database for nuclear materials, for increasing the basic knowledge of key phenomena which may occur in the event of a severe accident in a nuclear power plant. Applications are foreseen in the nuclear safety field to the physico-chemical interaction modelling, on the one hand the in-vessel core degradation producing the corium (fuel, zircaloy, steel, control rods) and on the other hand the ex-vessel molten corium-concrete interaction (MCCI). The key O-U-Zr ternary system, previously modelled, allows us to describe the first interaction of the fuel with zircaloy cladding. Then, the three binary systems Fe-U, Cr-U and Ni-U were modelled as a preliminary work for modelling the O-U-Zr-Fe-Cr-Ni multicomponent system, allowing us to introduce the steel components in the corium. In the existing database (TDBCR, thermodynamic data base for corium), Ag and In were introduced for modelling AIC (silver-indium-cadmium) control rods which are used in French pressurized water reactors (PWR). Elsewhere, B 4C is also used for control rods. That is why it was agreed to extend in the next years the database with two new components, B and C. Such a work needs the thermodynamic modelling of all the binary and pseudo-binary sub-systems resulting from the combination of B, B 2O 3 and C with the major components of TDBCR, O-U-Zr-Fe-Cr-Ni-Ag-In-Ba-La-Ru-Sr-Al-Ca-Mg-Si + Ar-H. The critical assessment of the very numerous experimental information available for the C-U and B-U binary systems was performed by using a classical optimization procedure and the Scientific Group Thermodata Europe (SGTE). New optimized Gibbs energy parameters are given, and comparisons between calculated and experimental equilibrium phase diagrams or thermodynamic properties are presented. The self-consistency obtained is quite satisfactory.

Development of a (147)Pm source for beta-backscatter thickness gauge applications.

PubMed

Kumar, Manoj; Udhayakumar, J; Nuwad, J; Shukla, Rakesh; Pillai, C G S; Dash, Ashutosh; Venkatesh, Meera

2011-03-01

This paper describes a method for the preparation of (147)Pm sources, utilized in the determination of graphite coating thickness on the inner surface of the zircaloy cladding tube of nuclear fuels. (147)Pm was adsorbed on a limited surface area [1.5mm (ϕ)×2mm (l)] of a cylindrical aluminum rod [1.5mm (ϕ)×10mm (l)]. In brief, the selected tip area [1.5mm (ϕ)×2mm (l)] was anodized at a current density of 15mA/cm(2) at 15°C in 3M·H(2)SO(4) for 2h followed by immersion of this area in 10μL of (147)Pm solution containing 37MBq (1mCi) of activity at pH 6.0 for 24h. The radioactive area was subsequently covered with a thin layer of Polymethyl Methacrylate (PMMA) to prevent leaching of (147)Pm from the source. The quantity of incorporated (147)Pm activity was assayed in a calibrated ion chamber. Quality control tests were carried out to ensure nonleachability, uniform distribution of activity and stability of the sources. Copyright © 2010 Elsevier Ltd. All rights reserved.

High-temperature oxidation kinetics of sponge-based E110 cladding alloy

DOE PAGES

Yan, Yong; Garrison, Benton E.; Howell, Mike; ...

2017-11-03

Two-sided oxidation experiments were recently conducted at 900°C–1200 °C in flowing steam with samples of sponge-based Zr-1Nb alloy E110. Although the old electrolytic E110 tubing exhibited a high degree of susceptibility to nodular corrosion and experienced breakaway oxidation rates in a relatively short time, the new sponge-based E110 demonstrated steam oxidation behavior comparable to Zircaloy-4. Sample weight gain and oxide layer thickness measurements were performed on oxidized E110 specimens and compared to oxygen pickup and oxide layer thickness calculations using the Cathcart-Pawel correlation. Our study shows that the sponge-based E110 follows the parabolic law at temperatures above 1015 °C. Atmore » or below 1015 °C, the oxidation rate was very low when compared to Zircaloy-4 and can be represented by a cubic expression. No breakaway oxidation was observed at 1000 °C for oxidation times up to 10,000 s. Arrhenius expressions are given to describe the parabolic rate constants at temperatures above 1015 °C and cubic rate constants are provided for temperatures below 1015 °C. The weight gains calculated by our equations are in excellent agreement with the measured sample weight gains at all test temperatures. In addition to the as-fabricated E110 cladding sample, prehydrided E110 cladding with hydrogen concentrations in the 100–150 wppm range was also investigated. The effect of hydrogen content on sponge-based E110 oxidation kinetics was minimal. No significant difference was found between as-fabricated and hydrided samples with regard to oxygen pickup and oxide layer thickness for hydrogen contents below 150 wppm.« less

Interpretation of the results of the CORA-33 dry core BWR test

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

Ott, L.J.; Hagen, S.

All BWR degraded core experiments performed prior to CORA-33 were conducted under ``wet`` core degradation conditions for which water remains within the core and continuous steaming feeds metal/steam oxidation reactions on the in-core metallic surfaces. However, one dominant set of accident scenarios would occur with reduced metal oxidation under ``dry`` core degradation conditions and, prior to CORA-33, this set had been neglected experimentally. The CORA-33 experiment was designed specifically to address this dominant set of BWR ``dry`` core severe accident scenarios and to partially resolve phenomenological uncertainties concerning the behavior of relocating metallic melts draining into the lower regions ofmore » a ``dry`` BWR core. CORA-33 was conducted on October 1, 1992, in the CORA tests facility at KfK. Review of the CORA-33 data indicates that the test objectives were achieved; that is, core degradation occurred at a core heatup rate and a test section axial temperature profile that are prototypic of full-core nuclear power plant (NPP) simulations at ``dry`` core conditions. Simulations of the CORA-33 test at ORNL have required modification of existing control blade/canister materials interaction models to include the eutectic melting of the stainless steel/Zircaloy interaction products and the heat of mixing of stainless steel and Zircaloy. The timing and location of canister failure and melt intrusion into the fuel assembly appear to be adequately simulated by the ORNL models. This paper will present the results of the posttest analyses carried out at ORNL based upon the experimental data and the posttest examination of the test bundle at KfK. The implications of these results with respect to degraded core modeling and the associated safety issues are also discussed.« less

Microstructure evolution of recrystallized Zircaloy-4 under charged particles irradiation

NASA Astrophysics Data System (ADS)

Gaumé, M.; Onimus, F.; Dupuy, L.; Tissot, O.; Bachelet, C.; Mompiou, F.

2017-11-01

Recrystallized zirconium alloys are used as nuclear fuel cladding tubes of Pressurized Water Reactors. During operation, these alloys are submitted to fast neutron irradiation which leads to their in-reactor deformation and to a change of their mechanical properties. These phenomena are directly related to the microstructure evolution under irradiation and especially to the formation of -type dislocation loops. In the present work, the radiation damage evolution in recrystallized Zircaloy-4 has been studied using charged particles irradiation. The loop nucleation and growth kinetics, and also the helical climb of linear dislocations, were observed in-situ using a High Voltage Electron Microscope (HVEM) under 1 MeV electron irradiation at 673 and 723 K. In addition, 600 keV Zr+ ion irradiations were conducted at the same temperature. Transmission Electron Microscopy (TEM) characterizations have been performed after both types of irradiations, and show dislocation loops with a Burgers vector belonging to planes close to { 10 1 bar 0 } first order prismatic planes. The nature of the loops has been characterized. Only interstitial dislocation loops have been observed after ion irradiation at 723 K. However, after electron irradiation conducted at 673 and 723 K, both interstitial and vacancy loops were observed, the proportion of interstitial loops increasing as the temperature is increased. The loop growth kinetics analysis shows that as the temperature increases, the loop number density decreases and the loop growth rate tends to increase. An increase of the flux leads to an increase of the loop number density and a decrease of the loop growth rate. The results are compared to previous works and discussed in the light of point defects diffusion.

High-temperature oxidation kinetics of sponge-based E110 cladding alloy

NASA Astrophysics Data System (ADS)

Yan, Yong; Garrison, Benton E.; Howell, Mike; Bell, Gary L.

2018-02-01

Two-sided oxidation experiments were recently conducted at 900°C-1200 °C in flowing steam with samples of sponge-based Zr-1Nb alloy E110. Although the old electrolytic E110 tubing exhibited a high degree of susceptibility to nodular corrosion and experienced breakaway oxidation rates in a relatively short time, the new sponge-based E110 demonstrated steam oxidation behavior comparable to Zircaloy-4. Sample weight gain and oxide layer thickness measurements were performed on oxidized E110 specimens and compared to oxygen pickup and oxide layer thickness calculations using the Cathcart-Pawel correlation. Our study shows that the sponge-based E110 follows the parabolic law at temperatures above 1015 °C. At or below 1015 °C, the oxidation rate was very low when compared to Zircaloy-4 and can be represented by a cubic expression. No breakaway oxidation was observed at 1000 °C for oxidation times up to 10,000 s. Arrhenius expressions are given to describe the parabolic rate constants at temperatures above 1015 °C and cubic rate constants are provided for temperatures below 1015 °C. The weight gains calculated by our equations are in excellent agreement with the measured sample weight gains at all test temperatures. In addition to the as-fabricated E110 cladding sample, prehydrided E110 cladding with hydrogen concentrations in the 100-150 wppm range was also investigated. The effect of hydrogen content on sponge-based E110 oxidation kinetics was minimal. No significant difference was found between as-fabricated and hydrided samples with regard to oxygen pickup and oxide layer thickness for hydrogen contents below 150 wppm.

The European scene regarding spallation neutron sources

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

Bauer, G.S.

1996-06-01

In Europe, a short pulse spallation neutron source, ISIS, has been operating for over 10 years, working its way up to a beam power level of 200 kW. A continuous source, SINQ, designed for a beam power of up to 1 MW, is scheduled to start operating at the end of 1996, and a detailed feasibility study has been completed for a 410 kW short pulse source, AUSTRON. Each of these sources seems to have settled for a target concept which is at or near the limits of its feasibility: The ISIS depleted uranium plate targets, heavy water cooled andmore » Zircaloy clad, have so far not shown satisfactory service time and operation is likely to continue with a Ta-plate target, which, in the past has been used successfully for the equivalent of one full-beam-year before it was taken out of service due to degrading thermal properties. SINQ will initially use a rod target, made of Zircaloy only, but plans exist to move on to clad lead rods as quickly as possible. Apart from the not yet explored effect of hydrogen and helium production, there are also concerns about the generation of 7-Be in the cooling water from the spallation of oxygen, which might result in undesirably high radioactivity in the cooling plant room. A Liquid metal target, also under investigation for SINQ, would not only reduce this problem to a level of about 10 %, but would also minimize the risk of radiolytic corrosion in the beam interaction zone. Base on similar arguments, AUSTRON has been designed for edge cooled targets, but thermal and stress analyses show, that this concept is not feasible at higher power levels.« less

Development of new ferritic steels as cladding material for metallic fuel fast breeder reactor

NASA Astrophysics Data System (ADS)

Tokiwai, Moriyasu; Horie, Masaaki; Kako, Kenji; Fujiwara, Masayuki

1993-09-01

The excellent thermal, chemical and neutronic properties of metallic fuel (U-Pu-Zr alloy) will lead to drastic improvements in fast reactor safety and the related fuel cycle economy. Some new high molybdenum 12Cr ferritic stainless steel candidate cladding alloys have been designed to achieve the mechanical properties required for high performance metallic fuel elements. These candidate claddings were irradiated by ion bombardment and tested to determine their strength and creep rupture properties. A 12Cr-8Mo and a 12Cr-8Mo-0.1Y 2O 3 steel were fabricated into cladding via a powder metallurgy process and by a mechanical alloying process, respectively. These claddings had two and three times the creep rupture strength (pressurized at 650°C for 10000 h) of a conventional 12Cr ferritic steel (HT-9). These two steels also showed no void formation up to 350 dpa by Ni 3+ irradiation. A zircaloy-2 lined steel cladding tube has also been fabricated for the purpose of reducing fuel-cladding interdiffusion and chemical interaction.

Fabrication of seamless calandria tubes by cold pilgering route using 3-pass and 2-pass schedules

NASA Astrophysics Data System (ADS)

Saibaba, N.

2008-12-01

Calandria tube is a large diameter, extremely thin walled zirconium alloy tube which has diameter to wall thickness ratio as high as 90-95. Such tubes are conventionally produced by the 'welded route', which involves extrusion of slabs followed by a series of hot and cold rolling passes, intermediate anneals, press forming of sheets into circular shape and closing the gap by TIG welding. Though pilgering is a well established process for the fabrication of seamless tubes, production of extremely thin walled tubes offers several challenges during pilgering. Nuclear fuel complex (NFC), Hyderabad, has successfully developed a process for the production of Zircaloy-4 calandria tubes by adopting the 'seamless route' which involves hot extrusion of mother blanks followed by three-pass pilgering or two-pass pilgering schedules. This paper deals with standardization of the seamless route processes for fabrication of calandria tubes, comparison between the tubes produced by 2-pass and 3-pass pilgering schedules, role of ultrasonic test charts for control of process parameters, development of new testing methods for burst testing and other properties.

Radiation chemistry related to nuclear power technology

NASA Astrophysics Data System (ADS)

Ishigure, Kenkichi

A brief review is given to the radiation chemical problems, especially with the emphasis on water radiolysis, in the nuclear power technology. Radiation chemistry in aqueous system is pointed out to be closely related to the problems such as corrosion of Zircaloy, the formation of insoluble corrosion products or crud, stress corrosion cracking of stainless steel in BWR and the radioactive waste managements. The results of the constant extention rate tests on sensitized 304 stainless steel under irradiation are shown, and the computer calculations were carried out to simulate the model experiments on the release of crud from the corroding surface under irradiation and also the water radiolysis in core of BWR.

Fuel inspection and reconstitution experience at Surry Power Station

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

Brookmire, T.A.

Surry Power Station, located on the James River near Williamsburg, Virginia, has two Westinghouse pressurized water reactors. Unit 2 consistently sets a high standard of fuel performance (no indication of fuel failures in recent cycles), while unit 1, since cycle 6, has been plagued with numerous fuel failures. Both Surry units operate with Westinghouse standard 15 x 15 fuel. Virginia Power management set goals to reduce the coolant activity, thus reducing person-rem exposure and the associated costs of high coolant activity. To achieve this goal, extensive fuel examination campaigns were undertaken that included high-magnification video inspectionsa, debris cleaning, wet andmore » vacuum fuel sipping, fuel rod ultrasonic testing, and eddy current examination. In the summer of 1985, during cycle 8 operation, Kraftwerk Union reconstituted (repaired) the damage, once-burned assemblies from cycles 6 and 7 by replacing failed fuel rods with solid Zircaloy-4 rods. Currently, cycle 9 has operated for 5 months without any indication of fuel failure (the cycle 9 core has two reconstituted assemblies).« less

Modeling Early-Stage Processes of U-10 Wt.%Mo Alloy Using Integrated Computational Materials Engineering Concepts

NASA Astrophysics Data System (ADS)

Wang, Xiaowo; Xu, Zhijie; Soulami, Ayoub; Hu, Xiaohua; Lavender, Curt; Joshi, Vineet

2017-12-01

Low-enriched uranium alloyed with 10 wt.% molybdenum (U-10Mo) has been identified as a promising alternative to high-enriched uranium. Manufacturing U-10Mo alloy involves multiple complex thermomechanical processes that pose challenges for computational modeling. This paper describes the application of integrated computational materials engineering (ICME) concepts to integrate three individual modeling components, viz. homogenization, microstructure-based finite element method for hot rolling, and carbide particle distribution, to simulate the early-stage processes of U-10Mo alloy manufacture. The resulting integrated model enables information to be passed between different model components and leads to improved understanding of the evolution of the microstructure. This ICME approach is then used to predict the variation in the thickness of the Zircaloy-2 barrier as a function of the degree of homogenization and to analyze the carbide distribution, which can affect the recrystallization, hardness, and fracture properties of U-10Mo in subsequent processes.

Critical Safe Disposal of Spent Fuel: Behavior of Neutron Poisons

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

Kienzler, Bernhard; Gmal, Bernhard

2007-07-01

In contrast to Yucca Mountain, European repository concepts rely on deep underground conditions which guarantee permanently a reducing geochemical environment. As long as no water comes into contact with the disposed nuclear fuel, criticality is excluded by compliance with the disposal conditions (limitation of U/Pu in the canisters). Penetration of water into the canister may also be considered as a scenario. However, water in a disposal results in geochemical reactions proceeding over very long periods of time: (1) Presence of water allows the corrosion of the steel of the canister material forming hydrogen and iron corrosion products. (2) Hydrogen pressuresmore » affect the zircaloy cladding even at low temperatures. Failure of fuel cladding and spacers leads to changes in the geometrical configuration. (3) UO{sub 2} matrix corrosion results in geochemically controlled reformation of secondary phase. (4) Even if the dissolution rate of UO{sub 2} is low, elements accounting for burnup credit do not behave similar as uranium. Geochemical reactions are analyzed in detail and compositions are presented which have a high probability to be formed in the long-term needing to be analyzed with respect to K{sub eff}. (authors)« less

CVTR PROJECT. CAROLINAS VIRGINIA NUCLEAR POWER ASSOCIATES, INC. MONTHLY PROGRESS REPORT, MAY 1961

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

None

1961-10-31

The capsule A-2 was removed from the WTR reflector hole at the end of the WTR Cycle 13, and was stored in the WTR canal. The in-pile loop has operated for eight months and the test thimble was irradiated a total of 108 days. Tensile tests were completed on the extruded and annealed Zircaloy-4 Phase-II pressure tubes. The tensile properties varied with location in the pressure tube. The lowest values were obtained in the top flange where the material was fully annealed for ten hours at 800 deg C. Increased properties were achieved from working the material during extrusion operations.more » A shielding ring is provided to prevent streaming through a void generated by the rotating shield volley supports. It was determined that an additional thickness of iron or steel is required to compensate for the loss of shielding from the removal of one foot of concrete at the bottom of the trench. Various portions of the U-tube and fuel assemblies were homogenized in various axial regions for computer studies. The studies indicated a decrease of 500 hours in core life from non-uniform axial burnup. Pressure tube specimens are being tested under the impulsive test burst program. A test specimen experienced a 51% increase in O.D. under 20 impact blows before it failed. Observations of the tested specimens indicated ductilities far in excess of those predicted from the material's behavior in uniaxial tension. Teste on a Zircaloy-stainless steel joint were concluded after an extensive program of testing under various pressure, temperature and bending moment conditions. No sign of leakage was noted throughout the program. Subsequent inspection of the joint showed cracks in the sleeve portion of the joint. Analysis of the test water indicated a chloride content of approx 88 ppm. A test fuel assembly was dismantled and converted to a four baffle design. Modifications were made to the prototype control-rod-drive system. The alignment between ths vertical and horizontal miter gears was improved by charging the mounting of horizontal shaft and bearings. Scram tests were resumed; these tests indicated that the dashpot was acting too soon. The dashpot is being modified. (auth)« less

Laser and Pressure Resistance Weld of Thin-Wall Cladding for LWR Accident-Tolerant Fuels

NASA Astrophysics Data System (ADS)

Gan, J.; Jerred, N.; Perez, E.; Haggard, D. C.

2017-12-01

FeCrAl alloy with typical composition of approximately Fe-15Cr-5Al is considered a primary candidate cladding material for light water reactor accident-tolerant fuel because of its superior resistance to oxidation in high-temperature steam compared with Zircaloy cladding. Thin-walled FeCrAl cladding at 350 μm wall thickness is required, and techniques for joining endplug to cladding need to be developed. Fusion-based laser weld and solid-state joining with pressure resistance weld were investigated in this study. The results of microstructural characterization, mechanical property evaluation by tensile testing, and hydraulic pressure burst testing of the welds for the cladding-endplug specimen are discussed.

Laser and Pressure Resistance Weld of Thin-Wall Cladding for LWR Accident-Tolerant Fuels

NASA Astrophysics Data System (ADS)

Gan, J.; Jerred, N.; Perez, E.; Haggard, D. C.

2018-02-01

FeCrAl alloy with typical composition of approximately Fe-15Cr-5Al is considered a primary candidate cladding material for light water reactor accident-tolerant fuel because of its superior resistance to oxidation in high-temperature steam compared with Zircaloy cladding. Thin-walled FeCrAl cladding at 350 μm wall thickness is required, and techniques for joining endplug to cladding need to be developed. Fusion-based laser weld and solid-state joining with pressure resistance weld were investigated in this study. The results of microstructural characterization, mechanical property evaluation by tensile testing, and hydraulic pressure burst testing of the welds for the cladding-endplug specimen are discussed.

Study of iodine migration in zirconia using stable and radioactive ion implantation

NASA Astrophysics Data System (ADS)

Chevarier, N.; Brossard, F.; Chevarier, A.; Crusset, D.; Moncoffre, N.

1998-03-01

The large uranium fission cross section leading to iodine and the behaviour of this element in the cladding tube during energy production and afterwards during waste storage is a crucial problem, especially for 129I which is a very long half-life isotope ( T = 1.59 × 10 7yr). Since a combined external and internal oxidation of the zircaloy cladding tube occurs during the reactor processing, iodine diffusion parameters in zirconia are needed. In order to obtain these data, stable iodine atoms were first introduced by ion implantation into zirconia with an energy of 200 keV and a dose equal to 8 × 10 15at cm -2. Diffusion profiles were measured using 3 MeV alpha-particle Rutherford Backscattering Spectrometry at each step of the annealing procedure between 700°C and 900°C. In such experiments a reduced iodine concentration was observed, which correlated to a diffusion-like process. Similar analysis has been performed using radioactive 131I implanted at a very low dose of 10 9 at cm -2. In this case the iodine release is deduced from gamma-ray spectroscopy measurements. The results are discussed in this paper.

High pressure hydriding of sponge-Zr in steam-hydrogen mixtures

NASA Astrophysics Data System (ADS)

Soo Kim, Yeon; Wang, Wei-E.; Olander, D. R.; Yagnik, S. K.

1997-07-01

Hydriding kinetics of thin sponge-Zr layers metallurgically bonded to a Zircaloy disk has been studied by thermogravimetry in the temperature range 350-400°C in 7 MPa hydrogen-steam mixtures. Some specimens were prefilmed with a thin oxide layer prior to exposure to the reactant gas; all were coated with a thin layer of gold to avoid premature reaction at edges. Two types of hydriding were observed in prefilmed specimens, viz., a slow hydrogen absorption process that precedes an accelerated (massive) hydriding. At 7 MPa total pressure, the critical ratio of H 2/H 2O above which massive hydriding occurs at 400°C is ˜ 200. The critical H 2/H 20 ratio is shifted to ˜2.5 × 103 at 350°C. The slow hydriding process occurs only when conditions for hydriding and oxidation are approximately equally favorable. Based on maximum weight gain, the specimen is completely converted to δ-ZrH 2 by massive hydriding in ˜5 h at a hydriding rate of ˜10 -6 mol H/cm 2 s. Incubation times of 10-20 h prior to the onset of massive hydriding increases with prefilm oxide thickness in the range of 0-10 μm. By changing to a steam-enriched gas, massive hydriding that initially started in a steam-starved condition was arrested by re-formation of a protective oxide scale.

Final report on accident tolerant fuel performance analysis of APMT-Steel Clad/UO₂ fuel and APMT-Steel Clad/UN-U₃Si₅ fuel concepts

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

Unal, Cetin; Galloway, Jack D.

2014-09-12

In FY2014 our group completed and documented analysis of new Accident Tolerant Fuel (ATF) concepts using BISON. We have modeled the viability of moving from Zircaloy to stainless steel cladding in traditional light water reactors (LWRs). We have explored the reactivity penalty of this change using the MCNP-based burnup code Monteburns, while attempting to minimize this penalty by increasing the fuel pellet radius and decreasing the cladding thickness. Fuel performance simulations using BISON have also been performed to quantify changes to structural integrity resulting from thinner stainless steel claddings. We account for thermal and irradiation creep, fission gas swelling, thermalmore » swelling and fuel relocation in the models for both Zircaloy and stainless steel claddings. Additional models that account for the lower oxidation stainless steel APMT are also invoked where available. Irradiation data for HT9 is used as a fallback in the absence of appropriate models. In this study the isotopic vectors within each natural element are varied to assess potential reactivity gains if advanced enrichment capabilities were levied towards cladding technologies. Recommendations on cladding thicknesses for a robust cladding as well as the constitutive components of a less penalizing composition are provided. In the first section (section 1-3), we present results accepted for publication in the 2014 TOPFUEL conference regarding the APMT/UO₂ ATF concept (J. Galloway & C. Unal, Accident Tolerant and Neutronically Favorable LWR Cladding, Proceedings of WRFPM 2014, Sendai, Japan, Paper No.1000050). Next we discuss our preliminary findings from the thermo-mechanical analysis of UN-U₃Si₅ fuel with APMT clad. In this analysis we used models developed from limited data that need to be updated when the irradiation data from ATF-1 test is available. Initial results indicate a swelling rate less than 1.5% is needed to prevent excessive clad stress.« less

BISON Modeling of Reactivity-Initiated Accident Experiments in a Static Environment

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

Folsom, Charles P.; Jensen, Colby B.; Williamson, Richard L.

2016-09-01

In conjunction with the restart of the TREAT reactor and the design of test vehicles, modeling and simulation efforts are being used to model the response of Accident Tolerant Fuel (ATF) concepts under reactivity insertion accident (RIA) conditions. The purpose of this work is to model a baseline case of a 10 cm long UO2-Zircaloy fuel rodlet using BISON and RELAP5 over a range of energy depositions and with varying reactor power pulse widths. The results show the effect of varying the pulse width and energy deposition on both thermal and mechanical parameters that are important for predicting failure ofmore » the fuel rodlet. The combined BISON/RELAP5 model captures coupled thermal and mechanical effects on the fuel-to-cladding gap conductance, cladding-to-coolant heat transfer coefficient and water temperature and pressure that would not be capable in each code individually. These combined effects allow for a more accurate modeling of the thermal and mechanical response in the fuel rodlet and thermal-hydraulics of the test vehicle.« less

Dose dependence of true stress parameters in irradiated bcc, fcc, and hcp metals

NASA Astrophysics Data System (ADS)

Byun, T. S.

2007-04-01

The dose dependence of true stress parameters has been investigated for nuclear structural materials: A533B pressure vessel steels, modified 9Cr-1Mo and 9Cr-2WVTa ferritic martensitic steels, 316 and 316LN stainless steels, and Zircaloy-4. After irradiation to significant doses, these alloys show radiation-induced strengthening and often experience prompt necking at yield followed by large necking deformation. In the present work, the critical true stresses for deformation and fracture events, such as yield stress (YS), plastic instability stress (PIS), and true fracture stress (FS), were obtained from uniaxial tensile tests or calculated using a linear strain-hardening model for necking deformation. At low dose levels where no significant embrittlement was detected, the true fracture stress was nearly independent of dose. The plastic instability stress was also independent of dose before the critical dose-to-prompt-necking at yield was reached. A few bcc alloys such as ferritic martensitic steels experienced significant embrittlement at doses above ∼1 dpa; and the true fracture stress decreased with dose. The materials fractured before yield at or above 10 dpa.

Characterization of thermal-hydraulic and ignition phenomena in prototypic, full-length boiling water reactor spent fuel pool assemblies after a complete loss-of-coolant accident.

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

Lindgren, Eric Richard; Durbin, Samuel G

2007-04-01

The objective of this project was to provide basic thermal-hydraulic data associated with a SFP complete loss-of-coolant accident. The accident conditions of interest for the SFP were simulated in a full-scale prototypic fashion (electrically-heated, prototypic assemblies in a prototypic SFP rack) so that the experimental results closely represent actual fuel assembly responses. A major impetus for this work was to facilitate code validation (primarily MELCOR) and reduce questions associated with interpretation of the experimental results. It was necessary to simulate a cluster of assemblies to represent a higher decay (younger) assembly surrounded by older, lower-power assemblies. Specifically, this program providedmore » data and analysis confirming: (1) MELCOR modeling of inter-assembly radiant heat transfer, (2) flow resistance modeling and the natural convective flow induced in a fuel assembly as it heats up in air, (3) the potential for and nature of thermal transient (i.e., Zircaloy fire) propagation, and (4) mitigation strategies concerning fuel assembly management.« less

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

Not Available

The methods cover: C in solutions, F (electrode), elements by atomic emission spectrometry, inorganic anions by ion chromatography, Hg in water/solids/sludges, As, Se, Bi, Pb, data calculations for SST (single shell tank?) samples, Sb, Tl, Ag, Pu, O/M ratio, ignition weight loss, pH value, ammonia (N), Cr(VI), alkalinity, U, C sepn. from soil/sediment/sludge, Pu purif., total N, water, C and S, surface Cl/F, leachable Cl/F, outgassing of Ge detector dewars, gas mixing, gas isotopic analysis, XRF of metals/alloys/compounds, H in Zircaloy, H/O in metals, inpurity extraction, reduced/total Fe in glass, free acid in U/Pu solns, density of solns, Kr/Xe isotopesmore » in FFTF cover gas, H by combustion, MS of Li and Cs isotopes, MS of lanthanide isotopes, GC operation, total Na on filters, XRF spectroscopy QC, multichannel analyzer operation, total cyanide in water/solid/sludge, free cyanide in water/leachate, hydrazine conc., ICP-MS, {sup 99}Tc, U conc./isotopes, microprobe analysis of solids, gas analysis, total cyanide, H/N{sub 2}O in air, and pH in soil.« less

Fission gas release during power bumping at high burnup

NASA Astrophysics Data System (ADS)

Cunningham, M. E.; Freshley, M. D.; Lanning, D. D.

1993-03-01

Research to define the behavior of Zircaloy-clad light-water reactor fuel irradiated to high burnup levels was conducted by the High Burnup Effects Program (HBEP). One activity conducted by the HBEP was to "bump" the power level of irradiated, commercial light-water reactor fuel rods to design limit linear heat generation rates at end-of-life. These bumping irradiations simulated end-of-life design limit linear heat generation rates and provided data on the effects of short-term, high power irradiations at high burnup applicable to the design and operating constraints imposed by maximum allowable fuel rod internal gas pressure limits. Based on net fission gas release during the bumping irradiations, it was observed that higher burnup rods had greater rod-average fractional fission gas release than lower burnup rods at equal bumping powers. It was also observed that a hold period of 48 hours at the peak power was insufficient to achieve equilibrium fission gas release. Finally, differences in the prebump location of fission gas, i.e., within the UO 2 matrix or at grain boundaries, affected the fission gas release during the bumping irradiations.

Secondary Startup Neutron Sources as a Source of Tritium in a Pressurized Water Reactor (PWR) Reactor Coolant System (RCS)

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

Shaver, Mark W.; Lanning, Donald D.

2010-02-01

The hypothesis of this paper is that the Zircaloy clad fuel source is minimal and that secondary startup neutron sources are the significant contributors of the tritium in the RCS that was previously assigned to release from fuel. Currently there are large uncertainties in the attribution of tritium in a Pressurized Water Reactor (PWR) Reactor Coolant System (RCS). The measured amount of tritium in the coolant cannot be separated out empirically into its individual sources. Therefore, to quantify individual contributors, all sources of tritium in the RCS of a PWR must be understood theoretically and verified by the sum ofmore » the individual components equaling the measured values.« less

Estimation of carbon 14 inventory in hull and end-piece wastes from Japanese commercial reprocessing operation

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

Tomofumi Sakuragi; Hiromi Tanabe; Emiko Hirose

2013-07-01

Hull and end-piece wastes generated from reprocessing plant operations are expected to be disposed of in a deep underground repository as Group 2 TRU wastes under the Japanese classification system. The activated metals that compose the spent fuel assemblies such as Zircaloy claddings and stainless steel nozzles are mixed and compressed after fuel dissolution, and then stuffed into stainless steel canisters. Carbon 14 is a typical activated product in the hulls and end-pieces and is mainly generated by the {sup 14}N(n,p){sup 14}C reaction. In the previous safety assessment of the TRU waste in Japan, the radionuclides inventory was calculated bymore » ORIGEN-2 code. Some conservative assumptions and preliminary estimates were used in this calculation. For example, total radionuclides generated from a single type of fuel assembly (45 GWd/tU for a PWR unit), and the thickness of the Zircaloy oxide film on the hulls (80 μm) were both overestimated. The second assumption in particular has a large effect on exposure dose evaluation. Therefore, it is essential to have a realistic source term evaluation regarding such items as the C-14 inventory and its distribution to waste parts. In the present study, a C-14 inventory of the hull and end-piece wastes from the operation of a commercial reprocessing plant in Japan corresponding to 32,000 tU (16,000 tU in each BWR and PWR) was calculated. Analysis using individual irradiation conditions and fuel characteristics was conducted on 6 types of fuel assemblies for BWRs and 12 types for PWRs (4 pile types x 3 burnup limits). The oxide film thickness data for each fuel type cladding were obtained from the published literature. Activation calculations were performed by using ORIGEN-2 code. For the amount of spent assembly and other waste characteristics, representative values were assumed based on the published literature. As a preliminary experiment, C-14 in irradiated BWR claddings was measured and found to be consistent with the calculated activation. The total C-14 inventory was estimated as 4.46x10{sup 14} Bq, consisting of 2.58x10{sup 14} Bq for BWRs and 1.87x10{sup 14} Bq for PWRs, and is consistent with the safety assessment of 4.4x10{sup 14} Bq. However, the distribution of the C-14 inventory to hull oxide, which was estimated under the assumption of instantaneous radionuclide release in the safety assessment, decreased from 5.72x10{sup 13} Bq (13% of the total) in the previous assessment to 1.30x10{sup 13} Bq (2.9% of the total; consisting of 1.48x10{sup 12} for BWRs and 1.15x10{sup 13} for PWRs). In other words, the exposure dose peak is reduced to approximate 25% of its previous value due to the use of detailed oxide film data that the BWR cladding has a thin oxide film. Other instantaneous release components for C-14 such as the fuel residual were negligible. (authors)« less

Advanced Pellet-Cladding Interaction Modeling using the US DOE CASL Fuel Performance Code: Peregrine

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

Montgomery, Robert O.; Capps, Nathan A.; Sunderland, Dion J.

The US DOE’s Consortium for Advanced Simulation of LWRs (CASL) program has undertaken an effort to enhance and develop modeling and simulation tools for a virtual reactor application, including high fidelity neutronics, fluid flow/thermal hydraulics, and fuel and material behavior. The fuel performance analysis efforts aim to provide 3-dimensional capabilities for single and multiple rods to assess safety margins and the impact of plant operation and fuel rod design on the fuel thermo-mechanical-chemical behavior, including Pellet-Cladding Interaction (PCI) failures and CRUD-Induced Localized Corrosion (CILC) failures in PWRs. [1-3] The CASL fuel performance code, Peregrine, is an engineering scale code thatmore » is built upon the MOOSE/ELK/FOX computational FEM framework, which is also common to the fuel modeling framework, BISON [4,5]. Peregrine uses both 2-D and 3-D geometric fuel rod representations and contains a materials properties and fuel behavior model library for the UO2 and Zircaloy system common to PWR fuel derived from both open literature sources and the FALCON code [6]. The primary purpose of Peregrine is to accurately calculate the thermal, mechanical, and chemical processes active throughout a single fuel rod during operation in a reactor, for both steady state and off-normal conditions.« less

Advanced Pellet Cladding Interaction Modeling Using the US DOE CASL Fuel Performance Code: Peregrine

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

Jason Hales; Various

The US DOE’s Consortium for Advanced Simulation of LWRs (CASL) program has undertaken an effort to enhance and develop modeling and simulation tools for a virtual reactor application, including high fidelity neutronics, fluid flow/thermal hydraulics, and fuel and material behavior. The fuel performance analysis efforts aim to provide 3-dimensional capabilities for single and multiple rods to assess safety margins and the impact of plant operation and fuel rod design on the fuel thermomechanical- chemical behavior, including Pellet-Cladding Interaction (PCI) failures and CRUD-Induced Localized Corrosion (CILC) failures in PWRs. [1-3] The CASL fuel performance code, Peregrine, is an engineering scale codemore » that is built upon the MOOSE/ELK/FOX computational FEM framework, which is also common to the fuel modeling framework, BISON [4,5]. Peregrine uses both 2-D and 3-D geometric fuel rod representations and contains a materials properties and fuel behavior model library for the UO2 and Zircaloy system common to PWR fuel derived from both open literature sources and the FALCON code [6]. The primary purpose of Peregrine is to accurately calculate the thermal, mechanical, and chemical processes active throughout a single fuel rod during operation in a reactor, for both steady state and off-normal conditions.« less

Core thermal response and hydrogen generation of the N Reactor hydrogen mitigation design basis accident

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

White, M.D.; Lombardo, N.J.; Heard, F.J.

1988-04-01

Calculations were performed to determine core heatup, core damage, and subsequent hydrogen production of a hypothetical loss-of-cooling accident at the Department of Energy's N Reactor. The thermal transient response of the reactor core was solved using the TRUMP-BD computer program. Estimates of whole-core thermal damage and hydrogen production were made by weighting the results of multiple half-length pressure tube simulations at various power levels. The Baker-Just and Wilson parabolic rate equations for the metal-water chemical reactions modeled the key phenomena of chemical energy and hydrogen evolution. Unlimited steam was assumed available for continuous oxidation of exposed Zircaloy-2 surfaces and formore » uranium metal with fuel cladding beyond the failure temperature (1038 C). Intact fuel geometry was modeled. Maximum fuel temperatures (1181 C) in the cooled central regions of the core were predicted to occur one-half hour into the accident scenario. Maximum fuel temperatures of 1447 C occurred in the core GSCS-regions at the end of the 10-h transient. After 10-h 26% of the fuel inventory was predicted to have failed. Peak hydrogen evolution equaled 42 g/s, while 10-h integrated hydrogen evolution equaled 167 kg. 12 refs., 12 figs., 2 tabs.« less

Power ramp induced iodine and cesium redistribution in LWR fuel rods

NASA Astrophysics Data System (ADS)

Sontheimer, F.; Vogl, W.; Ruyter, I.; Markgraf, J.

1980-01-01

Volatile fission product migration in LWR fuel rods which are power ramped above a certain threshold beyond the envelope of their previous power history, plays an important role in stress corrosion cracking of Zircaloy. This may cause fuel rods to fail already at stresses below the yield strength. In the HFR, Petten, many power ramp experiments have been performed with subsequent examination of the ramped rods for fission product distribution. This study describes the measurement of iodine and cesium distribution using γ-spectroscopy of I-131 and Cs-137. An evaluation method is presented which makes the determination of absolute amounts of I/Cs feasible. It is shown that a threshold for I/Cs redistribution exists beyond which it depends strongly on local fuel rod power and fuel type.

Effects of hydrogen on thermal creep behaviour of Zircaloy fuel cladding

NASA Astrophysics Data System (ADS)

Suman, Siddharth; Khan, Mohd Kaleem; Pathak, Manabendra; Singh, R. N.

2018-01-01

Zirconium alloys are extensively used for nuclear fuel cladding. Creep is one of the most likely degradation mechanisms for fuel cladding during reactor operating and repository conditions. Fuel cladding tubes undergo waterside corrosion during service and hydrogen is produced as a result of it-a fraction of which is picked up by cladding. Hydrogen remains in solid solution up to terminal solid solubility and it precipitates as brittle hydride phase in the zirconium metal matrix beyond this limiting concentration. Hydrogen, either in solid solution or as precipitated hydride, alters the creep behaviour of zirconium alloys. The present article critically reviews the influence of hydrogen on thermal creep behaviour of zirconium alloys, develops the systematic understanding of this multifaceted phenomenon, and delineates the thrust areas which require further investigations.

Study and development of 22 kW peak power fiber coupled short pulse Nd:YAG laser for cleaning applications

NASA Astrophysics Data System (ADS)

Choubey, Ambar; Vishwakarma, S. C.; Vachhani, D. M.; Singh, Ravindra; Misra, Pushkar; Jain, R. K.; Arya, R.; Upadhyaya, B. N.; Oak, S. M.

2014-11-01

Free running short pulse Nd:YAG laser of microsecond pulse duration and high peak power has a unique capability to ablate material from the surface without heat propagation into the bulk. Applications of short pulse Nd:YAG lasers include cleaning and restoration of marble, stones, and a variety of metals for conservation. A study on the development of high peak power short pulses from Nd:YAG laser along with its cleaning and conservation applications has been performed. A pulse energy of 1.25 J with 55 μs pulse duration and a maximum peak power of 22 kW has been achieved. Laser beam has an M2 value of ~28 and a pulse-to-pulse stability of ±2.5%. A lower value of M2 means a better beam quality of the laser in multimode operation. A top hat spatial profile of the laser beam was achieved at the exit end of 200 μm core diameter optical fiber, which is desirable for uniform cleaning. This laser system has been evaluated for efficient cleaning of surface contaminations on marble, zircaloy, and inconel materials for conservation with cleaning efficiency as high as 98%. Laser's cleaning quality and efficiency have been analysed by using a microscope, a scanning electron microscope (SEM), and X-ray photon spectroscopy (XPS) measurements.

Material distribution in light water reactor-type bundles tested under severe accident conditions

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

Noack, V.; Hagen, S.J.L.; Hofmann, P.

1997-02-01

Severe fuel damage experiments simulating small-break loss-of-coolant accidents have been carried out in the CORA out-of-pile test facility at Forschungszentrum Karlsruhe. Rod bundles with electrically heated fuel rod simulators containing annular UO{sub 2} pellets, UO{sub 2} full pellet rods, and absorber rods of two kinds (Ag/In/Cd to represent pressurized water reactor conditions and B{sub 4}C to represent boiling water reactor and VVER-1000 fuel elements) were subjected to temperature transients up to 2,300 K. A special method was applied to determine the axial mass distribution of bundle materials. The low-temperature melt formation by various interactions between zirconium and components of absorbermore » and spacer grids strongly influences the bundle degradation and material relocation. Absorber materials can separate from the fuel by a noncoherent relocation of the materials at different temperatures. The distributions of solidified materials in the different test bundles show a clear dependence on the axial temperature profile. Coolant channel blockages are observed mainly at the lower end of the bundle, i.e., near the lowest elevation at which an oxidation excursion resulting from the highly exothermic zirconium-steam reaction had been experienced. This elevation corresponds with a steep axial temperature gradient in the maximum temperature attained. Oxide layers on Zircaloy result in reduced melt formation.« less

SiC-CMC-Zircaloy-4 Nuclear Fuel Cladding Performance during 4-Point Tubular Bend Testing

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

IJ van Rooyen; WR Lloyd; TL Trowbridge

2013-09-01

The U.S. Department of Energy Office of Nuclear Energy (DOE NE) established the Light Water Reactor Sustainability (LWRS) program to develop technologies and other solutions to improve the reliability, sustain the safety, and extend the life of current reactors. The Advanced LWR Nuclear Fuel Development Pathway in the LWRS program encompasses strategic research focused on improving reactor core economics and safety margins through the development of an advanced fuel cladding system. Recent investigations of potential options for “accident tolerant” nuclear fuel systems point to the potential benefits of silicon carbide (SiC) cladding. One of the proposed SiC-based fuel cladding designsmore » being investigated incorporates a SiC ceramic matrix composite (CMC) as a structural material supplementing an internal Zircaloy-4 (Zr-4) liner tube, referred to as the hybrid clad design. Characterization of the advanced cladding designs will include a number of out-of-pile (nonnuclear) tests, followed by in-pile irradiation testing of the most promising designs. One of the out-of-pile characterization tests provides measurement of the mechanical properties of the cladding tube using four point bend testing. Although the material properties of the different subsystems (materials) will be determined separately, in this paper we present results of 4-point bending tests performed on fully assembled hybrid cladding tube mock-ups, an assembled Zr-4 cladding tube mock-up as a standard and initial testing results on bare SiC-CMC sleeves to assist in defining design parameters. The hybrid mock-up samples incorporated SiC-CMC sleeves fabricated with 7 polymer impregnation and pyrolysis (PIP) cycles. To provide comparative information; both 1- and 2-ply braided SiC-CMC sleeves were used in this development study. Preliminary stress simulations were performed using the BISON nuclear fuel performance code to show the stress distribution differences for varying lengths between loading points and clad configurations. The 2-ply sleeve samples show a higher bend momentum compared to those of the 1-ply sleeve samples. This is applicable to both the hybrid mock-up and bare SiC-CMC sleeve samples. Comparatively both the 1- and 2-ply hybrid mock-up samples showed a higher bend stiffness and strength compared with the standard Zr-4 mock-up sample. The characterization of the hybrid mock-up samples showed signs of distress and preliminary signs of fraying at the protective Zr-4 sleeve areas for the 1-ply SiC-CMC sleeve. In addition, the microstructure of the SiC matrix near the cracks at the region of highest compressive bending strain shows significant cracking and flaking. The 2-ply SiC-CMC sleeve samples showed a more bonded, cohesive SiC matrix structure. This cracking and fraying causes concern for increased fretting during the actual use of the design. Tomography was proven as a successful tool to identify open porosity during pre-test characterization. Although there is currently insufficient data to make conclusive statements regarding the overall merit of the hybrid cladding design, preliminary characterization of this novel design has been demonstrated.« less

On the Potential of MAX phases for Nuclear Applications

NASA Astrophysics Data System (ADS)

Tallman, Darin Joseph

Materials within nuclear reactors experience some of the harshest environments currently known to man, including long term operation in extreme temperatures, corrosive media, and fast neutron fluences with up to 100 displacements per atom, dpa. In order to improve the efficiency and safety of current and future reactors, new materials are required to meet these harsh demands. The M n+1AXn phases, a growing family of ternary nano-layered ceramics, possess a desirable combination of metallic and ceramic properties. They are composed of an early transition metal (M), a group 13--16 element (A), and carbon and/or nitrogen (X). The MAX phases are being proposed for use in such extreme environments because of their unique combination of high fracture toughness values and thermal conductivities, machinability, oxidation resistance, and ion irradiation damage tolerance. Previous ion irradiation studies have shown that Ti3SiC2 and Ti3AlC2 resist irradiation damage, maintaining crystallinity up to 50 dpa. The aim of this work was to explore the effect of neutron irradiation, up to 9 dpa and at temperatures of 100 to 1000 °C, on select MAX phases for the first time. The MAX phases Ti3SiC2, Ti 3AlC2, Ti2AlC, and Ti2AlN were synthesized, and irradiated in test reactors that simulate in-pile conditions of nuclear reactors. X-ray diffraction, XRD, pattern refinements of samples revealed a distortion of the crystal lattice after low temperature irradiation, which was not observed after high temperature irradiations. Additionally, the XRD results indicated that Ti3AlC2 and Ti2AlN dissociated after relatively low neutron doses. This led us to focus on Ti 3SiC2 and Ti2AlC. For the first time, dislocation loops were observed in Ti3SiC 2 and Ti2AlC as a result of neutron irradiation. At 1 x 1023 loops/m3, the loop density in Ti2 AlC after irradiation to 0.1 dpa at 700°C was 1.5 orders of magnitude greater than that observed in Ti3SiC2, at 3 x 1021 loops/m3. The Ti2AlC composition appeared more prone to microcracking that Ti3SiC2. Additionally, exceptionally large denuded zones, up to 1 mum in width after 9 dpa irradiations at 500°C, were observed in Ti3SiC2, indicating that point defects readily diffuse to the grain boundaries. Denuded zones of this width, to our knowledge, have never been observed. In comparison, TiC impurity particles were highly damaged with various dislocation loops and defect clusters after irradiation. It is thus apparent that the A-layer, interleaved between MX blocks in the MAX phase nanolayered structure, readily accommodates and/or annihilates point defects, providing significant irradiation damage tolerance. Comparison of defect densities, post-irradiation microstructure, and electrical resistivity showed Ti3SiC2 to have the highest irradiation tolerance. Diffusion bonding of MAX phases to Zircaloy-4 was studied in the 1100 to 1300°C temperature range. The out diffusion of the A-group element into Zircaloy-4 formed Zr-intermetallic compounds that were roughly an order of magnitude thicker in Ti2AlC than Ti3SiC 2. Helium permeability results suggest that the MAX phases behave similarly to other sintered ceramics. Based on the totality of our results, Ti 3SiC2 remains a promising candidate for high temperature nuclear applications, and warrants future exploration. This work provides the foundation for understanding the response of the MAX phases to neutron irradiation, and can now be used to finely tune ion irradiation studies to accurately simulate reactor conditions.

A Multi-Stage Wear Model for Grid-to-Rod Fretting of Nuclear Fuel Rods

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

Blau, Peter Julian

The wear of fuel rod cladding against the supporting structures in the cores of pressurized water nuclear reactors (PWRs) is an important and potentially costly tribological issue. Grid-to-rod fretting (GTRF), as it is known, involves not only time-varying contact conditions, but also elevated temperatures, flowing hot water, aqueous tribo-corrosion, and the embrittling effects of neutron fluences. The multi-stage, closed-form analytical model described in this paper relies on published out-of-reactor wear and corrosion data and a set of simplifying assumptions to portray the conversion of frictional work into wear depth. The cladding material of interest is a zirconium-based alloy called Zircaloy-4,more » and the grid support is made of a harder and more wear-resistant material. Focus is on the wear of the cladding. The model involves an incubation stage, a surface oxide wear stage, and a base alloy wear stage. The wear coefficient, which is a measure of the efficiency of conversion of frictional work into wear damage, can change to reflect the evolving metallurgical condition of the alloy. Wear coefficients for Zircaloy-4 and for a polyphase zirconia layer were back-calculated for a range of times required to wear to a critical depth. Inputs for the model, like the friction coefficient, are taken from the tribology literature in lieu of in-reactor tribological data. Concepts of classical fretting were used as a basis, but are modified to enable the model to accommodate the complexities of the PWR environment. Factors like grid spring relaxation, pre-oxidation of the cladding, multiple oxide phases, gap formation, impact, and hydrogen embrittlement are part of the problem definition but uncertainties in their relative roles limits the ability to validate the model. Sample calculations of wear depth versus time in the cladding illustrate how GTRF wear might occur in a discontinuous fashion during months-long reactor operating cycles. A means to account for grid/rod gaps and repetitive impact effects on GTRF wear is proposed« less

Uniform corrosion of FeCrAl alloys in LWR coolant environments

NASA Astrophysics Data System (ADS)

Terrani, K. A.; Pint, B. A.; Kim, Y.-J.; Unocic, K. A.; Yang, Y.; Silva, C. M.; Meyer, H. M.; Rebak, R. B.

2016-10-01

The corrosion behavior of commercial and model FeCrAl alloys and type 310 stainless steel was examined by autoclave tests and compared to Zircaloy-4, the reference cladding materials in light water reactors. The corrosion studies were carried out in three distinct water chemistry environments found in pressurized and boiling water reactor primary coolant loop conditions for up to one year. The structure and morphology of the oxides formed on the surface of these alloys was consistent with thermodynamic predictions. Spinel-type oxides were found to be present after hydrogen water chemistry exposures, while the oxygenated water tests resulted in the formation of very thin and protective hematite-type oxides. Unlike the alloys exposed to oxygenated water tests, the alloys tested in hydrogen water chemistry conditions experienced mass loss as a function of time. This mass loss was the result of net sum of mass gain due to parabolic oxidation and mass loss due to dissolution that also exhibits parabolic kinetics. The maximum thickness loss after one year of LWR water corrosion in the absence of irradiation was ∼2 μm, which is inconsequential for a ∼300-500 μm thick cladding.

Development of an Engineered Producet Storage Concept for the UREX+1 Combined Transuraqnic?Lanthanide Product Streams

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

Dr. Sean M. McDeavitt; Thomas J. Downar; Dr. Temitope A. Taiwo

2009-03-01

The U.S. Department of Energy is developing next generation processing methods to recycle uranium and transuranic (TRU) isotopes from spent nuclear fuel. The objective of the 3-year project described in this report was to develop near-term options for storing TRU oxides isolated through the uranium extraction (UREX+) process. More specifically, a Zircaloy matrix cermet was developed as a storage form for transuranics with the understanding that the cermet also has the ability to serve as a inert matrix fuel form for TRU burning after intermediate storage. The goals of this research projects were: 1) to develop the processing steps requiredmore » to transform the effluent TRU nitrate solutions and the spent Xircaloy cladding into a zireonium matrix cermet sotrage form; and 2) to evaluate the impact of phenomena that govern durability of the storage form, material processing, and TRU utiliztion in fast reactor fuel. This report represents a compilation of the results generated under this program. The information is presented as a brief technical narrative in the following sections with appended papers, presentations and academic theses to provide a detailed review of the project's accomplishments.« less

Uniform corrosion of FeCrAl alloys in LWR coolant environments

DOE PAGES

Terrani, K. A.; Pint, B. A.; Kim, Y. -J.; ...

2016-06-29

The corrosion behavior of commercial and model FeCrAl alloys and type 310 stainless steel was examined by autoclave tests and compared to Zircaloy-4, the reference cladding materials in light water reactors. The corrosion studies were carried out in three distinct water chemistry environments found in pressurized and boiling water reactor primary coolant loop conditions for up to one year. The structure and morphology of the oxides formed on the surface of these alloys was consistent with thermodynamic predictions. Spinel-type oxides were found to be present after hydrogen water chemistry exposures, while the oxygenated water tests resulted in the formation ofmore » very thin and protective hematite-type oxides. Unlike the alloys exposed to oxygenated water tests, the alloys tested in hydrogen water chemistry conditions experienced mass loss as a function of time. This mass loss was the result of net sum of mass gain due to parabolic oxidation and mass loss due to dissolution that also exhibits parabolic kinetics. Finally, the maximum thickness loss after one year of LWR water corrosion in the absence of irradiation was ~2 μm, which is inconsequential for a ~300–500 μm thick cladding.« less

Deterministic Local Sensitivity Analysis of Augmented Systems - II: Applications to the QUENCH-04 Experiment Using the RELAP5/MOD3.2 Code System

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

Ionescu-Bujor, Mihaela; Jin Xuezhou; Cacuci, Dan G.

2005-09-15

The adjoint sensitivity analysis procedure for augmented systems for application to the RELAP5/MOD3.2 code system is illustrated. Specifically, the adjoint sensitivity model corresponding to the heat structure models in RELAP5/MOD3.2 is derived and subsequently augmented to the two-fluid adjoint sensitivity model (ASM-REL/TF). The end product, called ASM-REL/TFH, comprises the complete adjoint sensitivity model for the coupled fluid dynamics/heat structure packages of the large-scale simulation code RELAP5/MOD3.2. The ASM-REL/TFH model is validated by computing sensitivities to the initial conditions for various time-dependent temperatures in the test bundle of the Quench-04 reactor safety experiment. This experiment simulates the reflooding with water ofmore » uncovered, degraded fuel rods, clad with material (Zircaloy-4) that has the same composition and size as that used in typical pressurized water reactors. The most important response for the Quench-04 experiment is the time evolution of the cladding temperature of heated fuel rods. The ASM-REL/TFH model is subsequently used to perform an illustrative sensitivity analysis of this and other time-dependent temperatures within the bundle. The results computed by using the augmented adjoint sensitivity system, ASM-REL/TFH, highlight the reliability, efficiency, and usefulness of the adjoint sensitivity analysis procedure for computing time-dependent sensitivities.« less

Light Water Breeder Reactor fuel rod design and performance characteristics (LWBR Development Program)

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

Campbell, W.R.; Giovengo, J.F.

1987-10-01

Light Water Breeder Reactor (LWBR) fuel rods were designed to provide a reliable fuel system utilizing thorium/uranium-233 mixed-oxide fuel while simultaneously minimizing structural material to enhance fuel breeding. The fuel system was designed to be capable of operating successfully under both load follow and base load conditions. The breeding objective required thin-walled, low hafnium content Zircaloy cladding, tightly spaced fuel rods with a minimum number of support grid levels, and movable fuel rod bundles to supplant control rods. Specific fuel rod design considerations and their effects on performance capability are described. Successful completion of power operations to over 160 percentmore » of design lifetime including over 200 daily load follow cycles has proven the performance capability of the fuel system. 68 refs., 19 figs., 44 tabs.« less

Determination of very low concentrations of hydrogen in zirconium alloys by neutron imaging

NASA Astrophysics Data System (ADS)

Buitrago, N. L.; Santisteban, J. R.; Tartaglione, A.; Marín, J.; Barrow, L.; Daymond, M. R.; Schulz, M.; Grosse, M.; Tremsin, A.; Lehmann, E.; Kaestner, A.; Kelleher, J.; Kabra, S.

2018-05-01

Zr-based alloys are used in nuclear power plants because of a unique combination of very low neutron absorption and excellent mechanical properties and corrosion resistance at operating conditions. However, Hydrogen (H) or Deuterium ingress due to waterside corrosion during operation can embrittle these materials. In particular, Zr alloys are affected by Delayed Hydride Cracking (DHC), a stress-corrosion cracking mechanism operating at very low H content (∼100-300 wt ppm), which involves the diffusion of H to the crack tip. H content in Zr alloys is commonly determined by destructive techniques such as inert gas fusion and vacuum extraction. In this work, we have used neutron imaging to non-destructively quantify the spatial distribution of H in Zr alloys specimens with a resolution of ∼5 wt ppm, an accuracy of ∼10 wt ppm and a spatial resolution of ∼25 μm × 5 mm x 10 mm. Non-destructive experiments performed on a comprehensive set of calibrated specimens of Zircaloy-2 and Zr2.5%Nb at four neutron facilities worldwide show the typical precision and repeatability of the technique. We have observed that the microstructure of the alloy plays an important role on the homogeneity of H across a specimen. We propose several strategies for performing H determinations without calibrated specimens, with the most precise results for neutrons having wavelengths longer than 5.7 Å.

Alternate Fuel Cycle Technologies/Thorium Fuel Cycle Technology Programs. Quarterly report for period 1 April--30 June 1978

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

Vondra, B.L.

1978-08-01

Voloxidation and dissolution studies: rotary-kiln heat-transfer tests are under way using a small rotary kiln along with the development of a mathematical model to determine kiln-heat-flux profiles necessary to maintain a desired temperature gradient. The erosion/corrosion test for evaluating materials of construction is operational. Fuel from a BWR (Big Rock Point) yielded more fine solid residue on dissolution than in previous tests with PWR fuel. Two additional parametric voloxidation tests with H.B. Robinson fuel compared air vs pure oxygen atmospheres at 550{sup 0}C; overall tritium release and subsequent fuel dissolution were equivalent. Thorium dissolution studies: the dissolution rate of thoriamore » in fluoride-catalyzed 8 to 14 M HNO{sub 3} (100{sup 0}C) was max between 0.04 to 0.06 M HF; at higher fluoride concentrations, ThF{sub 4}.5H{sub 2}O precipitated. The rate of zircaloy dissolution continued to increase with increasing fluoride concentration. Stainless-steel-clad (Th,U)0{sub 2} fuel rods irradiated in the NRX reactor were sheared, voloxidized, and dissolved. {le}10% of the tritium was released during voloxidation in air at 600{sup 0}C. Carbon-14 removal from off-gas and fixation: carbon dioxide removal with Linde 13X molecular sieves to less than 100 ppB was experimentally verified using 300 ppM CO in air. Decontamination factors from 3000 to 7500 were obtained for CO{sub 2} removal in the gas-slurry stirred-tank reactor with CA(OH){sub 2}.or Ba(0H){sub 2}/sup .8H2O./. With Ba(OH){sub 2}.H{sub 2}0{sup 2} in a fixed-bed column, decontamination factors of about 30,000 were obtained.« less

Performance of U3Si2 Fuel in a Reactivity Insertion Accident

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

Cheng, Lap Y.; Cuadra, Arantxa; Todosow, Michael

In this study we examined the performance of the U3Si2 fuel cladded with Zircaloy (Zr) in a reactivity insertion accident (RIA) in a PWR core. The power excursion as a result of a $1 reactivity insertion was calculated by a TRACE PWR plant model using point-kinetics, for alternative cores with UO2 and U3Si2 fuel assemblies. The point-kinetics parameters (feedback coefficients, prompt-neutron lifetime and group constants for six delayed-neutron groups) were obtained from beginning-of-cycle equilibrium full core calculations with PARCS. In the PARCS core calculations, the few-group parameters were developed utilizing the TRITON/NEWT tools in the SCALE package. In order tomore » assess the fuel response in finer detail (e.g. the maximum fuel temperature) the power shape and thermal boundary conditions from the TRACE/PARCS calculations were used to drive a BISON model of a fuel pin with U3Si2 and UO2 respectively. For a $1 reactivity transient both TRACE and BISON predicted a higher maximum fuel temperature for the UO2 fuel than the U3Si2 fuel. Furthermore, BISON is noted to calculate a narrower gap and a higher gap heat transfer coefficient than TRACE. This resulted in BISON predicting consistently lower fuel temperatures than TRACE. This study also provides a systematic comparison between TRACE and BISON using consistent transient boundary conditions. The TRACE analysis of the RIA only reflects the core-wide response in power. A refinement to the analysis would be to predict the local peaking in a three-dimensional core as a result of control rod ejection.« less

Capture of Tritium Released from Cladding in the Zirconium Recycle Process

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

Spencer, Barry B.; Walker, T. B.; Bruffey, S. H.

2016-08-31

Zirconium may be recovered from the Zircaloy® cladding of used nuclear fuel (UNF) for recycle or to reduce the quantities of high-level waste destined for a geologic repository. Recovery of zirconium using a chlorination process is currently under development at the Oak Ridge National Laboratory. The approach is to treat the cladding with chlorine gas to convert the zirconium in the alloy (~98 wt % of the alloy mass) to zirconium tetrachloride. A significant fraction of the tritium (0–96%) produced in nuclear fuel during irradiation may be found in zirconium-based cladding and could be released from the cladding when themore » solid matrix is destroyed by the chlorination reaction. To prevent uncontrolled release of radioactive tritium to other parts of the plant or to the environment, a method to recover the tritium may be required. The focus of this effort was to (1) identify potential methods for the recovery of tritium from the off-gas of the zirconium recycle process, (2) perform scoping tests on selected recovery methods using nonradioactive gas simulants, and (3) select a process design appropriate for testing on radioactive gas streams generated by the engineering-scale zirconium recycle demonstrations on radioactive used cladding.« less

Capture of Tritium Released from Cladding in the Zirconium Recycle Process

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

Spencer, Barry B.; Walker, T. B.; Bruffey, Stephanie H.

2016-08-31

This report is issued as the first revision to FCRD-MRWFD-2016-000297. Zirconium may be recovered from the Zircaloy® cladding of used nuclear fuel (UNF) for recycle or to reduce the quantities of high-level waste destined for a geologic repository. Recovery of zirconium using a chlorination process is currently under development at the Oak Ridge National Laboratory. The approach is to treat the cladding with chlorine gas to convert the zirconium in the alloy (~98 wt % of the alloy mass) to zirconium tetrachloride. A significant fraction of the tritium (0–96%) produced in nuclear fuel during irradiation may be found in zirconium-basedmore » cladding and could be released from the cladding when the solid matrix is destroyed by the chlorination reaction. To prevent uncontrolled release of radioactive tritium to other parts of the plant or to the environment, a method to recover the tritium may be required. The focus of this effort was to (1) identify potential methods for the recovery of tritium from the off-gas of the zirconium recycle process, (2) perform scoping tests on selected recovery methods using non-radioactive gas simulants, and (3) select a process design appropriate for testing on radioactive gas streams generated by the engineering-scale zirconium recycle demonstrations on radioactive used cladding.« less

Severe Accident Scoping Simulations of Accident Tolerant Fuel Concepts for BWRs

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

Robb, Kevin R.

2015-08-01

Accident-tolerant fuels (ATFs) are fuels and/or cladding that, in comparison with the standard uranium dioxide Zircaloy system, can tolerate loss of active cooling in the core for a considerably longer time period while maintaining or improving the fuel performance during normal operations [1]. It is important to note that the currently used uranium dioxide Zircaloy fuel system tolerates design basis accidents (and anticipated operational occurrences and normal operation) as prescribed by the US Nuclear Regulatory Commission. Previously, preliminary simulations of the plant response have been performed under a range of accident scenarios using various ATF cladding concepts and fully ceramicmore » microencapsulated fuel. Design basis loss of coolant accidents (LOCAs) and station blackout (SBO) severe accidents were analyzed at Oak Ridge National Laboratory (ORNL) for boiling water reactors (BWRs) [2]. Researchers have investigated the effects of thermal conductivity on design basis accidents [3], investigated silicon carbide (SiC) cladding [4], as well as the effects of ATF concepts on the late stage accident progression [5]. These preliminary analyses were performed to provide initial insight into the possible improvements that ATF concepts could provide and to identify issues with respect to modeling ATF concepts. More recently, preliminary analyses for a range of ATF concepts have been evaluated internationally for LOCA and severe accident scenarios for the Chinese CPR1000 [6] and the South Korean OPR-1000 [7] pressurized water reactors (PWRs). In addition to these scoping studies, a common methodology and set of performance metrics were developed to compare and support prioritizing ATF concepts [8]. A proposed ATF concept is based on iron-chromium-aluminum alloys (FeCrAl) [9]. With respect to enhancing accident tolerance, FeCrAl alloys have substantially slower oxidation kinetics compared to the zirconium alloys typically employed. During a severe accident, FeCrAl would tend to generate heat and hydrogen from oxidation at a slower rate compared to the zirconium-based alloys in use today. The previous study, [2], of the FeCrAl ATF concept during station blackout (SBO) severe accident scenarios in BWRs was based on simulating short term SBO (STSBO), long term SBO (LTSBO), and modified SBO scenarios occurring in a BWR-4 reactor with MARK-I containment. The analysis indicated that FeCrAl had the potential to delay the onset of fuel failure by a few hours depending on the scenario, and it could delay lower head failure by several hours. The analysis demonstrated reduced in-vessel hydrogen production. However, the work was preliminary and was based on limited knowledge of material properties for FeCrAl. Limitations of the MELCOR code were identified for direct use in modeling ATF concepts. This effort used an older version of MELCOR (1.8.5). Since these analyses, the BWR model has been updated for use in MELCOR 1.8.6 [10], and more representative material properties for FeCrAl have been modeled. Sections 2 4 present updated analyses for the FeCrAl ATF concept response during severe accidents in a BWR. The purpose of the study is to estimate the potential gains afforded by the FeCrAl ATF concept during BWR SBO scenarios.« less

Study of a ;hot; particle with a matrix of U-bearing metallic Zr: Clue to supercriticality during the Chernobyl nuclear accident

NASA Astrophysics Data System (ADS)

Pöml, P.; Burakov, B.

2017-05-01

This paper is dedicated to the 30th anniversary of the severe nuclear accident that occurred at the Chernobyl NPP on 26 April 1986. A detailed study on a Chernobyl "hot" particle collected from contaminated soil was performed. Optical and electron microscopy, as well as quantitative x-ray microbeam analysis methods were used to determine the properties of the sample. The results show that the particle (≈ 240 x 165 μm) consists of a metallic Zr matrix containing 2-3 wt. % U and bearing veins of an U,Nb admixture. The metallic Zr matrix contains two phases with different amounts of O with the atomic proportions (U,Zr,Nb)0.73O0.27 and (U,Zr,Nb)0.61O0.39. The results confirm the interaction between UO2 fuel and zircaloy cladding in the reactor core. To explain the process of formation of the particle, its properties are compared to laboratory experiments. Because of the metallic nature of the particle it is concluded that it must have formed during a very high temperature (> 2400∘C) process that lasted for only a very short time (few microseconds or less); otherwise the particle should have been oxidised. Such a rapid very high temperature process indicates that at least part of the reactor core could have been supercritical prior to an explosion as it was previously suggested in the literature.

Phase 1A Final Report for the AREVA Team Enhanced Accident Tolerant Fuels Concepts

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

Morrell, Mike E.

In response to the Department of Energy (DOE) funded initiative to develop and deploy lead fuel assemblies (LFAs) of Enhanced Accident Tolerant Fuel (EATF) into a US reactor within 10 years, AREVA put together a team to develop promising technologies for improved fuel performance during off normal operations. This team consisted of the University of Florida (UF) and the University of Wisconsin (UW), Savannah River National Laboratory (SRNL), Duke Energy and Tennessee Valley Authority (TVA). This team brought broad experience and expertise to bear on EATF development. AREVA has been designing; manufacturing and testing nuclear fuel for over 50 yearsmore » and is one of the 3 large international companies supplying fuel to the nuclear industry. The university and National Laboratory team members brought expertise in nuclear fuel concepts and materials development. Duke and TVA brought practical utility operating experience. This report documents the results from the initial “discovery phase” where the team explored options for EATF concepts that provide enhanced accident tolerance for both Design Basis (DB) and Beyond Design Basis Events (BDB). The main driver for the concepts under development were that they could be implemented in a 10 year time frame and be economically viable and acceptable to the nuclear fuel marketplace. The economics of fuel design make this DOE funded project very important to the nuclear industry. Even incremental changes to an existing fuel design can cost in the range of $100M to implement through to LFAs. If this money is invested evenly over 10 years then it can take the fuel vendor several decades after the start of the project to recover their initial investment and reach a breakeven point on the initial investment. Step or radical changes to a fuel assembly design can cost upwards of $500M and will take even longer for the fuel vendor to recover their investment. With the projected lifetimes of the current generation of nuclear power plants large scale investment by the fuel vendors is difficult to justify. Specific EATF enhancements considered by the AREVA team were; Improved performance in DB and BDB conditions; Reduced release to the environment in a catastrophic accident; Improved performance during normal operating conditions; Improved performance if US reactors start to load follow; Equal or improved economics of the fuel; and Improvements to the fuel behavior to support future transportation and storage of the used nuclear fuel (UNF). In pursuit of the above enhancements, EATF technology concepts that our team considered were; Additives to the fuel pellets which included; Chromia doping to increase fission gas retention. Chromia doping has the potential to improve load following characteristics, improve performance of the fuel pellet during clad failure, and potentially lock up cesium into the fuel matrix; Silicon Carbide (SiC) Fibers to improve thermal heat transfer in normal operating conditions which also improves margin in accident conditions and the potential to lock up iodine into the fuel matrix; Nano-diamond particles to enhance thermal conductivity; Coatings on the fuel cladding; and Nine coatings on the existing Zircaloy cladding to increase coping time and reduce clad oxidation and hydrogen generation during accident conditions, as well as reduce hydrogen pickup and mitigate hydride reorientation in the cladding. To facilitate the development process AREVA adopted a formal “Gate Review Process” (GR) that was used to review results and focus resources onto promising technologies to reduce costs and identify the technologies that would potentially be carried forward to LFAs within a 10 year period. During the initial discovery phase of the project AREVA took the decision to be relatively hands off and allow our university and National Laboratory partners to be free thinking and consider options that would not be constrained by preconceived ideas from the fuel vendor. To counter this and to keep the partners focused, the GR process was utilized. During this GR process each of the team members presented their findings to a board made up of technical experts from utilities, fuel manufacturing experts, fuel technical experts, and fuel research and development (R&D) experts. During the initial 2 years of the project there were several major accomplishments. These accomplishments, along with the implications for successfully implementing EATF, are; The experimental spark plasma sintering process (SPS) process was successfully used to produce fuel pellets containing either 10% SiC whiskers or nano-diamond particles. The ability to use this process enables the thermal margin enhancements of the fuel additives to be realized. Without the SPS process, the conventional process cannot support adding pellet additives in the required quantities; Coatings of Ti2AlC were successfully applied to Zircaloy-4 cladding. Testing of Ti2AlC coatings at Loss of Cooling Accident (LOCA) conditions showed reduced cladding oxidation compared to present un-coated Zircaloy-4 cladding. This achievement allows the presently used cladding system to be retained so that the 10 year schedule can be met. Having to implement a new cladding material will extend the development schedule beyond 10 years; Several documents were produced to support future development, testing, and licensing of EATF, including a design requirements traceability matrix, a draft business plan, a draft test plan, a draft regulatory plan, and the acceptance criteria for lead fuel assembly insertion into a commercial reactor. This preparatory work lays the foundation for ensuring the future development plans address all the areas required to test, license, and manufacture the new EATF; and In addition, the high velocity oxy-fuel and electrophoretic deposition (EPD) coating application processes were dropped from further consideration due to their inability to meet manufacturing criteria. This allows the resources to be focused on the most promising EATF concepts identified. Future development opportunities that were identified during this work include; The use of SiC or diamond requires that a new pellet production technique (Spark Plasma Sintering), be developed. This entails investment in developing, proving and implementing a new commercial pellet production process. Development of the process to apply thinner coatings is required; Coatings cannot be too “thick” or they will displace a significant volume of water in the core resulting in reduced thermal hydraulic characteristics; Application of the coating at high temperature can affect the Zircaloy substrate. This will require the development and implementation of a new cladding coating manufacturing process; and Replace the Cold Spray (CS) cladding coating application with the Physical Vapor Deposition (PVD) process to eliminate duplication of work and provide greater control over coating thicknesses. This can result in a reduction in the final cycle economic penalty of coatings.« less

Data summary report for fission product release test VI-6

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

Osborne, M.F.; Lorenz, R.A.; Travis, J.R.

Test VI-6 was the sixth test in the VI series conducted in the vertical furnace. The fuel specimen was a 15.2-cm-long section of a fuel rod from the BR3 reactor in Belgium. The fuel had experienced a burnup of {approximately}42 MWd/kg, with inert gas release during irradiation of {approximately}2%. The fuel specimen was heated in an induction furnace at 2300 K for 60 min, initially in hydrogen, then in a steam atmosphere. The released fission products were collected in three sequentially operated collection trains designed to facilitate sampling and analysis. The fission product inventories in the fuel were measured directlymore » by gamma-ray spectrometry, where possible, and were calculated by ORIGEN2. Integral releases were 75% for {sup 85}Kr, 67% for {sup 129}I, 64% for {sup 125}Sb, 80% for both {sup 134}Cs and {sup 137}Cs, 14% for {sup 154}Eu, 63% for Te, 32% for Ba, 13% for Mo, and 5.8% for Sr. Of the totals released from the fuel, 43% of the Cs, 32% of the Sb, and 98% of the Eu were deposited in the outlet end of the furnace. During the heatup in hydrogen, the Zircaloy cladding melted, ran down, and reacted with some of the UO{sub 2} and fission products, especially Te and Sb. The total mass released from the furnace to the collection system, including fission products, fuel, and structural materials, was 0.57 g, almost equally divided between thermal gradient tubes and filters. The release behaviors for the most volatile elements, Kr and Cs, were in good agreement with the ORNL Diffusion Model.« less

PCI fuel failure analysis: a report on a cooperative program undertaken by Pacific Northwest Laboratory and Chalk River Nuclear Laboratories.

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

Mohr, C.L.; Pankaskie, P.J.; Heasler, P.G.

Reactor fuel failure data sets in the form of initial power (P/sub i/), final power (P/sub f/), transient increase in power (..delta..P), and burnup (Bu) were obtained for pressurized heavy water reactors (PHWRs), boiling water reactors (BWRs), and pressurized water reactors (PWRs). These data sets were evaluated and used as the basis for developing two predictive fuel failure models, a graphical concept called the PCI-OGRAM, and a nonlinear regression based model called PROFIT. The PCI-OGRAM is an extension of the FUELOGRAM developed by AECL. It is based on a critical threshold concept for stress dependent stress corrosion cracking. The PROFITmore » model, developed at Pacific Northwest Laboratory, is the result of applying standard statistical regression methods to the available PCI fuel failure data and an analysis of the environmental and strain rate dependent stress-strain properties of the Zircaloy cladding.« less

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

Wang, Hong; Wang, Jy-An John

We studied behavior of surrogate nuclear fuel rods made of Zircaloy-4 (Zry-4) cladding with alumina pellets under reversed cyclic bending. Tests were performed under load or moment control at 5 Hz, and an empirical correlation was established between rod fatigue life and amplitude of the applied moment. Fatigue response of Zry-4 cladding was further characterized by using flexural rigidity. Degradation of flexural rigidity was shown to depend on the moment applied and the prefatigue condition of specimens. Pellet-to-pellet interface (PPI), pellet-to-cladding interface (PCI), and pellet condition all affect surrogate rod failure. Bonding/debonding of PPI/PCI and pellet fracturing contribute to surrogatemore » rod bending fatigue. Also, the effect of sensor spacing on curvature measurement using three-point deflections was studied; the method based on effective specimen gauge length is effective in sensor spacing correction. Finally, we developed the database and gained understanding in this study such that it will serve as input to analysis of SNF vibration integrity.« less

Hippo/crates-in-situ deformation strain and testure studies using neutron time-of-flight diffraction.

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

Vogel, S. C.; Hartig, C.; Brissier, T. D.

2005-01-01

In situ deformation studies by diffraction allow studying of deformation mechanisms and provide valuable data to validate and improve deformation models. In particular, deformation studies using time-of-flight neutrons provide averages over large numbers of grains and allow to probing the response of lattice planes parallel and perpendicular to the applied load simultaneously. In this paper we describe the load-frame CRATES, designed for the HIPPO neutron time-of-flight diffractometer at LANSCE. The HIPPO/CRATES combination allows probing up to 20 diffraction vectors simultaneously and provides rotation of the sample in the beam while under load. With this, deformation texture, i.e. the change ofmore » grain orientation due to plastic deformation, or strain pole figures may be measured. We report initial results of a validation experiment, comparing deformation of a Zircaloy specimen measured using the NPD neutron diffractometer with results obtained for the same material using HIPPO/CRATES.« less

Hot Cell Installation and Demonstration of the Severe Accident Test Station

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

Linton, Kory D.; Burns, Zachary M.; Terrani, Kurt A.

A Severe Accident Test Station (SATS) capable of examining the oxidation kinetics and accident response of irradiated fuel and cladding materials for design basis accident (DBA) and beyond design basis accident (BDBA) scenarios has been successfully installed and demonstrated in the Irradiated Fuels Examination Laboratory (IFEL), a hot cell facility at Oak Ridge National Laboratory. The two test station modules provide various temperature profiles, steam, and the thermal shock conditions necessary for integral loss of coolant accident (LOCA) testing, defueled oxidation quench testing and high temperature BDBA testing. The installation of the SATS system restores the domestic capability to examinemore » postulated and extended LOCA conditions on spent fuel and cladding and provides a platform for evaluation of advanced fuel and accident tolerant fuel (ATF) cladding concepts. This document reports on the successful in-cell demonstration testing of unirradiated Zircaloy-4. It also contains descriptions of the integral test facility capabilities, installation activities, and out-of-cell benchmark testing to calibrate and optimize the system.« less

Finite-element model to predict roll-separation force and defects during rolling of U-10Mo alloys

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

Soulami, Ayoub; Burkes, Douglas E.; Joshi, Vineet V.

This study used a finite element code, LSDYNA, as a predictive tool to optimize the rolling process. Simulations of the hot rolling of U-10Mo coupons encapsulated in low-carbon steel were conducted following two different schedules. Model predictions of the roll-separation force and roll pack thicknesses at different stages of the rolling process were compared with experimental measurements. The study reported here discussed various attributes of the rolled coupons revealed by the model (e.g., waviness and thickness non-uniformity like dog boning). To investigate the influence of the cladding material on these rolling defects, other cases were simulated:  hot rolling with alternative can materials, namely, 304 stainless steel and Zircaloy-2, and bare-rolling.

PARTIAL ECONOMIC STUDY OF STEAM COOLED HEAVY WATER MODERATED REACTORS

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

None

1960-04-01

Steam-cooled reactors are compared with CAHDU for costs of Calandria tubes, pressure tubes. heavy water moderator, heavy water reflector, fuel supply, heat exchanger, and turbine generator. A direct-cycle lightsteam-cooled heavy- water-moderated pressure-tube reactor formed the basic reactor design for the study. Two methods of steam circulation through the reactor were examined. In both cases the steam was generated outside the reactor and superheated in the reactor core. One method consisted of a series of reactor and steam generator passes. The second method consisted of the Loeffler cycle and its modifications. The fuel was assumed to be natural cylindrical UO/sub 2/more » pellets sheathed in a hypothetical material with the nuclear properties of Zircaloy, but able to function at temperatures to 900 deg F. For the conditions assumed, the longer the rod, the higher the outlet temperature and therefore the higher the efficiency. The turbine cycle efficiency was calculated on the assumption that suitable steam generators are available. As the neutron losses to the pressure tubes were significant, an economic analysis of insulated pressure tubes is included. A description of the physics program for steam-cooled reactors is included. Results indicated that power from the steam-cooled reactor would cost 1.4 mills/ kwh compared with 1.25 mills/kwh for CANDU. (M.C.G.)« less

Surface modification techniques for increased corrosion tolerance of zirconium fuel cladding

NASA Astrophysics Data System (ADS)

Carr, James Patrick, IV

Corrosion is a major issue in applications involving materials in normal and severe environments, especially when it involves corrosive fluids, high temperatures, and radiation. Left unaddressed, corrosion can lead to catastrophic failures, resulting in economic and environmental liabilities. In nuclear applications, where metals and alloys, such as steel and zirconium, are extensively employed inside and outside of the nuclear reactor, corrosion accelerated by high temperatures, neutron radiation, and corrosive atmospheres, corrosion becomes even more concerning. The objectives of this research are to study and develop surface modification techniques to protect zirconium cladding by the incorporation of a specific barrier coating, and to understand the issues related to the compatibility of the coatings examined in this work. The final goal of this study is to recommend a coating and process that can be scaled-up for the consideration of manufacturing and economic limits. This dissertation study builds on previous accident tolerant fuel cladding research, but is unique in that advanced corrosion methods are tested and considerations for implementation by industry are practiced and discussed. This work will introduce unique studies involving the materials and methods for accident tolerant fuel cladding research by developing, demonstrating, and considering materials and processes for modifying the surface of zircaloy fuel cladding. This innovative research suggests that improvements in the technique to modify the surface of zirconium fuel cladding are likely. Three elements selected for the investigation of their compatibility on zircaloy fuel cladding are aluminum, silicon, and chromium. These materials are also currently being investigated at other labs as alternate alloys and coatings for accident tolerant fuel cladding. This dissertation also investigates the compatibility of these three elements as surface modifiers, by comparing their microstructural and mechanical properties. To test their application for use in corrosive atmospheres, the corrosion behaviors are also compared in steam, water, and boric-acid environments. Various methods of surface modification were attempted in this investigation, including dip coating, diffusion bonding, casting, sputtering, and evaporation. The benefits and drawbacks of each method are discussed with respect to manufacturing and economic limits. Characterization techniques utilized in this work include optical microscopy, scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, nanoindentation, adhesion testing, and atomic force microscopy. The composition, microstructure, hardness, modulus, and coating adhesion were studied to provide encompassing properties to determine suitable comparisons and to choose an ideal method to scale to industrial applications. The experiments, results, and detailed discussions are presented in the following chapters of this dissertation research.

Morphological analysis of zirconium nuclear fuel retaining rods braided with SiC: Quality assurance and defect identification

NASA Astrophysics Data System (ADS)

Glazoff, Michael V.; Hiromoto, Robert; Tokuhiro, Akira

2014-08-01

In the after-Fukushima world, the stability of materials under extreme conditions is an important issue for the safety of nuclear reactors. Among the methods explored currently to improve zircaloys’ thermal stability in off-normal conditions, using a protective coat of the SiC filaments is considered because silicon carbide is well known for its remarkable chemical inertness at high temperatures. A typical SiC fiber contains ∼50,000 individual filaments of 5-10 μm in diameter. In this paper, an effort was made to develop and apply mathematical morphology to the process of automatic defect identification in Zircaloy-4 rods braided with the protective layer of the silicon carbide filament. However, the issues of the braiding quality have to be addressed to ensure its full protective potential. We present the original mathematical morphology algorithms that allow solving this problem of quality assurance successfully. In nuclear industry, such algorithms are used for the first time, and could be easily generalized to the case of automated continuous monitoring for defect identification in the future.

Morphological Analysis of Zirconium Nuclear Fuel Retaining Rods Braided with SiC: Quality Assurance and Defect Identification

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

Michael V Glazoff; Robert Hiromoto; Akira Tokuhiro

In the after-Fukushima world, the stability of materials under extreme conditions is an important issue for the safety of nuclear reactors. Among the methods explored currently to improve zircaloys’ thermal stability in off-normal conditions, using a protective coat of the SiC filaments is considered because silicon carbide is well known for its remarkable chemical inertness at high temperatures. A typical SiC fiber contains ~50,000 individual filaments of 5 – 10 µm in diameter. In this paper, an effort was made to develop and apply mathematical morphology to the process of automatic defect identification in Zircaloy-4 rods braided with the protectivemore » layer of the silicon carbide filament. However, the issues of the braiding quality have to be addressed to ensure its full protective potential. We present the original mathematical morphology algorithms that allow solving this problem of quality assurance successfully. In nuclear industry, such algorithms are used for the first time, and could be easily generalized to the case of automated continuous monitoring for defect identification in the future.« less

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

Verkerk, B.

In 1959 a fuel development program was undertaken based on UO/sub 2/ in which it was intended to study all variables that could influence the quality of fabricated UO/sub 2/-pellets. Later this program was extended to a study of electrolytic UO/sub 2/ with the fabrication of swaged or vibratory compacted fuel elements in mind, and recently the study of the UO/sub 2/-PuO/sub 2/ system was incorporated in it. In order to obtain a better knowledge of the UO/sub 2/- powders that can be used for sintering purposes, an extensive study was made of various preparation methods. A small plutonium laboratorymore » containing equipment for the preparation of UO/sub 2/-- PuO/sub 2/ pellets containing 1 to 10% PuO/sub 2/ was set up and preliminary experiments were performed. Work on a small scale was done on pressing and sintering of UO/sub 2/ made along various routes. The reduction process was also studied. For the regeneration of scrap, especially for the case of enriched material, a 5-kg batch dissolution and precipitation plant was built. This installation is also used for various precipitation studies on a larger scale. Within the scope of tue fuel development program the study of canning materials is also of great importance. For the ship-propulsion reactor Zircaloy-2 was chosen as canning material. Various welding experiments were done in an argon-arc welding chamber and it was found that under well selected conditions very satisfactory end-cap welds could be obtained. 1n the corrosion program it became clear that proper conditioning is of utmost importance. Means of pre-operation treatment are being studied. In the HFR a low-temperature, low-pressure loop for the irradiation of capsules is in regular operation. The pressurized loop now under construction was designed for testing of fuel rods and clusters as planned for the ship-propulsion reactor, under conditions close to those of the actual reactor. The facilities for the post- irradiation measurements consist of two lead cells. (auth)« less

Characterisation of high temperature refractory ceramics for nuclear applications

NASA Astrophysics Data System (ADS)

Bottomley, P. D. W.; Wiss, Th; Janssen, A.; Cremer, B.; Thiele, H.; Manara, D.; Scheindlin, M.; Murray-Farthing, M.; Lajarge, P.; Menna, M.; Bouexière, D.; Rondinella, V. V.

2012-03-01

The ternary oxide ceramic system UO2-ZrO2-FeO is a refractory system that is of great relevance to the nuclear industry as it represents one of the main systems resulting from the interaction of the Zircaloy cladding, the UO2 fuel and the structural elements of a nuclear reactor. It is particularly the high temperature properties that require investigation; that is, when substantial overheating of the nuclear core occurs and interactions can lead to its degradation, melting and result in a severe nuclear accident. There has been much work on the UO2-ZrO2 system and also on the ternary system with FeO but there is still a need to examine 2 further aspects; firstly the effect of sub-oxidized systems, the UO2-Zr and FeO-Zr systems, and secondly the effect of Fe/Zr or Fe/U ratios on the melting point of the U-Zr-Fe oxide system. Samples of UO2-Zr and UO2-ZrO2-FeO were fabricated at ITU and then characterized by optical microscopy (OM) and X-ray diffraction to determine the ceramic's structure and verify the composition. Thereafter the samples are to be melted by laser flash heating and their liquidus and solidus temperatures determined by pyrometry. This programme is currently ongoing. The frozen samples, after testing, were then sectioned, polished and the molten zone micro-analytically examined by OM & SEM-EDS in order to determine its structure and composition and to compare with the existing phase diagrams. Examples of results from these systems will be given. Finally, a reacted Zr-FeO thermite mixture was examined, which had been used to generate high temperatures during tests of reactor melt-concrete interactions. The aim was to assess the reaction and estimate the heat generation from this novel technique. These results allow verification or improvement of the phase diagram and are of primary importance as input to models used to predict materials interactions in a severe nuclear accident.

TRANSURANUS: a fuel rod analysis code ready for use

NASA Astrophysics Data System (ADS)

Lassmann, K.

1992-06-01

TRANSURANUS is a computer program for the thermal and mechanical analysis of fuel rods in nuclear reactors and was developed at the European Institute for Transuranium Elements (TUI). The TRANSURANUS code consists of a clearly defined mechanical-mathematical framework into which physical models can easily be incorporated. Besides its flexibility for different fuel rod designs the TRANSURANUS code can deal with very different situations, as given for instance in an experiment, under normal, off-normal and accident conditions. The time scale of the problems to be treated may range from milliseconds to years. The code has a comprehensive material data bank for oxide, mixed oxide, carbide and nitride fuels, Zircaloy and steel claddings and different coolants. During its development great effort was spent on obtaining an extremely flexible tool which is easy to handle, exhibiting very fast running times. The total development effort is approximately 40 man-years. In recent years the interest to use this code grew and the code is in use in several organisations, both research and private industry. The code is now available to all interested parties. The paper outlines the main features and capabilities of the TRANSURANUS code, its validation and treats also some practical aspects.

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

Jensen, Colby B.; Folsom, Charles P.; Davis, Cliff B.

Experimental testing in the Multi-Static Environment Rodlet Transient Test Apparatus (SERTTA) will lead the rebirth of transient fuel testing in the United States as part of the Accident Tolerant Fuels (ATF) progam. The Multi-SERTTA is comprised of four isolated pressurized environments capable of a wide variety of working fluids and thermal conditions. Ultimately, the TREAT reactor as well as the Multi-SERTTA test vehicle serve the purpose of providing desired thermal-hydraulic boundary conditions to the test specimen. The initial ATF testing in TREAT will focus on reactivity insertion accident (RIA) events using both gas and water environments including typical PWR operatingmore » pressures and temperatures. For the water test environment, a test configuration is envisioned using the expansion tank as part of the gas-filled expansion volume seen by the test to provide additional pressure relief. The heat transfer conditions during the high energy power pulses of RIA events remains a subject of large uncertainty and great importance for fuel performance predictions. To support transient experiments, the Multi-SERTTA vehicle has been modeled using RELAP5 with a baseline test specimen composed of UO2 fuel in zircaloy cladding. The modeling results show the influence of the designs of the specimen, vehicle, and transient power pulses. The primary purpose of this work is to provide input and boundary conditions to fuel performance code BISON. Therefore, studies of parameters having influence on specimen performance during RIA transients are presented including cladding oxidation, power pulse magnitude and width, cladding-to-coolant heat fluxes, fuel-to-cladding gap, transient boiling effects (modified CHF values), etc. The results show the great flexibility and capacity of the TREAT Multi-SERTTA test vehicle to provide testing under a wide range of prototypic thermal-hydraulic conditions as never done before.« less

A study into the impact of interface roughness development on mechanical degradation of oxides formed on zirconium alloys

NASA Astrophysics Data System (ADS)

Platt, P.; Wedge, S.; Frankel, P.; Gass, M.; Howells, R.; Preuss, M.

2015-04-01

As a cladding material used to encapsulate nuclear fuel pellets, zirconium alloys are the primary barrier separating the fuel and a pressurised steam or lithiated water environment. Degradation mechanisms such as oxidation can be the limiting factor in the life-time of the fuel assembly. Key to controlling oxidation, and therefore allowing increased burn-up of fuel, is the development of a mechanistic understanding of the corrosion process. In an autoclave, the oxidation kinetics for zirconium alloys are typically cyclical, with periods of accelerated kinetics being observed in steps of ∼2 μm oxide growth. These periods of accelerated oxidation are immediately preceded by the development of a layer of lateral cracks near the metal-oxide interface, which may be associated with the development of interface roughness. The present work uses scanning electron microscopy to carry out a statistical analysis of changes in the metal-oxide interface roughness between three different alloys at different stages of autoclave oxidation. The first two alloys are Zircaloy-4 and ZIRLO™ for which analysis is carried out at stages before, during and after first transition. The third alloy is an experimental low tin alloy, which under the same oxidation conditions and during the same time period does not appear to go through transition. Assessment of the metal-oxide interface roughness is primarily carried out based on the root mean square of the interface slope known as the Rdq parameter. Results show clear trends with relation to transition points in the corrosion kinetics. Discussion is given to how this relates to the existing mechanistic understanding of the corrosion process, and the components required for possible future modelling approaches.

Survey of Thermal-Fluids Evaluation and Confirmatory Experimental Validation Requirements of Accident Tolerant Cladding Concepts with Focus on Boiling Heat Transfer Characteristics

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

Brown, Nicholas R.; Wysocki, Aaron J.; Terrani, Kurt A.

The U.S. Department of Energy Office of Nuclear Energy (DOE-NE) Advanced Fuels Campaign (AFC) is working closely with the nuclear industry to develop fuel and cladding candidates with potentially enhanced accident tolerance, also known as accident tolerant fuel (ATF). Thermal-fluids characteristics are a vital element of a holistic engineering evaluation of ATF concepts. One vital characteristic related to boiling heat transfer is the critical heat flux (CHF). CHF plays a vital role in determining safety margins during normal operation and also in the progression of potential transient or accident scenarios. This deliverable is a scoping survey of thermal-fluids evaluation andmore » confirmatory experimental validation requirements of accident tolerant cladding concepts with a focus on boiling heat transfer characteristics. The key takeaway messages of this report are: 1. CHF prediction accuracy is important and the correlations may have significant uncertainty. 2. Surface conditions are important factors for CHF, primarily the wettability that is characterized by contact angle. Smaller contact angle indicates greater wettability, which increases the CHF. Surface roughness also impacts wettability. Results in the literature for pool boiling experiments indicate changes in CHF by up to 60% for several ATF cladding candidates. 3. The measured wettability of FeCrAl (i.e., contact angle and roughness) indicates that CHF should be investigated further through pool boiling and flow boiling experiments. 4. Initial measurements of static advancing contact angle and surface roughness indicate that FeCrAl is expected to have a higher CHF than Zircaloy. The measured contact angle of different FeCrAl alloy samples depends on oxide layer thickness and composition. The static advancing contact angle tends to decrease as the oxide layer thickness increases.« less

Microstructural Characterization of Irradiated U0.7ZrH1.6 Using Ultrasonic Techniques

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

Ramuhalli, Pradeep; Jacob, Richard E.; MacFarlan, Paul J.

In recent years, there has been an increased level of effort to understand the changes in microstructure that occur due to irradiation of nuclear fuel. The primary driver for this increased effort is the potential for designing new fuels that are safer and more reliable, in turn enabling new and improved reactor technologies. Much of the data on microstructural change in irradiated fuels is generated through a host of post irradiation examination techniques such as optical microscopy (OM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) to determine grain structure, porosity, crack geometry, etc. in irradiated fuels. Such “traditional”more » examination techniques were recently used to characterize a novel new fuel consisting of U0.17ZrH1.6 pellets bonded to zircaloy-2 cladded with lead-bismuth eutectic before and after irradiation. However, alternative methods such as ultrasonic inspection can provide an opportunity for nondestructively assessing microstructure in both in-pile and post-irradiation examinations. In this paper, we briefly describe initial results of ultrasonic examination of the U0.17ZrH1.6 pellets (unirradiated and irradiated), in a post-irradiation examination study. Data indicate some correlation with microstructural changes due to irradiation; however, it is not clear what the specific microstructural changes are that are influencing the ultrasonic measurements. Interestingly, specimens with nominally identical burnup show differences in ultrasonic signatures, indicating apparent microstructural differences between these specimens. A summary of the experimental study, preliminary data and findings are presented in this short paper. Additional details of the analysis will be included in the presentation.« less

Finite-element model to predict roll-separation force and defects during rolling of U-10Mo alloys

NASA Astrophysics Data System (ADS)

Soulami, Ayoub; Burkes, Douglas E.; Joshi, Vineet V.; Lavender, Curt A.; Paxton, Dean

2017-10-01

A major goal of the Convert Program of the U.S. Department of Energy's National Nuclear Security Administration (DOE/NNSA) is to enable high-performance research reactors to operate with low-enriched uranium rather than the high-enriched uranium currently used. To this end, uranium alloyed with 10 wt% molybdenum (U-10Mo) represents an ideal candidate because of its stable gamma phase, low neutron caption cross section, acceptable swelling response, and predictable irradiation behavior. However, because of the complexities of the fuel design and the need for rolled monolithic U-10Mo foils, new developments in processing and fabrication are necessary. This study used a finite-element code, LS-DYNA, as a predictive tool to optimize the rolling process. Simulations of the hot rolling of U-10Mo coupons encapsulated in low-carbon steel were conducted following two different schedules. Model predictions of the roll-separation force and roll pack thicknesses at different stages of the rolling process were compared with experimental measurements. The study reported here discussed various attributes of the rolled coupons revealed by the model (e.g., waviness and thickness non-uniformity like dog-boning). To investigate the influence of the cladding material on these rolling defects, other cases were simulated: hot rolling with alternative can materials, namely, 304 stainless steel and Zircaloy-2, and bare-rolling. Simulation results demonstrated that reducing the mismatch in strength between the coupon and can material improves the quality of the rolled sheet. Bare-rolling simulation results showed a defect-free rolled coupon. The finite-element model developed and presented in this study can be used to conduct parametric studies of several process parameters (e.g., rolling speed, roll diameter, can material, and reduction).

Preliminary Modeling of Accident Tolerant Fuel Concepts under Accident Conditions

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

Gamble, Kyle A.; Hales, Jason D.

2016-12-01

The catastrophic events that occurred at the Fukushima-Daiichi nuclear power plant in 2011 have led to widespread interest in research of alternative fuels and claddings that are proposed to be accident tolerant. Thus, the United States Department of Energy through its NEAMS (Nuclear Energy Advanced Modeling and Simulation) program has funded an Accident Tolerant Fuel (ATF) High Impact Problem (HIP). The ATF HIP is funded for a three-year period. The purpose of the HIP is to perform research into two potential accident tolerant concepts and provide an in-depth report to the Advanced Fuels Campaign (AFC) describing the behavior of themore » concepts, both of which are being considered for inclusion in a lead test assembly scheduled for placement into a commercial reactor in 2022. The initial focus of the HIP is on uranium silicide fuel and iron-chromium-aluminum (FeCrAl) alloy cladding. Utilizing the expertise of three national laboratory participants (INL, LANL, and ANL) a comprehensive mulitscale approach to modeling is being used including atomistic modeling, molecular dynamics, rate theory, phase-field, and fuel performance simulations. In this paper, we present simulations of two proposed accident tolerant fuel systems: U3Si2 fuel with Zircaloy-4 cladding, and UO2 fuel with FeCrAl cladding. The simulations investigate the fuel performance response of the proposed ATF systems under Loss of Coolant and Station Blackout conditions using the BISON code. Sensitivity analyses are completed using Sandia National Laboratories’ DAKOTA software to determine which input parameters (e.g., fuel specific heat) have the greatest influence on the output metrics of interest (e.g., fuel centerline temperature). Early results indicate that each concept has significant advantages as well as areas of concern. Further work is required prior to formulating the proposition report for the Advanced Fuels Campaign.« less

Modelling Accident Tolerant Fuel Concepts

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

Hales, Jason Dean; Gamble, Kyle Allan Lawrence

2016-05-01

The catastrophic events that occurred at the Fukushima-Daiichi nuclear power plant in 2011 have led to widespread interest in research of alternative fuels and claddings that are proposed to be accident tolerant. The United States Department of Energy (DOE) through its Nuclear Energy Advanced Modeling and Simulation (NEAMS) program has funded an Accident Tolerant Fuel (ATF) High Impact Problem (HIP). The ATF HIP is a three-year project to perform research on two accident tolerant concepts. The final outcome of the ATF HIP will be an in-depth report to the DOE Advanced Fuels Campaign (AFC) giving a recommendation on whether eithermore » of the two concepts should be included in their lead test assembly scheduled for placement into a commercial reactor in 2022. The two ATF concepts under investigation in the HIP are uranium silicide fuel and iron-chromium-aluminum (FeCrAl) alloy cladding. Utilizing the expertise of three national laboratory participants (Idaho National Laboratory, Los Alamos National Laboratory, and Argonne National Laboratory), a comprehensive multiscale approach to modeling is being used that includes atomistic modeling, molecular dynamics, rate theory, phase-field, and fuel performance simulations. Model development and fuel performance analysis are critical since a full suite of experimental studies will not be complete before AFC must prioritize concepts for focused development. In this paper, we present simulations of the two proposed accident tolerance fuel systems: U3Si2 fuel with Zircaloy-4 cladding, and UO2 fuel with FeCrAl cladding. Sensitivity analyses are completed using Sandia National Laboratories’ Dakota software to determine which input parameters (e.g., fuel specific heat) have the greatest influence on the output metrics of interest (e.g., fuel centerline temperature). We also outline the multiscale modelling approach being employed. Considerable additional work is required prior to preparing the recommendation report for the Advanced Fuels Campaign.« less

Mechanism-based modeling of solute strengthening: Application to thermal creep in Zr alloy

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

Wen, Wei; Capolungo, Laurent; Tome, Carlos N.

In this paper, a crystallographic thermal creep model is proposed for Zr alloys that accounts for the hardening contribution of solutes via their time-dependent pinning effect on dislocations. The core-diffusion model proposed by Soare and Curtin (2008a) is coupled with a recently proposed constitutive modeling framework (Wang et al., 2017, 2016) accounting for the heterogeneous distribution of internal stresses within grains. The Coble creep mechanism is also included. This model is, in turn, embedded in the effective medium crystallographic VPSC framework and used to predict creep strain evolution of polycrystals under different temperature and stress conditions. The simulation results reproducemore » the experimental creep data for Zircaloy-4 and the transition between the low (n~1), intermediate (n~4) and high (n~9) power law creep regimes. This is achieved through the dependence on local aging time of the solute-dislocation binding energy. The anomalies in strain rate sensitivity (SRS) are discussed in terms of core-diffusion effects on dislocation junction strength. The mechanism-based model captures the primary and secondary creep regimes results reported by Kombaiah and Murty (2015a, 2015b) for a comprehensive set of testing conditions covering the 500–600 °C interval, stresses spanning 14–156 MPa, and steady state creep rates varying between 1.5·10 -9s -1 to 2·10 -3s -1. There are two major advantages to this model with respect to more empirical ones used as constitutive laws for describing thermal creep of cladding: 1) specific dependences on the nature of solutes and their concentrations are explicitly accounted for; 2) accident conditions in reactors, such as RIA and LOCA, usually take place in short times, and deformation takes place in the primary, not the steady-state creep stage. Finally, as a consequence, a model that accounts for the evolution with time of microstructure is more reliable for this kind of simulation.« less

Mechanism-based modeling of solute strengthening: Application to thermal creep in Zr alloy

DOE PAGES

Wen, Wei; Capolungo, Laurent; Tome, Carlos N.

2018-03-11

In this paper, a crystallographic thermal creep model is proposed for Zr alloys that accounts for the hardening contribution of solutes via their time-dependent pinning effect on dislocations. The core-diffusion model proposed by Soare and Curtin (2008a) is coupled with a recently proposed constitutive modeling framework (Wang et al., 2017, 2016) accounting for the heterogeneous distribution of internal stresses within grains. The Coble creep mechanism is also included. This model is, in turn, embedded in the effective medium crystallographic VPSC framework and used to predict creep strain evolution of polycrystals under different temperature and stress conditions. The simulation results reproducemore » the experimental creep data for Zircaloy-4 and the transition between the low (n~1), intermediate (n~4) and high (n~9) power law creep regimes. This is achieved through the dependence on local aging time of the solute-dislocation binding energy. The anomalies in strain rate sensitivity (SRS) are discussed in terms of core-diffusion effects on dislocation junction strength. The mechanism-based model captures the primary and secondary creep regimes results reported by Kombaiah and Murty (2015a, 2015b) for a comprehensive set of testing conditions covering the 500–600 °C interval, stresses spanning 14–156 MPa, and steady state creep rates varying between 1.5·10 -9s -1 to 2·10 -3s -1. There are two major advantages to this model with respect to more empirical ones used as constitutive laws for describing thermal creep of cladding: 1) specific dependences on the nature of solutes and their concentrations are explicitly accounted for; 2) accident conditions in reactors, such as RIA and LOCA, usually take place in short times, and deformation takes place in the primary, not the steady-state creep stage. Finally, as a consequence, a model that accounts for the evolution with time of microstructure is more reliable for this kind of simulation.« less

Analysis of the FeCrAl Accident Tolerant Fuel Concept Benefits during BWR Station Blackout Accidents

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

Robb, Kevin R

2015-01-01

Iron-chromium-aluminum (FeCrAl) alloys are being considered for fuel concepts with enhanced accident tolerance. FeCrAl alloys have very slow oxidation kinetics and good strength at high temperatures. FeCrAl could be used for fuel cladding in light water reactors and/or as channel box material in boiling water reactors (BWRs). To estimate the potential safety gains afforded by the FeCrAl concept, the MELCOR code was used to analyze a range of postulated station blackout severe accident scenarios in a BWR/4 reactor employing FeCrAl. The simulations utilize the most recently known thermophysical properties and oxidation kinetics for FeCrAl. Overall, when compared to the traditionalmore » Zircaloy-based cladding and channel box, the FeCrAl concept provides a few extra hours of time for operators to take mitigating actions and/or for evacuations to take place. A coolable core geometry is retained longer, enhancing the ability to stabilize an accident. Finally, due to the slower oxidation kinetics, substantially less hydrogen is generated, and the generation is delayed in time. This decreases the amount of non-condensable gases in containment and the potential for deflagrations to inhibit the accident response.« less

M3FT-16OR0203052-Test Design for FeCrAl Alloy Tube Irradiation in HFIR

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

Terrani, Kurt A.; Petrie, Christian M.

2016-05-01

This calculation summarizes thermal analyses of a flexible rabbit design for irradiating a variety of pressurized water reactor (PWR) cladding materials (stainless steel, iron-chromium aluminum [FeCrAl], Zircaloy, and Inconel) with variable dimensions at a temperature of 350 °C in the flux trap of the High Flux Isotope Reactor (HFIR). The design can accommodate standard cladding for outer diameters (ODs) of approximately 9.50 mm with thickness ranging from 0.30 mm to 0.70 mm. The length is generally between 10 and 50 mm. The specimens contain moly inserts with a variable OD that provides the heat flux necessary to achieve the designmore » temperature with such a small fixed gas gap. The primary outer containment is an Al-6061 housing with a slightly enlarged inner diameter (ID) of 9.60 mm. The specimen temperature is controlled by determining a helium/argon gas mixture specific to the as-built specimen and housing. Variables that affect the required gas mixture are the cladding material (thermal expansion, density, heat generation rate), cladding OD, housing ID, and cladding ID. This calculation documents the analyses performed to determine required gas mixtures for a variety of scenarios.« less

Analysis of Ignition Testing on K-West Basin Fuel

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

J. Abrefah; F.H. Huang; W.M. Gerry

Approximately 2100 metric tons of spent nuclear fuel (SNF) discharged from the N-Reactor have been stored underwater at the K-Basins in the 100 Area of the Hanford Site. The spent fuel has been stored in the K-East Basin since 1975 and in the K-West Basin since 1981. Some of the SNF elements in these basins have corroded because of various breaches in the Zircaloy cladding that occurred during fuel discharge operations and/or subsequent handling and storage in the basins. Consequently, radioactive material in the fuel has been released into the basin water, and water has leaked from the K-East Basinmore » into the soil below. To protect the Columbia River, which is only 380 m from the basins, the SNF is scheduled to be removed and transported for interim dry storage in the 200 East Area, in the central portion of the Site. However, before being shipped, the corroded fuel elements will be loaded into Multi-Canister OverPacks and conditioned. The conditioning process will be selected based on the Integrated Process Strategy (IPS) (WHC 1995), which was prepared on the basis of the dry storage concept developed by the Independent Technical Assessment (ITA) team (ITA 1994).« less

Design of pellet surface grooves for fission gas plenum

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

Carter, T.J.; Jones, L.R.; Macici, N.

1986-01-01

In the Canada deuterium uranium pressurized heavy water reactor, short (50-cm) Zircaloy-4 clad bundles are fueled on-power. Although internal void volume within the fuel rods is adequate for the present once-through natural uranium cycle, the authors have investigated methods for increasing the internal gas storage volume needed in high-power, high-burnup, experimental ceramic fuels. This present work sought to prove the methodology for design of gas storage volume within the fuel pellets - specifically the use of grooves pressed or machined into the relatively cool pellet/cladding interface. Preanalysis and design of pellet groove shape and volume was accomplished using the TRUMPmore » heat transfer code. Postirradiation examination (PIE) was used to check the initial design and heat transfer assumptions. Fission gas release was found to be higher for the grooved pellet rods than for the comparison rods with hollow or unmodified pellets. This had been expected from the initial TRUMP thermal analyses. The ELESIM fuel modeling code was used to check in-reactor performance, but some modifications were necessary to accommodate the loss of heat transfer surface to the grooves. It was concluded that for plenum design purposes, circumferential pellet grooves could be adequately modeled by the codes TRUMP and ELESIM.« less

Parametric and experimentally informed BWR Severe Accident Analysis Utilizing FeCrAl - M3FT-17OR020205041

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

Ott, Larry J.; Howell, Michael; Robb, Kevin R.

Iron-chromium-aluminum (FeCrAl) alloys are being considered as advanced fuel cladding concepts with enhanced accident tolerance. At high temperatures, FeCrAl alloys have slower oxidation kinetics and higher strength compared with zirconium-based alloys. FeCrAl could be used for fuel cladding and spacer or mixing vane grids in light water reactors and/or as channel box material in boiling water reactors (BWRs). There is a need to assess the potential gains afforded by the FeCrAl accident-tolerant-fuel (ATF) concept over the existing zirconium-based materials employed today. To accurately assess the response of FeCrAl alloys under severe accident conditions, a number of FeCrAl properties and characteristicsmore » are required. These include thermophysical properties as well as burst characteristics, oxidation kinetics, possible eutectic interactions, and failure temperatures. These properties can vary among different FeCrAl alloys. Oak Ridge National Laboratory has pursued refined values for the oxidation kinetics of the B136Y FeCrAl alloy (Fe-13Cr-6Al wt %). This investigation included oxidation tests with varying heating rates and end-point temperatures in a steam environment. The rate constant for the low-temperature oxidation kinetics was found to be higher than that for the commercial APMT FeCrAl alloy (Fe-21Cr-5Al-3Mo wt %). Compared with APMT, a 5 times higher rate constant best predicted the entire dataset (root mean square deviation). Based on tests following heating rates comparable with those the cladding would experience during a station blackout, the transition to higher oxidation kinetics occurs at approximately 1,500°C. A parametric study varying the low-temperature FeCrAl oxidation kinetics was conducted for a BWR plant using FeCrAl fuel cladding and channel boxes using the MELCOR code. A range of station blackout severe accident scenarios were simulated for a BWR/4 reactor with Mark I containment. Increasing the FeCrAl low-temperature oxidation rate constant (3 times and 10 times that of the rate constant for APMT) had a negligible impact on the early stages of the accident and minor impacts on the accident progression after the first relocation of the fuel. At temperatures below 1,500°C, increasing the rate constant for APMT by a factor of 10 still resulted in only minor FeCrAl oxidation. In general, the gains afforded by the FeCrAl enhanced ATF concept with respect to accident sequence timing and combustible gas generation are consistent with previous efforts. Compared with the traditional Zircaloy-based cladding and channel box system, the FeCrAl concept could provide a few extra hours of time for operators to take mitigating actions and/or for evacuations to take place. A coolable core geometry is retained longer, enhancing the ability to stabilize an accident. For example, a station blackout was simulated in which cooling water injection was lost 36 hours after shutdown. The timing to first fuel relocation was delayed by approximately 5 h for the FeCrAl ATF concept compared with that of the traditional Zircaloy-based cladding and channel box system.« less

Experimental and Numerical Investigation of Pressure Drop in Silicon Carbide Fuel Rod for Application in Pressurized Water Reactors

NASA Astrophysics Data System (ADS)

Abir, Ahmed Musafi

Spacer grids are used in Pressurized Water Reactors (PWRs) fuel assemblies which enhances heat transfer from fuel rods. However, there remain regions of low turbulence in between the spacer grids. To enhance turbulence in these regions surface roughness is applied on the fuel rod walls. Meyer [1] used empirical correlations to predict heat transfer and friction factor for artificially roughened fuel rod bundles at High Performance Light Water Reactors (LWRs). Their applicability was tested by Carrilho at University of South Carolina's (USC) Single Heated Element Loop Tester (SHELT). He attained a heat transfer and friction factor enhancement of 50% and 45% respectively, using Inconel nuclear fuel rods with square transverse ribbed surface. Following him Najeeb conducted a similar study due to three dimensional diamond shaped blocks in turbulent flow. He recorded a maximum heat transfer enhancement of 83%. At present, several types of materials are being used for fuel rod cladding including Zircaloy, Uranium oxide, etc. But researchers are actively searching for new material that can be a more practical alternative. Silicon Carbide (SiC) has been identified as a material of interest for application as fuel rod cladding [2]. The current study deals with the experimental investigation to find out the friction factor increase of a SiC fuel rod with 3D surface roughness. The SiC rod was tested at USC's SHELT loop. The experiment was conducted in turbulent flowing Deionized (DI) water at steady state conditions. Measurements of Flow rate and pressure drop were made. The experimental results were also validated by Computational Fluid Dynamics (CFD) analysis in ANSYS Fluent. To simplify the CFD analysis and to save computational resources the 3D roughness was approximated as a 2D one. The friction factor results of the CFD investigation was found to lie within +/-8% of the experimental results. A CFD model was also run with the energy equation turned on, and a heat generation of 8 kW applied to the rod. A maximum heat transfer enhancement of 18.4% was achieved at the highest flow rate investigated (i.e. Re=109204).

IN-PILE LOOP IRRADIATION OF AQUEOUS THORIA-URANIA SLURRY AT ELEVATED TEMPERATURE. DESIGN AND IN-PILE OPERATION OF LOOP L-2-27S

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

Savage, H.C.; Compere, E.L.; Baker, J.M.

1962-02-14

An in-pile pump loop, designed to fit within horizontal beam hole HB-2 of the Low-Intensity Test Reactor (LlTR), was used to circulate an aqueous thoria- urania slurry while exposed to reactor irradiation. The total loop volume was about 1600 ml, including pump and pressurizer, but the slurry was confined to the 900-ml volume of the main loop stream by means of a sintered stainless steel filter. The filter was an important feature of the loop design in that it provided a thoria-free filtrate as a purge stream to the pressurizer and pump bearings to prevent entry and accumulation of thoriamore » in these two regions. Corrosion-test specimens of Zircaloy-2, titanium, and type 347 stainless steel were placed in the loop at three different locations for exposure to three different levels of irradiation. Duplicate sets of specimens in each position were exposed to flow velocities of 8 and 22 fps, respectively. For the in-pile irradiation, thorium oxide containing 0.43 wt of enriched U, based on Th, was used. This thoria-urania was produced by air calcination at l225 deg C of coprecipit.ited oxalates and had a me.in particle size of l.7 mu . A Pd catalyst w-as dispersed in the slurry for liquid-phase recombination of the radiolytic gas. The loop was operated in beam-holc HB-2 of the LlTR from July 19 to October l9, l960. During this period slurry was continuously eireulated at 280 deg C for 2220 hr without incident; 1839 hr were at full reactor power (3 Mwt), at which the estimated average thermal flux over the 300volume core section was 5 x l0/sup 12/ neutrons/cm/sup 2/- see. At the start of in-pile operation the loop was charged to a concei tration of 979 g of Th and 3.83 g of fully enriched U per li (at 280 deg C) which was reduced by sampling to 748 g of Th idnd 2.74 g of U per liter at the end of the irradiiition period bascd on the assunmption that no losses had occurrcd. Siinmples of slurry were withdrawn at intervals for analyses to determine the effects of radiation on the thoria-urania slurry. (auth)« less

Pellet cladding mechanical interactions of ceramic claddings fuels under light water reactor conditions

NASA Astrophysics Data System (ADS)

Li, Bo-Shiuan

Ceramic materials such as silicon carbide (SiC) are promising candidate materials for nuclear fuel cladding and are of interest as part of a potential accident tolerant fuel design due to its high temperature strength, dimensional stability under irradiation, corrosion resistance, and lower neutron absorption cross-section. It also offers drastically lower hydrogen generation in loss of coolant accidents such as that experienced at Fukushima. With the implementation of SiC material properties to the fuel performance code, FRAPCON, performances of the SiC-clad fuel are compared with the conventional Zircaloy-clad fuel. Due to negligible creep and high stiffness, SiC-clad fuel allows gap closure at higher burnup and insignificant cladding dimensional change. However, severe degradation of SiC thermal conductivity with neutron irradiation will lead to higher fuel temperature with larger fission gas release. High stiffness of SiC has a drawback of accumulating large interfacial pressure upon pellet-cladding mechanical interactions (PCMI). This large stress will eventually reach the flexural strength of SiC, causing failure of SiC cladding instantly in a brittle manner instead of the graceful failure of ductile metallic cladding. The large interfacial pressure causes phenomena that were previously of only marginal significance and thus ignored (such as creep of the fuel) to now have an important role in PCMI. Consideration of the fuel pellet creep and elastic deformation in PCMI models in FRAPCON provide for an improved understanding of the magnitude of accumulated interfacial pressure. Outward swelling of the pellet is retarded by the inward irradiation-induced creep, which then reduces the rate of interfacial pressure buildup. Effect of PCMI can also be reduced and by increasing gap width and cladding thickness. However, increasing gap width and cladding thickness also increases the overall thermal resistance which leads to higher fuel temperature and larger fission gas release. An optimum design is sought considering both thermal and mechanical models of this ceramic cladding with UO2 and advanced high density fuels.

SINQ layout, operation, applications and R&D to high power

NASA Astrophysics Data System (ADS)

Bauer, G. S.; Dai, Y.; Wagner, W.

2002-09-01

Since 1997, the Paul Scherrer Institut (PSI) is operating a 1 MW class research spallation neutron source, named SINQ. SINQ is driven by a cascade of three accelerators, the final stage being a 590 MeV isochronous ring cyclotron which delivers a beam current of 1.8 mA at an rf-frequency of 51 MHz. Since for neutron production this is essentially a dc-device, SINQ is a continuous neutron source and is optimized in its design for high time average neutron flux. This makes the facility similar to a research reactor in terms of utilization, but, in terms of beam power, it is, by a large margin, the most powerful spallation neutron source currently in operation world wide. As a consequence, target load levels prevail in SINQ which are beyond the realm of existing experience, demanding a careful approach to the design and operation of a high power target. While the best neutronic performance of the source is expected for a liquid lead-bismuth eutectic target, no experience with such systems exists. For this reason a staged approach has been embarked upon, starting with a heavy water cooled rod target of Zircaloy-2 and proceeding via steel clad lead rods towards the final goal of a target optimised in both, neutronic performance and service life time. Experience currently accruing with a test target containing sample rods with different materials specimens will help to select the proper structural material and make dependable life time estimates accounting for the real operating conditions that prevail in the facility. In parallel, both theoretical and experimental work is going on within the MEGAPIE (MEGAwatt Pilot Experiment) project, a joint initiative by six European research institutions and JAERI (Japan), DOE (USA) and KAERI (Korea), to design, build, operate and explore a liquid lead-bismuth spallation target for 1MW of beam power, taking advantage of the existing spallation neutron facility SINQ.

System analysis with improved thermo-mechanical fuel rod models for modeling current and advanced LWR materials in accident scenarios

NASA Astrophysics Data System (ADS)

Porter, Ian Edward

A nuclear reactor systems code has the ability to model the system response in an accident scenario based on known initial conditions at the onset of the transient. However, there has been a tendency for these codes to lack the detailed thermo-mechanical fuel rod response models needed for accurate prediction of fuel rod failure. This proposed work will couple today's most widely used steady-state (FRAPCON) and transient (FRAPTRAN) fuel rod models with a systems code TRACE for best-estimate modeling of system response in accident scenarios such as a loss of coolant accident (LOCA). In doing so, code modifications will be made to model gamma heating in LWRs during steady-state and accident conditions and to improve fuel rod thermal/mechanical analysis by allowing axial nodalization of burnup-dependent phenomena such as swelling, cladding creep and oxidation. With the ability to model both burnup-dependent parameters and transient fuel rod response, a fuel dispersal study will be conducted using a hypothetical accident scenario under both PWR and BWR conditions to determine the amount of fuel dispersed under varying conditions. Due to the fuel fragmentation size and internal rod pressure both being dependent on burnup, this analysis will be conducted at beginning, middle and end of cycle to examine the effects that cycle time can play on fuel rod failure and dispersal. Current fuel rod and system codes used by the Nuclear Regulatory Commission (NRC) are compilations of legacy codes with only commonly used light water reactor materials, Uranium Dioxide (UO2), Mixed Oxide (U/PuO 2) and zirconium alloys. However, the events at Fukushima Daiichi and Three Mile Island accident have shown the need for exploration into advanced materials possessing improved accident tolerance. This work looks to further modify the NRC codes to include silicon carbide (SiC), an advanced cladding material proposed by current DOE funded research on accident tolerant fuels (ATF). Several additional fuels will also be analyzed, including uranium nitride (UN), uranium carbide (UC) and uranium silicide (U3Si2). Focusing on the system response in an accident scenario, an emphasis is placed on the fracture mechanics of the ceramic cladding by design the fuel rods to eliminate pellet cladding mechanical interaction (PCMI). The time to failure and how much of the fuel in the reactor fails with an advanced fuel design will be analyzed and compared to the current UO2/Zircaloy design using a full scale reactor model.

MELCOR Model of the Spent Fuel Pool of Fukushima Dai-ichi Unit 4

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

Carbajo, Juan J

2012-01-01

Unit 4 of the Fukushima Dai-ichi Nuclear Power Plant suffered a hydrogen explosion at 6:00 am on March 15, 2011, exactly 3.64 days after the earthquake hit the plant and the off-site power was lost. The earthquake occurred on March 11 at 2:47 pm. Since the reactor of this Unit 4 was defueled on November 29, 2010, and all its fuel was stored in the spent fuel pool (SFP4), it was first believed that the explosion was caused by hydrogen generated by the spent fuel, in particular, by the recently discharged core. The hypothetical scenario was: power was lost, coolingmore » to the SFP4 water was lost, pool water heated/boiled, water level decreased, fuel was uncovered, hot Zircaloy reacted with steam, hydrogen was generated and accumulated above the pool, and the explosion occurred. Recent analyses of the radioisotopes present in the water of the SFP4 and underwater video indicated that this scenario did not occur - the fuel in this pool was not damaged and was never uncovered the hydrogen of the explosion was apparently generated in Unit 3 and transported through exhaust ducts that shared the same chimney with Unit 4. This paper will try to answer the following questions: Could that hypothetical scenario in the SFP4 had occurred? Could the spent fuel in the SPF4 generate enough hydrogen to produce the explosion that occurred 3.64 days after the earthquake? Given the magnitude of the explosion, it was estimated that at least 150 kg of hydrogen had to be generated. As part of the investigations of this accident, MELCOR models of the SFP4 were prepared and a series of calculations were completed. The latest version of MELCOR, version 2.1 (Ref. 1), was employed in these calculations. The spent fuel pool option for BWR fuel was selected in MELCOR. The MELCOR model of the SFP4 consists of a total of 1535 fuel assemblies out of which 548 assemblies are from the core defueled on Nov. 29, 2010, 783 assemblies are older assemblies, and 204 are new/fresh assemblies. The total decay heat of the fuel in the pool was, at the time of the accident, 2.284 MWt, of which 1.872 MWt were from the 548 assemblies of the last core discharged and 0.412 MWt were from the older 783 assemblies. These decay heat values were calculated at Oak Ridge National Laboratory using the ORIGEN2.2 code (Ref. 2) - they agree with values reported elsewhere (Ref. 3). The pool dimensions are 9.9 m x 12.2 m x 11.8 m (height), and with the water level at 11.5 m, the pool volume is 1389 m3, of which only 1240 m3 is water, as some volume is taken by the fuel and by the fuel racks. The initial water temperature of the SFP4 was assumed to be 301 K. The fuel racks are made of an aluminum alloy but are modeled in MELCOR with stainless steel and B4C. MELCOR calculations were completed for different initial water levels: 11.5 m (pool almost full, water is only 0.3 m below the top rim), 4.4577 m (top of the racks), 4.2 m, and 4.026 m (top of the active fuel). A calculation was also completed for a rapid loss of water due to a leak at the bottom of the pool, with the fuel rapidly uncovered and oxidized in air. Results of these calculations are shown in the enclosed Table I. The calculation with the initial water level at 11.5 m (full pool) takes 11 days for the water to boil down to the top of the fuel racks, 11.5 days for the fuel to be uncovered, 14.65 days to generate 150 kg of hydrogen and 19 days for the pool to be completely dry. The calculation with the initial water level at 4.4577 m, takes 1.1 days to uncover the fuel and 4.17 days to generate 150 kg of hydrogen. The calculation with the initial water level at 4.02 m takes 3.63 days to generate 150 kg of hydrogen this is exactly the time when the actual explosion occurred in Unit 4. Finally, fuel oxidation in air after the pool drained the water in 20 minutes, generates only 10 kg of hydrogen this is because very little steam is available and Zircaloy (Zr) oxidation with the oxygen of the air does not generate hydrogen. MELCOR calculated water levels and hydrogen generated in the SFP4 as a function of time for initial water levels of 4.457 m, 4.2 m and 4.02 m are shown in Figs. 1 and 2. Water levels increase at the beginning due to the expansion of the water during the heat-up from 301 K to 373 K. Boiling occurs after the water temperature reaches 373 K. The total amount of hydrogen generated is ~2000 kg, this amount includes hydrogen generated from Zr, which is the largest amount (~1580 kg), from stainless steel (~360 kg), and from B4C (~60 kg). In theory, it is possible to generate up to 3.4 kg of hydrogen per assembly (from oxidation of Zr in the fuel cladding and box), or a total of 4,525 kg from the hot 1331 assemblies stored in the SFP4. The hydrogen generated from oxidation of steel and B4C will be additional. So the answers to the questions are YES according to these MELCOR calculations, enough hydrogen (150 kg) could be generated in the SFP4 3.64 days after the earthquake to produce ...« less

Status report on the cold neutron source of the Garching neutron research facility FRM-II

NASA Astrophysics Data System (ADS)

Gobrecht, K.; Gutsmiedl, E.; Scheuer, A.

2002-01-01

The new high flux research reactor of the Technical University of Munich (Technische Universität München, TUM) will be equipped with a cold neutron source (CNS). The centre of the CNS will be located in the D 2O-reflector tank at 400 mm from the reactor core axis close to the thermal neutron flux maximum. The power of 4500 W developed by the nuclear heating in the 16 l of liquid deuterium at 25 K, and in the structures, is evacuated by a two-phase thermal siphon avoiding film boiling and flooding. The thermal siphon is a single tube with counter current flow. It is inclined by 10° from vertical, and optimised for a deuterium flow rate of 14 g/s. Optimisation of structure design and material, as well as safety aspects will be discussed. Those parts of the structure, which are exposed to high thermal neutron flux, are made from Zircaloy 4 and 6061T6 aluminium. Structure failure due to embrittlement of the structure material under high rapid neutron flux is very improbable during the lifetime of the CNS (30 years). Double, in pile even triple, containment with inert gas liner guarantees lack of explosion risk and of tritium contamination to the environment. Adding a few percent of hydrogen (H 2) to the deuterium (D 2) will improve the moderating properties of our relatively small moderator volume. Nearly all of the hydrogen is bound in the form of HD molecules. A long-term change of the hydrogen content in the deuterium is avoided by storing the mixture not in a gas buffer volume but as a metal hydride at low pressure. The metal hydride storage system contains two getter beds, one with 250 kg of LaCo 3Ni 2, the other one with 150 kg of ZrCo 0.8Ni 0.2. Each bed can take the total gas inventory, both beds together can absorb the total gas inventory in <6 min at a pressure <3 bar. The new reactor will have 13 beam tubes, 4 of which are looking at the CNS, including two for very cold (VCN) and ultra-cold neutron (UCN) production. The latter will take place in the horizontal beam tube SR4, which will house an additional cryogenic moderator (e.g. solid deuterium). More than 60% of the experiments foreseen in the new neutron research facility will use cold neutrons from the CNS. The mounting of the hardware components of the CNS into the reactor has started in the spring of 2000. The CNS went into trial operation in the end of year 2000.

The effect of stress state on zirconium hydride reorientation

NASA Astrophysics Data System (ADS)

Cinbiz, Mahmut Nedim

Prior to storage in a dry-cask facility, spent nuclear fuel must undergo a vacuum drying cycle during which the spent fuel rods are heated up to elevated temperatures of ≤ 400°C to remove moisture the canisters within the cask. As temperature increases during heating, some of the hydride particles within the cladding dissolve while the internal gas pressure in fuel rods increases generating multi-axial hoop and axial stresses in the closed-end thin-walled cladding tubes. As cool-down starts, the hydrogen in solid solution precipitates as hydride platelets, and if the multiaxial stresses are sufficiently large, the precipitating hydrides reorient from their initial circumferential orientation to radial orientation. Radial hydrides can severely embrittle the spent nuclear fuel cladding at low temperature in response to hoop stress loading. Because the cladding can experience a range of stress states during the thermo-mechanical treatment induced during vacuum drying, this study has investigated the effect of stress state on the process of hydride reorientation during controlled thermo-mechanical treatments utilizing the combination of in situ X-ray diffraction and novel mechanical testing analyzed by the combination of metallography and finite element analysis. The study used cold worked and stress relieved Zircaloy-4 sheet containing approx. 180 wt. ppm hydrogen as its material basis. The failure behavior of this material containing radial hydrides was also studied over a range of temperatures. Finally, samples from reactor-irradiated cladding tubes were examined by X-ray diffraction using synchrotron radiation. To reveal the stress state effect on hydride reorientation, the critical threshold stress to reorient hydrides was determined by designing novel mechanical test samples which produce a range of stress states from uniaxial to "near-equibiaxial" tension when a load is applied. The threshold stress was determined after thermo-mechanical treatments by correlating the finite element stress-state results with the spatial distribution of hydride microstructures observed within the optical micrographs for each sample. Experiments showed that the hydride reorientation was enhanced as the stress biaxiality increased. The threshold stress decreased from 150 MPa to 80 MPa when stress biaxiality ratio increased from uniaxial tension to near-equibiaxial tension. This behavior was also predicted by classical nucleation theory based on the Gibbs free energy of transformation being assisted by the far-field stress. An analysis of in situ X-ray diffraction data obtained during a thermo-mechanical cycle typical of vacuum drying showed a complex lattice-spacing behavior of the hydride phase during the dissolution and precipitation. The in-plane hydrides showed bilinear lattice expansion during heating with the intrinsic thermal expansion rate of the hydrides being observed only at elevated temperatures as they dissolve. For radial hydrides that precipitate during cooling under stress, the spacing of the close-packed {111} planes oriented normal to the maximum applied stress was permanently higher than the corresponding {111} plane spacing in the other directions. This behavior is believed to be a result of a complex stress state within the precipitating plate-like hydrides that induces a strain component within the hydrides normal to its "plate" face (i.e., the applied stress direction) that exceeds the lattice spacing strains in the other directions. During heat-up, the lattice spacing of these same "plate" planes actually contract due to the reversion of the stress state within the plate-like hydrides as they dissolve. The presence of radial hydrides and their connectivity with in-plane hydrides was shown to increase the ductile-to-brittle transition temperature during tensile testing. This behavior can be understood in terms of the role of radial hydrides in promoting the initiation of a long crack that subsequently propagates under fracture mechanics conditions. Finally, the d-spacing of irradiated Zircaloy-4 and M5 cladding tubes was measured at room temperature and compared to that of unirradiated samples.

Simulation of irradiation hardening of Zircaloy within plate-type dispersion nuclear fuel elements

NASA Astrophysics Data System (ADS)

Jiang, Yijie; Wang, Qiming; Cui, Yi; Huo, Yongzhong; Ding, Shurong

2011-06-01

Within plate-type dispersion nuclear fuel elements, the metal matrix and cladding attacked continuously by fast neutrons undergo irradiation hardening, which might have remarkable effects upon the mechanical behaviors within fuel elements. In this paper, with the irradiation hardening effect of metal materials mainly considered together with irradiation growth effect of the cladding, the three-dimensional large-deformation constitutive relations for the metal matrix and cladding are developed. The method of virtual temperature increase in the previous studies is further developed to model the irradiation swelling of fuel particles; the method of anisotropic thermal expansion is introduced to model irradiation growth of the cladding; and a method of multi-step-temperature loading is proposed to simulate the coupling features of irradiation-induced swelling of the fuel particles together with irradiation growth of the cladding. Above all, based on the developed relationship between irradiation growth at certain burnup and the loaded virtual temperatures, with considering that certain burnup corresponds to certain fast neutron fluence, the time-dependent constitutive relation due to irradiation hardening effect is replaced by the virtual-temperature-dependent one which is introduced into the commercial software to simulate the irradiation hardening effects of the matrix and cladding. Numerical simulations of the irradiation-induced mechanical behaviors are implemented with the finite element method in consideration of the micro-structure of the fuel meat. The obtained results indicate that when the irradiation hardening effects are introduced into the constitutive relations of the metal matrix and cladding: (1) higher maximum Mises stresses for certain burnup at the matrix exist with the equivalent plastic strains remaining almost the same at lower burnups; (2) the maximum Mises stresses for certain burnup at the cladding are enhanced while the maximum equivalent plastic strains are reduced; and (3) the maximum first principal stresses for certain burnup at the matrix or the cladding are lower than the ones without the hardening effect, and the differences are found to increase with burnup; and the variation rules of the interfacial stresses are similar.

Ultra-High Temperature Steam Corrosion of Complex Silicates for Nuclear Applications: A Computational Study

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

Rashkeev, Sergey N.; Glazoff, Michael V.; Tokuhiro, Akira

2014-01-01

Stability of materials under extreme conditions is an important issue for safety of nuclear reactors. Presently, silicon carbide (SiC) is being studied as a cladding material candidate for fuel rods in boiling-water and pressurized water-cooled reactors (BWRs and PWRs) that would substitute or modify traditional zircaloy materials. The rate of corrosion of the SiC ceramics in hot vapor environment (up to 2200 degrees C) simulating emergency conditions of light water reactor (LWR) depends on many environmental factors such as pressure, temperature, viscosity, and surface quality. Using the paralinear oxidation theory developed for ceramics in the combustion reactor environment, we estimatedmore » the corrosion rate of SiC ceramics under the conditions representing a significant power excursion in a LWR. It was established that a significant time – at least 100 h – is required for a typical SiC braiding to significantly degrade even in the most aggressive vapor environment (with temperatures up to 2200 °C) which is possible in a LWR at emergency condition. This provides evidence in favor of using the SiC coatings/braidings for additional protection of nuclear reactor rods against off-normal material degradation during power excursions or LOCA incidents. Additionally, we discuss possibilities of using other silica based ceramics in order to find materials with even higher corrosion resistance than SiC. In particular, we found that zircon (ZrSiO4) is also a very promising material for nuclear applications. Thermodynamic and first-principles atomic-scale calculations provide evidence of zircon thermodynamic stability in aggressive environments at least up to 1535 degrees C.« less

Overview of the U.S. DOE Accident Tolerant Fuel Development Program

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

Jon Carmack; Frank Goldner; Shannon M. Bragg-Sitton

2013-09-01

The United States Fuel Cycle Research and Development Advanced Fuels Campaign has been given the responsibility to conduct research and development on enhanced accident tolerant fuels with the goal of performing a lead test assembly or lead test rod irradiation in a commercial reactor by 2022. The Advanced Fuels Campaign has defined fuels with enhanced accident tolerance as those that, in comparison with the standard UO2-Zircaloy system currently used by the nuclear industry, can tolerate loss of active cooling in the reactor core for a considerably longer time period (depending on the LWR system and accident scenario) while maintaining ormore » improving the fuel performance during normal operations and operational transients, as well as design-basis and beyond design-basis events. This paper provides an overview of the FCRD Accident Tolerant Fuel program. The ATF attributes will be presented and discussed. Attributes identified as potentially important to enhance accident tolerance include reduced hydrogen generation (resulting from cladding oxidation), enhanced fission product retention under severe accident conditions, reduced cladding reaction with high-temperature steam, and improved fuel-cladding interaction for enhanced performance under extreme conditions. To demonstrate the enhanced accident tolerance of candidate fuel designs, metrics must be developed and evaluated using a combination of design features for a given LWR design, potential improvements to that design, and the design of an advanced fuel/cladding system. The aforementioned attributes provide qualitative guidance for parameters that will be considered for fuels with enhanced accident tolerance. It may be unnecessary to improve in all attributes and it is likely that some attributes or combination of attributes provide meaningful gains in accident tolerance, while others may provide only marginal benefits. Thus, an initial step in program implementation will be the development of quantitative metrics. A companion paper in these proceedings provides an update on the status of establishing these quantitative metrics for accident tolerant LWR fuel.1 The United States FCRD Advanced Fuels Campaign has embarked on an aggressive schedule for development of enhanced accident tolerant LWR fuels. The goal of developing such a fuel system that can be deployed in the U.S. LWR fleet in the next 10 to 20 years supports the sustainability of clean nuclear power generation in the United States.« less

Crystallographic texture and microstructural changes in fusion welds of recrystallized Zry-4 rolled plates

NASA Astrophysics Data System (ADS)

Moya Riffo, A.; Vicente Alvarez, M. A.; Santisteban, J. R.; Vizcaino, P.; Limandri, S.; Daymond, M. R.; Kerr, D.; Okasinski, J.; Almer, J.; Vogel, S. C.

2017-05-01

This work presents a detailed characterization of the microstructural and crystallographic texture changes observed in the transition region in a weld between two Zircaloy-4 cold rolled and recrystallized plates. The microstructural study was performed by optical microscopy under polarized light and scanning electron microscopy (SEM). Texture changes were characterized at different lengthscales: in the micrometric size, orientation imaging maps (OIM) were constructed by electron backscatter diffraction (EBSD), in the millimetre scale, high energy XRD experiments were done at the Advanced Photon Source (USA) and compared to neutron diffraction texture determinations performed in the HIPPO instrument at Los Alamos National Laboratory. In the heat affected zone (HAZ) we observed the development of Widmanstätten microstructures, typical of the α(hcp) to β(bcc) phase transformation. Associated with these changes a rotation of the c-poles is found in the HAZ and fusion zone. While the base material shows the typical texture of a cold rolled plate, with their c-poles pointing 35° apart from the normal direction of the plate in the normal-transversal line, in the HAZ, c-poles align along the transversal direction of the plate and then re-orient along different directions, all of these changes occurring within a lengthscale in the order of mm. The evolution of texture in this narrow region was captured by both OIM and XRD, and is consistent with previous measurements done by Neutron Diffraction in the HIPPO diffractometer at Los Alamos National Laboratory, USA. The microstructural and texture changes along the HAZ were interpreted as arising due to the effect of differences in the cooling rate and β grain size on the progress of the different α variants during transformation. Fast cooling rates and large β grains are associated to weak variant selection during the β->α transformation, while slow cooling rates and fine β grains result in strong variant selection.

Crystallographic texture and microstructural changes in fusion welds of recrystallized Zry-4 rolled plates

DOE PAGES

Riffo, A. Moya; Vicente Alvarez, M. A.; Santisteban, J. R.; ...

2017-02-08

This study presents a detailed characterization of the microstructural and crystallographic texture changes observed in the transition region in a weld between two Zircaloy-4 cold rolled and recrystallized plates. The microstructural study was performed by optical microscopy under polarized light and scanning electron microscopy (SEM). Texture changes were characterized at different lengthscales: in the micrometric size, orientation imaging maps (OIM) were constructed by electron backscatter diffraction (EBSD), in the millimetre scale, high energy XRD experiments were done at the Advanced Photon Source (USA) and compared to neutron diffraction texture determinations performed in the HIPPO instrument at Los Alamos National Laboratory.more » In the heat affected zone (HAZ) we observed the development of Widmanstätten microstructures, typical of the α( hcp) to β( bcc) phase transformation. Associated with these changes a rotation of the c-poles is found in the HAZ and fusion zone. While the base material shows the typical texture of a cold rolled plate, with their c-poles pointing 35° apart from the normal direction of the plate in the normal-transversal line, in the HAZ, c-poles align along the transversal direction of the plate and then re-orient along different directions, all of these changes occurring within a lengthscale in the order of mm. The evolution of texture in this narrow region was captured by both OIM and XRD, and is consistent with previous measurements done by Neutron Diffraction in the HIPPO diffractometer at Los Alamos National Laboratory, USA. The microstructural and texture changes along the HAZ were interpreted as arising due to the effect of differences in the cooling rate and β grain size on the progress of the different α variants during transformation. Fast cooling rates and large β grains are associated to weak variant selection during the β–>α transformation, while slow cooling rates and fine β grains result in strong variant selection.« less

Crystallographic texture and microstructural changes in fusion welds of recrystallized Zry-4 rolled plates

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

Riffo, A. Moya; Vicente Alvarez, M. A.; Santisteban, J. R.

This study presents a detailed characterization of the microstructural and crystallographic texture changes observed in the transition region in a weld between two Zircaloy-4 cold rolled and recrystallized plates. The microstructural study was performed by optical microscopy under polarized light and scanning electron microscopy (SEM). Texture changes were characterized at different lengthscales: in the micrometric size, orientation imaging maps (OIM) were constructed by electron backscatter diffraction (EBSD), in the millimetre scale, high energy XRD experiments were done at the Advanced Photon Source (USA) and compared to neutron diffraction texture determinations performed in the HIPPO instrument at Los Alamos National Laboratory.more » In the heat affected zone (HAZ) we observed the development of Widmanstätten microstructures, typical of the α( hcp) to β( bcc) phase transformation. Associated with these changes a rotation of the c-poles is found in the HAZ and fusion zone. While the base material shows the typical texture of a cold rolled plate, with their c-poles pointing 35° apart from the normal direction of the plate in the normal-transversal line, in the HAZ, c-poles align along the transversal direction of the plate and then re-orient along different directions, all of these changes occurring within a lengthscale in the order of mm. The evolution of texture in this narrow region was captured by both OIM and XRD, and is consistent with previous measurements done by Neutron Diffraction in the HIPPO diffractometer at Los Alamos National Laboratory, USA. The microstructural and texture changes along the HAZ were interpreted as arising due to the effect of differences in the cooling rate and β grain size on the progress of the different α variants during transformation. Fast cooling rates and large β grains are associated to weak variant selection during the β–>α transformation, while slow cooling rates and fine β grains result in strong variant selection.« less

Spent fuel behavior under abnormal thermal transients during dry storage

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

Stahl, D.; Landow, M.P.; Burian, R.J.

1986-01-01

This study was performed to determine the effects of abnormally high temperatures on spent fuel behavior. Prior to testing, calculations using the CIRFI3 code were used to determine the steady-state fuel and cask component temperatures. The TRUMP code was used to determine transient heating rates under postulated abnormal events during which convection cooling of the cask surfaces was obstructed by a debris bed covering the cask. The peak rate of temperature rise during the first 6 h was calculated to be about 15/sup 0/C/h, followed by a rate of about 1/sup 0/C/h. A Turkey Point spent fuel rod segment wasmore » heated to approx. 800/sup 0/C. The segment deformed uniformly with an average strain of 17% at failure and a local strain of 60%. Pretest characterization of the spent fuel consisted of visual examination, profilometry, eddy-current examination, gamma scanning, fission gas collection, void volume measurement, fission gas analysis, hydrogen analysis of the cladding, burnup analysis, cladding metallography, and fuel ceramography. Post-test characterization showed that the failure was a pinhole cladding breach. The results of the tests showed that spent fuel temperatures in excess of 700/sup 0/C are required to produce a cladding breach in fuel rods pressurized to 500 psing (3.45 MPa) under postulated abnormal thermal transient cask conditions. The pinhole cladding breach that developed would be too small to compromise the confinement of spent fuel particles during an abnormal event or after normal cooling conditions are restored. This behavior is similar to that found in other slow ramp tests with irradiated and nonirradiated rod sections and nonirradiated whole rods under conditions that bracketed postulated abnormal heating rates. This similarity is attributed to annealing of the irradiation-strengthened Zircaloy cladding during heating. In both cases, the failure was a benign, ductile pinhole rupture.« less

Physical and mechanical metallurgy of zirconium alloys for nuclear applications: a multi-scale computational study

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

Glazoff, Michael Vasily

2014-10-01

In the post-Fukushima world, the stability of materials under extreme conditions is an important issue for the safety of nuclear reactors. Because the nuclear industry is going to continue using advanced zirconium cladding materials in the foreseeable future, it become critical to gain fundamental understanding of the several interconnected problems. First, what are the thermodynamic and kinetic factors affecting the oxidation and hydrogen pick-up by these materials at normal, off-normal conditions, and in long-term storage? Secondly, what protective coatings (if any) could be used in order to gain extremely valuable time at off-normal conditions, e.g., when temperature exceeds the criticalmore » value of 2200°F? Thirdly, the kinetics of oxidation of such protective coating or braiding needs to be quantified. Lastly, even if some degree of success is achieved along this path, it is absolutely critical to have automated inspection algorithms allowing identifying defects of cladding as soon as possible. This work strives to explore these interconnected factors from the most advanced computational perspective, utilizing such modern techniques as first-principles atomistic simulations, computational thermodynamics of materials, diffusion modeling, and the morphological algorithms of image processing for defect identification. Consequently, it consists of the four parts dealing with these four problem areas preceded by the introduction and formulation of the studied problems. In the 1st part an effort was made to employ computational thermodynamics and ab initio calculations to shed light upon the different stages of oxidation of ziraloys (2 and 4), the role of microstructure optimization in increasing their thermal stability, and the process of hydrogen pick-up, both in normal working conditions and in long-term storage. The 2nd part deals with the need to understand the influence and respective roles of the two different plasticity mechanisms in Zr nuclear alloys: twinning (at low T) and crystallographic slip (higher T’s). For that goal, a description of the advanced plasticity model is outlined featuring the non-associated flow rule in hcp materials including Zr. The 3rd part describes the kinetic theory of oxidation of the several materials considered to be perspective coating materials for Zr alloys: SiC and ZrSiO 4. In the 4th part novel and advanced projectional algorithms for defect identification in zircaloy coatings are described. In so doing, the author capitalized on some 12 years of his applied industrial research in this area. Our conclusions and recommendations are presented in the 5th part of this work, along with the list of used literature and the scripts for atomistic, thermodynamic, kinetic, and morphological computations.« less

Analysis of pellet cladding interaction and creep of U 3SIi2 fuel for use in light water reactors

NASA Astrophysics Data System (ADS)

Metzger, Kathryn E.

Following the accident at the Fukushima plant, enhancing the accident tolerance of the light water reactor (LWR) fleet became a topic of serious discussion. Under the direction of congress, the DOE office of Nuclear Energy added accident tolerant fuel development as a primary component to the existing Advanced Fuels Program. The DOE defines accident tolerant fuels as fuels that "in comparison with the standard UO2- Zircaloy system currently used by the nuclear industry, can tolerate loss of active cooling in the reactor core for a considerably longer time period (depending on the LWR system and accident scenario) while maintaining or improving the fuel performance during normal operations, operational transients, as well as design-basis and beyond design-basis events." To be economically viable, proposed accident tolerant fuels and claddings should be backward compatible with LWR designs, provide significant operating cost improvements such as power uprates, increased fuel burnup, or increased cycle length. In terms of safety, an alternative fuel pellet must have resistance to water corrosion comparable to UO2, thermal conductivity equal to or larger than that of UO2, and a melting temperature that allows the material to remain solid under power reactor conditions. Among the candidates, U3Si2 has a number of advantageous thermophysical properties, including; high density, high thermal conductivity at room temperature, and a high melting temperature. These properties support its use as an accident tolerant fuel while its high uranium density is capable of supporting uprates to the LWR fleet. This research characterizes U3Si2 pellets and analyzes U3Si2 under light water reactor conditions using the fuel performance code BISON. While some thermophysical properties for U3Si2 have been found in the literature, the irradiation behavior is sparse and limited to experience with dispersion fuels. Accordingly, the creep behavior for U3Si2 has been unknown, making it difficult to predict fuel-cladding mechanical behavior. This information is essential for designing accident tolerant fuel systems where ceramic claddings, like silicon carbide (SiC) are proposed. This research provides a model for both the thermal and irradiation creep behavior for U3Si2. This body of research is comprised of both experimental and modeling components. Characterization of the fuel microstructure includes; optical microscopy with pore and grain size analysis, helium pycnometry for density determination, mercury intrusion porosimetry, compositional analysis in the form of XRD, second phase identification using EDX, electrical resistance measurement via four point probe, determination of hardness and toughness through Vickers indentation testing, and determination of elastic properties using the impulse excitation method. Post-sintering grain size data allowed for the determination of grain boundary activation energy and diffusion coefficients, which were used to develop creep models. This was extended to lattice and irradiation enhanced diffusion in order to develop a U3Si2 creep model over thermal and irradiation creep regimes. In addition to the creep model, thermal and swelling behavior models for U3Si2 were implemented into the BISON fuel performance code. A series of simulations evaluated the performance and behavior of U3Si2 under typical light water reactor conditions with advanced SiC ceramic cladding. Simulation results show that fuel creep relieves stress in the ceramic cladding and postpones the. moment of fuel-clad contact. However, the stress reduction to the cladding is minimal because the fuel creep rate is low while the swelling rate is high. Future work should include the investigation of monolithic U3Si2 irradiation swelling since the current model relies upon the swelling data of U3Si2 particles in a metallic dispersion fuel. Additionally, planned thermal creep testing at the University of South Carolina can provide confirmation of the U3Si2 creep model contained herein.

Implementation and evaluation of fuel creep using advanced light-water reactor materials in FRAPCON 3.5

NASA Astrophysics Data System (ADS)

Carroll, Spencer

As current reactors approach the end of their operable lifetime, new reactors are needed if nuclear power is to continue being generated in the United States. Some utilities have already began construction on newer, more advanced LWR reactors, which use the same fuel as current reactors and have a similar but updated design. Others are researching next generation (GEN-IV) reactors which have new designs that utilize alternative fuel, coolants and other reactor materials. Many of these alternative fuels are capable of achieving higher burnups and are designed to be more accident tolerant than the currently used UO2 fuel. However, before these new materials can be used, extensive research must be done in order to obtain a detailed understanding of how the new fuels and other materials will interact. New fuels, such as uranium nitride (UN) and uranium carbide (UC) have several advantages over UO2, such as increased burnup capabilities and higher thermal conductivities. However, there are issues with each that prevent UC and UN from being used as direct replacements for UO2. Both UC and UN swell at a significantly higher rate than UO2 and neither fuel reacts favorably when exposed to water. Due to this, UC and UN are being considered more for GEN-IV reactors that use alternative coolant rather than for current LWRs. In an effort to increase accident tolerance, silicon carbide (SiC) is being considered for use as an alternative cladding. The high strength, high melting point and low oxidation of SiC make it an attractive cladding choice, especially in an accident scenario. However, as a ceramic, SiC is not ductile and will not creep outwards upon pellet-clad mechanical interaction (PCMI) which can cause a large build up in interfacial pressure. In order to understand the interaction between the high swelling fuels and unyielding SiC cladding, data on the properties and behaviors of these materials must be gathered and incorporated into FRAPCON. FRAPCON is a fuel performance code developed by PNNL and used by the Nuclear Regulatory Commission (NRC) as a licensing code for US reactors. FRAPCON will give insight into how these new fuel-cladding combinations will affect cladding hoop stress and help determine if the new materials are feasible for use in a reactor. To accurately simulate the interaction between the new materials, a soft pellet model that allows for stresses on the pellet to affect pellet deformation will have to be implemented. Currently, FRAPCON uses a rigid pellet model that does not allow for feedback of the cladding onto the pellet. Since SiC does not creep at the temperatures being considered and is not ductile, any PCMI create a much higher interfacial pressure than is possible with Zircaloy. Because of this, it is necessary to implement a model that allows for pellet creep to alleviate some of these cladding stresses. These results will then be compared to FEMAXI-6, a Japanese fuel performance code that already calculates pellet stress and allows for cladding feedback onto the pellet. This research is intended to be a continuation and verification of previous work done by USC on the analysis of accident tolerant fuels with alternative claddings and is intended to prove that a soft pellet model is necessary to accurately model any fuel with SiC cladding.

100-KE REACTOR CORE REMOVAL PROJECT ALTERNATIVE ANALYSIS WORKSHOP REPORT

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

HARRINGTON RA

2010-01-15

On December 15-16, 2009, a 100-KE Reactor Core Removal Project Alternative Analysis Workshop was conducted at the Washington State University Consolidated Information Center, Room 214. Colburn Kennedy, Project Director, CH2M HILL Plateau Remediation Company (CHPRC) requested the workshop and Richard Harrington provided facilitation. The purpose of the session was to select the preferred Bio Shield Alternative, for integration with the Thermal Shield and Core Removal and develop the path forward to proceed with project delivery. Prior to this workshop, the S.A. Robotics (SAR) Obstruction Removal Alternatives Analysis (565-DLV-062) report was issued, for use prior to and throughout the session, tomore » all the team members. The multidisciplinary team consisted ofrepresentatives from 100-KE Project Management, Engineering, Radcon, Nuclear Safety, Fire Protection, Crane/Rigging, SAR Project Engineering, the Department of Energy Richland Field Office, Environmental Protection Agency, Washington State Department of Ecology, Defense Nuclear Facility Safety Board, and Deactivation and Decommission subject matter experts from corporate CH2M HILL and Lucas. Appendix D contains the workshop agenda, guidelines and expectations, opening remarks, and attendance roster going into followed throughout the workshop. The team was successful in selecting the preferred alternative and developing an eight-point path forward action plan to proceed with conceptual design. Conventional Demolition was selected as the preferred alternative over two other alternatives: Diamond Wire with Options, and Harmonic Delamination with Conventional Demolition. The teams preferred alternative aligned with the SAR Obstruction Removal Alternative Analysis report conclusion. However, the team identified several Path Forward actions, in Appendix A, which upon completion will solidify and potentially enhance the Conventional Demolition alternative with multiple options and approaches to achieve project delivery. In brief, the Path Forward was developed to reconsider potential open air demolition areas; characterize to determine if any zircaloy exists, evaluate existing concrete data to determine additional characterization needs, size the new building to accommodate human machine interface and tooling, consider bucket thumb and use ofshape-charges in design, and finally to utilize complex-wide and industry explosive demolition lessons learned in the design approach. Appendix B documents these results from the team's use ofValue Engineering process tools entitled Weighted Analysis Alternative Matrix, Matrix Conclusions, Evaluation Criteria, and Alternative Advantages and Disadvantages. These results were further supported with the team's validation of parking-lot information sheets: memories (potential ideas to consider), issues/concerns, and assumptions, contained in Appendix C. Appendix C also includes the recorded workshop flipchart notes taken from the SAR Alternatives and Project Overview presentations. The SAR workshop presentations, including a 3-D graphic illustration demonstration video have been retained in the CHPRC project file, and were not included in this report due to size limitations. The workshop concluded with a round robin close-out where each member was engaged for any last minute items and meeting utility. In summary, the team felt the session was value added and looked forward to proceeding with the recommended actions and conceptual design.« less

(Project 14-6770) An Investigation to Establish Multiphysical Property Dataset of Nuclear Materials Based on in-situ Observations and Measurements

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

Tomar, Vikas; Haque, Aman; Hattar, Khalid

In-core nuclear materials including fuel pins and cladding materials fail due to issues including corrosion, mechanical wear, and pellet cladding interaction. In most such scenario microstructure dependent and corrosioninduced chemistry dependent property changes significantly affect performance of cladding, pellet, and housing. Emphasis of this work was on replace conventional pellet-cladding material models with a new straingradient viscoplasticity model that is informed by transmission electron microscopy (TEM) based measurements and by nanomechanical Raman spectroscopy (NMRS) based measurements. The TEM measurements are quantitative in nature and therefore reveal stress-strain relations with simultaneous insights into mechanisms of deformation at nanoscale. The NMRS measurementsmore » reveal the similar information at mesoscale along with additional information on relating local microstructural stresses with applied stresses. The resulting information is used to fit constants in the strain gradient viscoplasticity model as well as to validate one. During TEM measurements, a micro-electro-mechanical system based setup was developed with mechanical actuation, sensing, heating, and electrical loading. Contrary to post-mortem analysis or qualitative visualization, this setup combines direct visualization of the mechanisms behind deformation with measurement of stress, strain, thermal and electrical properties. The unique research philosophy of visualizing the microstructure at high resolution while measuring the properties led to fundamental understanding in grain size and temperature effects on measured mechanical properties such as fracture toughness. A key contribution is the role of mechanical loading boundary conditions to deconvolute the insitu TEM based nanoscale and NMRS based mesoscale data to bulk behavior. First the literature based pellet cladding mechanical interaction model based on the work of Retel’s and Williamson’s in literature work to predict tempurature and stress distribution in cladding and pellet at normal operating condition was analyzed. Later the data was fitted to find constants for a viscoplastic strain gradient model. The developed model still needs to be refined and calibrated using various experimental results. That remains the focus of future work. Overall, a major thrust of the work was therefore on active control of the microstructure (grain size, defect density and types) exploiting the multi-physics coupling in materials. In particular, using experiments the synergy of current density, mechanical stress and temperature were studied to annihilate defects and recrystallize grains. The developed model is being examined for implementation in BISON. Multiple invited talks, international journal publications, and conference publications were performed by students supported on this work. Another output is support multiple PhD and masters thesis students who will be an important asset for future basic nuclear research. Future Work Recommendations: A nuclear reactor operates under significant variations of thermal loads due to energy cycling and mechanical loads due to constraint effects. Significant thermal and chemical diffusion takes place at the pallet-cladding level. While the proposed work established new experimental approach and new dataset for Zircaloy-4, the irradiation level was in the range of 1-2 dpa. Samples with higher dpa need to be examined. Therefore, a continual of support of the performed work is essential. Currently, these are the only experiments that can measure the produced data. The work also needs to be extended to different fuel types and cladding types such as SiC and FeCrAl based claddings. A combination of datasets for these materials can then be used to analyze accurately predict behavior of critical pellet cladding systems in accident scenario with high heat flux and high thermal loads. This is a BIG unknown as if now.« less

TREAT Neutronics Analysis and Design Support, Part II: Multi-SERTTA-CAL

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

Bess, John D.; Woolstenhulme, Nicolas E.; Hill, Connie M.

2016-08-01

Experiment vehicle design is necessary in preparation for Transient Reactor Test (TREAT) facility restart and the resumption of transient testing to support Accident Tolerant Fuel (ATF) characterization and other future fuels testing requirements. Currently the most mature vehicle design is the Multi-SERTTA (Static Environments Rodlet Transient Test Apparatuses), which can accommodate up to four concurrent rodlet-sized specimens under separate environmental conditions. Robust test vehicle design requires neutronics analyses to support design development, optimization of the power coupling factor (PCF) to efficiently maximize energy generation in the test fuel rodlets, and experiment safety analyses. In integral aspect of prior TREAT transientmore » testing was the incorporation of calibration experiments to experimentally evaluate and validate test conditions in preparation of the actual fuel testing. The calibration experiment package established the test parameter conditions to support fine-tuning of the computational models to deliver the required energy deposition to the fuel samples. The calibration vehicle was designed to be as near neutronically equivalent to the experiment vehicle as possible to minimize errors between the calibration and final tests. The Multi-SERTTA-CAL vehicle was designed to serve as the calibration vehicle supporting Multi-SERTTA experimentation. Models of the Multi-SERTTA-CAL vehicle containing typical PWR-fuel rodlets were prepared and neutronics calculations were performed using MCNP6.1 with ENDF/B-VII.1 nuclear data libraries; these results were then compared against those performed for Multi-SERTTA to determine the similarity and possible design modification necessary prior to construction of these experiment vehicles. The estimated reactivity insertion worth into the TREAT core is very similar between the two vehicle designs, with the primary physical difference being a hollow Inconel tube running down the length of the calibration vehicle. Calculations of PCF indicate that on average there is a reduction of approximately 6.3 and 12.6%, respectively, for PWR fuel rodlets irradiated under wet and dry conditions. Changes to the primary or secondary vessel structure in the calibration vehicle can be performed to offset this discrepancy and maintain neutronic equivalency. Current possible modifications to the calibration vehicle include reduction of the primary vessel wall thickness, swapping Zircaloy-4 for stainless steel 316 in the secondary containment, or slight modification to the temperature and pressure of the water environment within the primary vessel. Removal of some of the instrumentation within the calibration vehicle can also serve to slightly increase the PCF. Future efforts include further modification and optimization of the Multi-SERTTA and Multi-SERTTA-CAL designs in preparation of actual TREAT transient testing. Experimental results from both test vehicles will be compared against calculational results and methods to provide validation and support additional neutronics analyses.« less

FUEL ASSEMBLY SHAKER TEST SIMULATION

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

Klymyshyn, Nicholas A.; Sanborn, Scott E.; Adkins, Harold E.

This report describes the modeling of a PWR fuel assembly under dynamic shock loading in support of the Sandia National Laboratories (SNL) shaker test campaign. The focus of the test campaign is on evaluating the response of used fuel to shock and vibration loads that a can occur during highway transport. Modeling began in 2012 using an LS-DYNA fuel assembly model that was first created for modeling impact scenarios. SNL’s proposed test scenario was simulated through analysis and the calculated results helped guide the instrumentation and other aspects of the testing. During FY 2013, the fuel assembly model was refinedmore » to better represent the test surrogate. Analysis of the proposed loads suggested the frequency band needed to be lowered to attempt to excite the lower natural frequencies of the fuel assembly. Despite SNL’s expansion of lower frequency components in their five shock realizations, pretest predictions suggested a very mild dynamic response to the test loading. After testing was completed, one specific shock case was modeled, using recorded accelerometer data to excite the model. Direct comparison of predicted strain in the cladding was made to the recorded strain gauge data. The magnitude of both sets of strain (calculated and recorded) are very low, compared to the expected yield strength of the Zircaloy-4 material. The model was accurate enough to predict that no yielding of the cladding was expected, but its precision at predicting micro strains is questionable. The SNL test data offers some opportunity for validation of the finite element model, but the specific loading conditions of the testing only excite the fuel assembly to respond in a limited manner. For example, the test accelerations were not strong enough to substantially drive the fuel assembly out of contact with the basket. Under this test scenario, the fuel assembly model does a reasonable job of approximating actual fuel assembly response, a claim that can be verified through direct comparison of model results to recorded test results. This does not offer validation for the fuel assembly model in all conceivable cases, such as high kinetic energy shock cases where the fuel assembly might lift off the basket floor to strike to basket ceiling. This type of nonlinear behavior was not witnessed in testing, so the model does not have test data to be validated against.a basis for validation in cases that substantially alter the fuel assembly response range. This leads to a gap in knowledge that is identified through this modeling study. The SNL shaker testing loaded a surrogate fuel assembly with a certain set of artificially-generated time histories. One thing all the shock cases had in common was an elimination of low frequency components, which reduces the rigid body dynamic response of the system. It is not known if the SNL test cases effectively bound all highway transportation scenarios, or if significantly greater rigid body motion than was tested is credible. This knowledge gap could be filled through modeling the vehicle dynamics of a used fuel conveyance, or by collecting acceleration time history data from an actual conveyance under highway conditions.« less

Influence of oxide microstructure on corrosion behavior of zirconium-based model alloys

NASA Astrophysics Data System (ADS)

Silva, Marcelo Jose Gomes Da

The extensive utilization of zirconium-based alloys in fuel cladding and other reactor internal components in the nuclear power industry has led to the continuous improvement of these alloys. At the present moment, demands for better performing nuclear fuel cladding materials are increasing. Also, new reactor designs have been proposed that would require the materials to withstand even more rigorous conditions. One of the factors that limit s fuel cladding utilization in nuclear reactors is uniform corrosion and the consequent hydriding of the fuel. In an attempt to develop mechanistic understanding of the role of alloying elements in the growth of a stable protective oxide, a series of model zirconium-based alloys was prepared (Zr-xFe-yCr, Zr-xCu-yMo, Zr-xNb-ySn, for various x and y, pure Zr and Zircaloy-4) and examined with advanced characterization techniques. The alloys were corrosion tested in autoclaves under three different conditions: 360°C water, 500°C steam and 500°C supercritical water in excess of 400 days. These autoclave testing conditions simulate nuclear reactor environment for both current designs (360°C water) and the new supercritical water reactor (500°C steam and 500°C supercritical water) proposed by the generation-IV initiative. The oxide films formed were systematically examined at the Advanced Photon Source using microbeam synchrotron radiation diffraction and fluorescence of cross-sectional samples to determine the oxide phases present and their crystallographic texture as a function of distance from the metal/oxide interface. Also, the overall texture of the oxide layers was investigated using synchrotron radiation diffraction in frontal geometry. The corrosion kinetics is a function of the alloy system and showed a wide range of behaviors, from immediately unstable oxide growth to stable behavior. The corrosion weight gains from testing at high temperature are a factor of five higher than those measured at 360°C but the protectiveness ranking of the alloys is similar. Measured pole figures from different oxides in different corrosion regimes showed that monoclinic oxides grow in slightly distinct directions: protective oxides grow along the (-904)m pole, whether non-protective oxides grow along or close to the (-302)m pole. The angle in between these two directions ((-904)m and (-302)m) is about 6°. Microbeam synchrotron radiation diffraction and fluorescence was performed in the oxide layers and systematic differences are observed in protective and non-protective oxides, both near the oxide/metal interface and in the bulk of the oxide layers. The non-protective oxide interfaces show a smooth transition from metal to oxide with metal diffraction peaks disappearing as the monoclinic oxide peaks appear. In contrast, in a protective oxide, a complex structure near the oxide/metal interface was seen, showing peaks from Zr 3O suboxide and a highly oriented tetragonal oxide phase with specific orientation relationships with the monoclinic oxide and the base metal. The highly oriented tetragonal phase, only present in protective oxides, is believed to be a precursor to the formation of monoclinic oxide found in the bulk of the oxide layer. This plane may promote stable growth by causing the oxide to form in a manner that maximizes occupation of the substrate surface and minimizes stress accumulation, leading to more stable oxide growth. The association seen in this work of the precursor oxide phase with protective oxides and its orientation relationship with the monoclinic oxide, combined with the difference in oxide growth direction seen between protective and non-protective oxides, is interpreted as evidence that this phase allows a more properly oriented oxide to grow, in a way that minimizes stress accumulation and therefore delays the oxide transition to larger oxide thicknesses.

Fuel Pond Sludge - Lessons Learned from Initial De-sludging of Sellafield's Pile Fuel Storage Pond - 12066

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

Carlisle, Derek; Adamson, Kate

2012-07-01

The Pile Fuel Storage Pond (PFSP) at Sellafield was built and commissioned between the late 1940's and early 1950's as a storage and cooling facility for irradiated fuel and isotopes from the two Windscale Pile reactors. The pond was linked via submerged water ducts to each reactor, where fuel and isotopes were discharged into skips for transfer along the duct to the pond. In the pond the fuel was cooled then de-canned underwater prior to export for reprocessing. The plant operated successfully until it was taken out of operation in 1962 when the First Magnox Fuel Storage Pond took overmore » fuel storage and de-canning operations on the site. The pond was then used for storage of miscellaneous Intermediate Level Waste (ILW) and fuel from the UK's Nuclear Programme for which no defined disposal route was available. By the mid 1970's the import of waste ceased and the plant, with its inventory, was placed into a passive care and maintenance regime. By the mid 1990s, driven by the age of the facility and concern over the potential challenge to dispose of the various wastes and fuels being stored, the plant operator initiated a programme of work to remediate the facility. This programme is split into a number of key phases targeted at sustained reduction in the hazard associated with the pond, these include: - Pond Preparation: Before any remediation work could start the condition of the pond had to be transformed from a passive store to a plant capable of complex retrieval operations. This work included plant and equipment upgrades, removal of redundant structures and the provision of a effluent treatment plant for removing particulate and dissolved activity from the pond water. - Canned Fuel Retrieval: Removal of canned fuel, including oxide and carbide fuels, is the highest priority within the programme. Handling and export equipment required to remove the canned fuel from the pond has been provided and treatment routes developed utilising existing site facilities to allow the fuel to be reprocessed or conditioned for long term storage. - Sludge Retrieval: In excess of 300 m{sup 3} of sludge has accumulated in the pond over many years and is made up of debris arising from fuel and metallic corrosion, wind blown debris and bio-organic materials. The Sludge Retrieval Project has provided the equipment necessary to retrieve the sludge, including skip washer and tipper machines for clearing sludge from the pond skips, equipment for clearing sludge from the pond floor and bays, along with an 'in pond' corral for interim storage of retrieved sludge. Two further projects are providing new plant processing routes, which will initially store and eventually passivate the sludge. - Metal Fuel Retrieval: Metal Fuel from early Windscale Pile operations and various other sources is stored within the pond; the fuel varies considerably in both form and condition. A retrieval project is planned which will provide fuel handling, conditioning, sentencing and export equipment required to remove the metal fuel from the pond for export to on site facilities for interim storage and disposal. - Solid Waste Retrieval: A final retrieval project will provide methods for handling, retrieval, packaging and export of the remaining solid Intermediate Level Waste within the pond. This includes residual metal fuel pieces, fuel cladding (Magnox, aluminium and zircaloy), isotope cartridges, reactor furniture, and miscellaneous activated and contaminated items. Each of the waste streams requires conditioning to allow it to be and disposed of via one of the site treatment plants. - Pond Dewatering and Dismantling: Delivery of the above projects will allow operations to progressively remove the radiological inventory, thereby reducing the hazard/risk posed by the plant. This will then allow subsequent dewatering of the pond and dismantling of the structure. (authors)« less

Fundamental experiments on hydride reorientation in zircaloy

NASA Astrophysics Data System (ADS)

Colas, Kimberly B.

In the current study, an in-situ X-ray diffraction technique using synchrotron radiation was used to follow directly the kinetics of hydride dissolution and precipitation during thermomechanical cycles. This technique was combined with conventional microscopy (optical, SEM and TEM) to gain an overall understanding of the process of hydride reorientation. Thus this part of the study emphasized the time-dependent nature of the process, studying large volume of hydrides in the material. In addition, a micro-diffraction technique was also used to study the spatial distribution of hydrides near stress concentrations. This part of the study emphasized the spatial variation of hydride characteristics such as strain and morphology. Hydrided samples in the shape of tensile dog-bones were used in the time-dependent part of the study. Compact tension specimens were used during the spatial dependence part of the study. The hydride elastic strains from peak shift and size and strain broadening were studied as a function of time for precipitating hydrides. The hydrides precipitate in a very compressed state of stress, as measured by the shift in lattice spacing. As precipitation proceeds the average shift decreases, indicating average stress is reduced, likely due to plastic deformation and morphology changes. When nucleation ends the hydrides follow the zirconium matrix thermal contraction. When stress is applied below the threshold stress for reorientation, hydrides first nucleate in a very compressed state similar to that of unstressed hydrides. After reducing the average strain similarly to unstressed hydrides, the average hydride strain reaches a constant value during cool-down to room temperature. This could be due to a greater ease of deforming the matrix due to the applied far-field strain which would compensate for the strains due to thermal contraction. Finally when hydrides reorient, the average hydride strains become tensile during the first precipitation regime and remain constant in the tensile direction during the second precipitation regime. This could be due to the fact that the face of reoriented hydride platelet is in compression once these platelets have grown to a sufficient size. The second goal of this study was to perform a spatially resolved study of the effect of a stress concentration such as a notch or a crack on hydride reorientation. Using SEM and image analysis, it was found that a sharp crack induces a different hydride microstructure than a blunt notch. In the case of sharp crack, hydrides are more localized and align more with the defect than for blunt notches. The hydride connectivity also increases close to a stress concentration which will assist in crack propagation during DHC. Using TEM, the microstructure of hydrides grown near crack tips were observed to be similar to that of circumferential hydrides grown in the bulk. The orientation relationship studied with SEM and micro-X-ray diffraction was found to be in most cases δ(111)// α(0002) for hydrides grown both near and far from stress concentrations. Using the same micro-X-ray diffraction technique local hydride and matrix elastic strains were measured and observed to vary significantly from grain to grain. It was however observed that hydrides grown close to the stress concentration are in tension in the face of the platelet, similar to reoriented hydrides, while those grown far from the stress concentration are in tension, similar to circumferential hydrides. The orders of magnitude of the measured strains in the hydrides and the zirconium matrix compared well to those predicted by finite element models. This study shows that it is possible to study hydride dissolution and precipitation in-situ using time-dependent techniques. It was found that the precipitation temperature is lowered by hydride reorientation. The evolution of hydride strains during precipitation was found to be different for unstressed, stressed and reoriented hydrides. The reoriented hydride fraction and connectivity increase with number of cycles which could lead to more dangerous microstructure for storage of spent fuel. Pre-existing cracks were also found to affect hydride connectivity and morphology which directly impacts DHC and fuel integrity. (Abstract shortened by UMI.).

Department of Defense Joint Technical Architecture Version 2.0

DTIC Science & Technology

1998-05-26

Mandates 2.1-5 2.1.4.1 Year 2000 (Y2K) Compliance 2.1-5 2.1.4.2 Defense Information Infrastructure Common Operating Environment (DU COE) 2.1-5 2.1.5...2.2.2.2.1.6 Communications Services 2.2-11 2.2.2.2.1.7 Operating System Services 2.2-11 2.2.2.2.2 Application Platform Cross-Area Services 2.2- 12 ...2.2.2.2.2.1 Internationalization Services 2.2- 12 2.2.2.2.2.2 Security Services 2.2- 12 2.2.2.2.2.3 System Management Services 2.2- 12 2.2.2.2.2.4

46 CFR 69.177 - Markings.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 13 14 15 16 17 18 19 20 220 and under 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 230 3.2 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 240 4.7 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 250 6.3 3.3 2.0 2.0 2.0 2.0 2.0 2.0 2.0 260 8.0 4.8 2.1 2.0 2.0 2.0 2.0 2.0 2.0 270 9.9 6.4 3.5 2.0 2.0 2.0 2.0 2.0 2.0 280 11.8 8.1 4.9 2.1 2.0 2.0...

Word Criticality Analysis. MOS: 44B. Skill Levels 1 & 2.

DTIC Science & Technology

1981-09-01

IILh2- 51,1 2- 96,1 2- 40.A a- sv;t t. 94.1 2- Soil 2- 12,2 2- list 2-Z5,1 2- 170i 1. 10,1 2- 95.) 2- 19.1 Z- 50.1 1- 411 * 3 Slits 2- 57j,1 0 3...46.1 2- 44,1 2- 43,1 2- 411J 2- . , 1 2- 53,1 2- .2. 2- 51,1 2- Soil 2- 49,1 2- 68.1 2- 47.1 4 APIII’l~if 2-.2 , SATTERIFS Z- 25,1 2 1 6 PIJ$1| " 2...9s1 2 9 1 2 lt 2 71 2 6 o -63,1 2- 94𔃻 2- 00 2- 0,1 2- 95,1 2- 96,1 2-10001 2- 96.1 A USL 2, 91.1 2 59,1 2- 16.1 2- 51 -1- 40,1 2’ 401 2- 31,2 2- 30#2

10 CFR 2.1000 - Scope of subpart J.

Code of Federal Regulations, 2013 CFR

2013-01-01

... repository at a geologic repository operations area noticed under §§ 2.101(f)(8) or 2.105(a)(5), and for an..., except for the following provisions: §§ 2.301; 2.303; 2.307; 2.309; 2.312; 2.313; 2.314; 2.315; 2.316; 2.317(a); 2.318; 2.319; 2.320; 2.321; 2.322; 2.323; 2.324; 2.325; 2.326; 2.327; 2.328; 2.330; 2.331; 2...

10 CFR 2.1000 - Scope of subpart J.

Code of Federal Regulations, 2014 CFR

2014-01-01

... repository at a geologic repository operations area noticed under §§ 2.101(f)(8) or 2.105(a)(5), and for an..., except for the following provisions: §§ 2.301; 2.303; 2.307; 2.309; 2.312; 2.313; 2.314; 2.315; 2.316; 2.317(a); 2.318; 2.319; 2.320; 2.321; 2.322; 2.323; 2.324; 2.325; 2.326; 2.327; 2.328; 2.330; 2.331; 2...

Design and Analysis of Multi-Sensor Sequential Detection System

DTIC Science & Technology

1991-07-01

7 - A7Ŗ y - 2 Y21 -~ TI 21D2 T 2 -DI T2 2 Tj I e I11 921 f e-21Y-92 T -X-iIx-Liil X f- TD T2 +D2 f e fj e-1Y-2 1 1 log T T1-D1 2 T 2 D2 2. -’! IL...T2 +D2 X2 1 e-X2(T 2 -9 21) _1 e-x 2( T2 +D2 -IL21) q2 2 2 20 T40= 2 x-L2 Y - 2 e2(T 2-D2 -1) _ 1 e-X2(T2-9 21) T2 -D 2 2 2 T2 - 2 X2 2( TD 2 IL2 ) q10...0.5 * exp((-l) * (t - u)); retumn(i); ) double P2(ujl,t,d) double u,I, td ; double i; i= I - 0.5 * exp((-I) * (u - t)) - 0.5 *exp((-l) *(t + d - u

Ruthenium-catalyzed metathesis reactions of ortho- and meta-dialkenyl-carboranes: efficient ring-closing and acyclic diene polymerization reactions.

PubMed

Guron, Marta; Wei, Xiaolan; Carroll, Patrick J; Sneddon, Larry G

2010-07-05

The ruthenium-catalyzed metathesis reactions of dialkenyl-substituted ortho- and meta-carboranes provide excellent routes to both cyclic-substituted o-carboranes and new types of main-chain m-carborane polymers. The adjacent positions of the two olefins in the 1,2-(alkenyl)(2)-o-carboranes strongly favor the formation of ring-closed (RCM) products with the reactions of 1,2-(CH(2)=CHCH(2))(2)-1,2-C(2)B(10)H(10) (1), 1,2-(CH(2)=CH(CH(2))(3)CH(2))(2)-1,2-C(2)B(10)H(10) (2), 1,2-(CH(2)=CHSiMe(2))(2)-1,2-C(2)B(10)H(10) (3), 1,2-(CH(2)=CHCH(2)SiMe(2))(2)-1,2-C(2)B(10)H(10) (4), and 1,2-[CH(2)=CH(CH(2))(4)SiMe(2)](2)-1,2-C(2)B(10)H(10) (5) affording 1,2-(-CH(2)CH=CHCH(2)-)-C(2)B(10)H(10) (10), 1,2-[-CH(2)(CH(2))(3)CH=CH(CH(2))(3)CH(2)-]-1,2-C(2)B(10)H(10) (11), 1,2-[-SiMe(2)CH=CHSiMe(2)-]-1,2-C(2)B(10)H(10) (12), 1,2-[-SiMe(2)CH(2)CH=CHCH(2)SMe(2)-]-C(2)B(10)H(10) (13), and 1,2-[-SiMe(2)(CH(2))(4)CH=CH(CH(2))(4)SiMe(2)-]-C(2)B(10)H(10) (14), respectively, in 72-97% yields. On the other hand, the reaction of 1,2-(CH(2)-CHCH(2)OC(=O))(2)-1,2-C(2)B(10)H(10) (6) gave cyclo-[1,2-(1',8'-C(=O)OCH(2)CH=CHCH(2)OC(=O))-1,2-C(2)B(10)H(10)](2) (15a) and polymer 15b resulting from intermolecular metathesis reactions. The nonadjacent positions of the alkenyl groups in the 1,7-(alkenyl)(2)-m-carboranes, 1,7-(CH(2)=CHCH(2))(2)-1,7-C(2)B(10)H(10) (7), 1,7-(CH(2)=CH(CH(2))(3)CH(2))(2)-1,7-C(2)B(10)H(10) (8), and 1,7-(CH(2)=CHCH(2)SiMe(2))(2)-1,7-C(2)B(10)H(10) (9), disfavor the formation of RCM products, and in these cases, acyclic diene metathesis polymerizations (ADMET) produced new types of main chain m-carborane polymers. The structures of 3, 9, 11, 12, 13, and 15a were crystallographically confirmed.

(Phosphinoalkyl)silanes. 4.(1) Hydrozirconation as a Non-Photochemical Route to (Phosphinopropyl)silanes: Facile Assembly of the Bis(3-(diphenylphosphino)propyl)silyl ("biPSi") Ligand Framework. Access to the Related Poly(3-(dimethylsilyl)propyl)phosphines R(n)()P(CH(2)CH(2)CH(2)SiMe(2)H)(3)(-)(n)() (n = 1, R = Ph; n = 0).

PubMed

Zhou, Xiaobing; Stobart, Stephen R.; Gossage, Robert A.

1997-08-13

Treatment of SiEt(3)(CH=CH(2)) with ZrCp(2)HCl (Schwartz's reagent) followed by reaction with PPh(2)Cl provides a high-yield (75%) route to Ph(2)PCH(2)CH(2)SiEt(3), and accordingly hydrozirconation of CH(2)=CHCH(2)SiHMe(2) affords the intermediate ZrCp(2)(CH(2)CH(2)CH(2)SiHMe(2))Cl (2). The latter, which is very sensitive to hydrolysis and reacts with HCl forming SiHMe(2)Pr(n)() and with NBS or I(2) affording SiHMe(2)CH(2)CH(2)CH(2)X (X = Br (3), I (4)), behaves similarly with PPh(2)Cl, PPhCl(2), or PBr(3) undergoing cleavage to the known Ph(2)PCH(2)CH(2)CH(2)SiMe(2)H (i.e. chelH, A) and the novel bis- and tris(silylpropyl)phosphines PhP(CH(2)CH(2)CH(2)SiMe(2)H)(2) (5) and P(CH(2)CH(2)CH(2)SiMe(2)H)(3) (6), respectively, with concomitant formation of ZrCp(2)Cl(2). Corresponding hydroboration of allylsilanes is facile, but subsequent phosphine halide cleavage yields (phosphinoalkyl)silanes only as constituents of intractable mixtures. Hydrozirconation followed by phosphination with PPh(2)Cl also converts SiHMe(CH(2)CH=CH(2))(2) to SiHMe(CH(2)CH(2)CH(2)PPh(2))(2) (i.e. biPSiH, B) together with a propyl analogue Ph(2)PCH(2)CH(2)CH(2)SiMe(Pr(n)())H (7) of A (ca. 2:1 ratio), as well as SiH(CH(2)CH=CH(2))(3) to a mixture (ca. 5:2:1 ratio) of SiH(CH(2)CH(2)CH(2)PPh(2))(3) (i.e. triPSiH, C), a new analogue SiH(Pr(n)())(CH(2)CH(2)CH(2)PPh(2))(2) (8) of B, and a further analogue Ph(2)PCH(2)CH(2)CH(2)SiHPr(n)()(2) (9) of A. A further analogue SiH(2)(CH(2)CH(2)CH(2)PPh(2))(2) (10) of biPSiH (B) is obtained similarly starting from SiH(2)(CH(2)CH=CH(2))(2). Steric control of silylalkyl cleavage from 2 is indicated by the fact that, like PPh(2)Cl (which forms B), two further biPSiH analogues SiH(Me)[CH(2)CH(2)CH(2)P(n-hex)(2)](2) (11) and SiH(Me)(CH(2)CH(2)CH(2)PPhBz)(2) (12) were obtained using P(n-hex)(2)Cl (i.e. n-hex = CH(3)(CH(2))(4)CH(2)-) or PPhBzCl (i.e. Bz = -CH(2)C(6)H(5)), respectively, whereas neither PPr(i)(2)Cl nor PBu(t)(2)Cl led to (phosphinoalkyl)silane formation. The surface-substrate linking reagent Ph(2)PCH(2)CH(2)CH(2)Si(OEt)(3) (D) is formed efficiently by similar means from Si(OEt)(3)(CH(2)CH=CH(2)). NMR data ((1)H, (13)C, (29)Si, (31)P) for 2-12 have been measured and are discussed.

The preparation, characterisation and in vitro cytotoxicity of potentially chemotherapeutic heterobimetallic complexes containing early and late transition metals.

PubMed

Wedgwood, Janet L; Kresinski, Roman A; Merry, Stephen; Platt, Andrew W G

2003-06-01

The reactions of phosphine Ph(2)P(CH(2))(2)SO(3)Na with Cp(2)M'Cl(2) (M'=Ti, Zr) in aqueous solution give the metallophosphines, Cp(2)Ti(OSO(2)(CH(2))(2)PPh(2))(2) (Cp=cyclopentadienyl) and CpZr(OH)(OSO(2)(CH(2))(2)PPh(2))(2). These react with CODM"Cl(2) (M"=Pd, Pt) (COD=1,5-cyclooctadiene) in dichloromethane to give heterobimetallic complexes Cp(2)Ti(OSO(2)(CH(2))(2)PPh(2))(2)M"Cl(2) and CpZr(OH)(OSO(2)(CH(2))(2) PPh(2))(2)M"Cl(2) respectively. The compounds are characterised by infrared and NMR spectroscopies and elemental analysis. Electrospray mass spectra of the complexes are reported and compared to those of Cp(2)M'Cl(2) in water and dimethylsulfoxide (DMSO). For zirconocene dichloride and its product heterobimetallic complexes, the addition of ethylenediamine tetraacetic acid disodium salt (Na(2)H(2)EDTA) was found to be an effective ionisation enhancement agent for the electrospray mass spectral studies. Cytotoxicity studies for the previously reported Cl(2)Pt(PPh(2)(CH(2))(2)SO(3)H)(2).3.5H(2)O (Wedgwood et al., Inorg. Chim. Acta 290 (1999) 189), and the compounds Cp(2)Ti(OSO(2)(CH(2))(2) PPh(2))(2).1.5H(2)O and Cp(2)Ti(OSO(2)(CH(2))(2)PPh(2))(2)PtCl(2).4H(2)O reported here, have been evaluated by colony formation assay against cisplatin-sensitive and -resistant cell lines L929 and L929/R to highlight potential chemotherapeutic activity. The compound Cl(2)Pt(PPh(2)(CH(2))(2)SO(3)H)(2).3.5H(2)O overcomes cisplatin resistance.

A Dynamic Retention Model for Air Force Officers: Theory and Estimates

DTIC Science & Technology

1984-12-01

9YOS STAY 2 2 2 1 1973 PIL ACAD 9YOS STAY 2 2 2 2 1 1973 PIL ACAD 9YOS STAY 2 2 2 2 2 4 1973 PIL ACAD 9YOS STAY 2 2 2...2 16 .37 1973 PIL ACAD 9YOS STAY 2 2 2 15 15 1973 PIL ACAD 9YOS STAY 2 2 14 14 14 1973 PIL ACAD 9YOS STAY 2 13 13 13 13 1973 PIL ACAD 9YOS STAY 2...13 13 13 31 1973 PIL ACAD 9YOS LEAVE 2 2 2 2 2 1 1973 PIL ACAD 9YOS LEAVE 2 7 1973 PIL ACAD 9YOS LEAVE 2 2 1 1973 PIL ACAD 9YOS LEAVE 2 2 2

Study Techniques for Controlling Flavor Intensity in Compressed Foods. Phase 1

DTIC Science & Technology

1973-01-01

sweet --- 1 - - -- sour (vinegar) 2 1-2 1-2 1-2 tomato 1-2 1-2 1-2 1-2 pork - i-2 1-2 1-2 cayenne pepper 1 1 )H-1 1 catsup spice 1 1-2 1-2 1-2 onion...1 1 1 Sour 2 1-2 1-2 1 3 Tomato 1-2 ) (-1 1-2 1-2 1-2 Pork - )(-1 1-2 1 - Cayenne Pepper 1 - ) (-1 - - Catsup Spice 1 1-2 1-2 1-2 2 Onion - - )(-i 1...Pork 1-2 1-2 1-2 1 - Cayenne Pepper 1 - 71 - - Catsup Spice 1-2 1-2 1-2 1-2 1 Onion - - ) H-i Salt )(-1 1 )( )(-1 1 Cardboard 1 )(-1 )( 1 - Red Pepper

Marine Coatings Performance for Different Ship Areas. Volume 1

DTIC Science & Technology

1979-07-01

Operating Service Conditions 2.3.3 Survey of the Major Coating Manufacturers for Coatings Criteria 2.4 Compilation of Service Histories 2.5 Analysis of...Compiled Service Histories 2.5.1 Background Information 2.5.2 Analytical Objective 2.5.3 Comparative Analysis 2.6 Laboratory Tests 2.6.1 Discussion...Service Histories Questionnaire i . . . [11 . . . III iv 1-1 1-1 1-1 1-1 1-2 1-5 1-5 1-5 1-5 2-2 2-2 2-2 2-2 2-5 2-5 2-5 2-5 2-5 2-6 2-7 2-8 2-8 2-8 2-8 2

Copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides

NASA Astrophysics Data System (ADS)

Peyronel, Giorgio; Malavasi, Wanda; Pignedoli, Anna

Some copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides (Tu 2X 2) were prepared and studied by infrared spectroscopy and conductometry: 3CuX.2Tu 2X 2(XCl,I), CuBr.Tu 2Br 2, 4CuBr.3.5Tu 2Br 2.MeOH, 2CuBr.Tu 2Br 2.0.66EtOH, 3CuI.2Tu 2I 2, 2AgCl.2.5Tu 2Cl 2, 3AgCl.2Tu 2Cl 2.0.5EtOH, 3AgCl.Tu 2Cl 2, 2AgBr.2Tu 2Br 2.0.5Tu 2(NO 3) 2.H 2O, AgBr.Tu 2Br 2, 4AgBr.Tu 2Br 2, 4AgI.0.5Tu 2I 2.EtOH, AuCl.1.5Tu 2Cl 2, 4AuCl.3.5Tu 2Cl 2.2DMF, AuBr.4Tu 2Br 2, AuBr.2Tu 2Br 2.1.5DMF, AuI.5Tu 2I 2, AuI.Tu 2I 2. A decrease of the ν(NH), δ(NH 2) and ν(CN 2) frequencies and an increase of the ν(CS) frequencies indicate an N-coordination of the dithioformamidinium cation to the metal ions; ν(MN) and ν(MX) frequencies are tentatively assigned in the far-infrared spectra.

Environmental Impact Analysis Process. Deployment Area Selection and Land Withdrawal/Acquisition DEIS. Chapter II. Comparative Analysis of Alternatives.

DTIC Science & Technology

1980-12-01

2.3.17 Housing 2-139 2.3.18 Public Finance 2-142 2.3.19 Educational Services 2-143 2.3.20 Health Services Personnel 2-143 2.3.21 Public Safety 2...2-161 2.4.16 Population 2-161 2.4.17 Housing 2-161 2.4.18 Public Finance 2-162 2.4.19 Educational Services 2-162 2.4.20 Health Services Personnel 2...2.5.17 Housing 2-167 2.5.18 Public Finance 2-168 2.5.19 Educational Services 2-168 2.5.20 Health Services Personnel 2-168 2.5.21 Public Safety 2-168

Novel thioarsenates {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]}: introducing an anionic second ligand to modify MnII complex cations of 2,2'-bipyridine.

PubMed

Liu, Guang-Ning; Guo, Guo-Cong; Wang, Ming-Sheng; Huang, Jin-Shun

2014-03-14

Two novel manganese thioarsenates, {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 (1, 2,2'-bipy = 2,2'-bipyridine) and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]} (2), containing thiocyanate-modified Mn-2,2'-bipy complex cations were synthesized. They feature two terminal [Mn(2,2'-bipy)2(SCN)](+) complex cations bridged by a polyanion {[Mn(2,2'-bipy)]2(As(V)S4)2}(2-) for 1 and a cyclic thioarsenate anion (As(III)2S6)(2-) for 2. In 2, the [As(III)2(S2)2S2](2-) anion can be described as two (As(III)S3)(3-) trigonal-pyramids interlinked through S-S bonds. The method to obtain new metal complex cations shown here, introducing an anionic second ligand to modify the number of coordination sites and the charges of the metal complex cations simultaneously, is different from the traditional methods, varying either the TM center or the organic ligand or employing mixed neutral organic ligands, and may open up a new route for preparing novel chalcogenidometalates. Compounds 1 and 2 exhibit wide optical gaps of 2.20 and 2.67 eV, respectively, and photoluminescence with the emission maxima occurring around 440 nm. Magnetic measurements show the presence of antiferromagnetic interactions between Mn(II) centers in the two compounds.

Reactions of vanadium dioxide molecules with acetylene: infrared spectra of VO2(η(2)-C2H2)(x) (x = 1, 2) and OV(OH)CCH in solid neon.

PubMed

Zhou, Xiaojie; Chen, Mohua; Zhou, Mingfei

2013-07-03

Reactions of vanadium dioxide molecules with acetylene have been studied by matrix isolation infrared spectroscopy. Reaction intermediates and products are identified on the basis of isotopic substitutions as well as density functional frequency calculations. Ground state vanadium dioxide molecule reacts with acetylene in forming the side-on-bonded VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes spontaneously on annealing in solid neon. The VO2(η(2)-C2H2) complex is characterized to have a (2)B2 ground state with C2v symmetry, whereas the VO2(η(2)-C2H2)2 complex has a (2)A ground state with C2 symmetry. The VO2(η(2)-C2H2) and VO2(η(2)-C2H2)2 complexes are photosensitive. The VO2(η(2)-C2H2) complex rearranges to the OV(OH)CCH molecule upon UV-vis light excitation.

Novel Guanidinium-Based Ionic Liquids for Highly Efficient SO2 Capture.

PubMed

Lu, Xiaoxing; Yu, Jing; Wu, Jianzhou; Guo, Yongsheng; Xie, Hujun; Fang, Wenjun

2015-06-25

The application of ionic liquids (ILs) for acidic gas absorption has long been an interesting and challenging issue. In this work, the ethyl sulfate ([C2OSO3](-)) anion has been introduced into the structure of guanidinium-based ILs to form two novel low-cost ethyl sulfate ILs, namely 2-ethyl-1,1,3,3-tetramethylguanidinium ethyl sulfate ([C2(2)(C1)2(C1)2(3)gu][C2OSO3]) and 2,2-diethyl-1,1,3,3-tetramethylguanidinium ethyl sulfate ([(C2)2(2)(C1)2(C1)2(3)gu][C2OSO3]). The ethyl sulfate ILs, together with 2-ethyl-1,1,3,3-tetramethylguanidinium bis(trifluoromethylsulfonyl)imide ([C2(2)(C1)2(C1)2(3)gu][NTf2]) and 2,2-diethyl-1,1,3,3-tetramethylguanidinium bis(trifluoromethylsulfonyl)imide ([(C2)2(2)(C1)2(C1)2(3)gu][NTf2]), are employed to evaluate the SO2 absorption and desorption performance. The recyclable ethyl sulfate ILs demonstrate high absorption capacities of SO2. At a low pressure of 0.1 bar and at 20 °C, 0.71 and 1.08 mol SO2 per mole of IL can be captured by [C2(2)(C1)2(C1)2(3)gu][C2OSO3] and [(C2)2(2)(C1)2(C1)2(3)gu][C2OSO3], respectively. The absorption enthalpy for SO2 absorption with [C2(2)(C1)2(C1)2(3)gu][C2OSO3] and [(C2)2(2)(C1)2(C1)2(3)gu][C2OSO3] are -3.98 and -3.43 kcal mol(-1), respectively. While those by [C2(2)(C1)2(C1)2(3)gu][NTf2] and [(C2)2(2)(C1)2(C1)2(3)gu][NTf2] turn out to be only 0.17 and 0.24 mol SO2 per mole of IL under the same conditions. It can be concluded that the guanidinium ethyl sulfate ILs show good performance for SO2 capture. Quantum chemistry calculations reveal nonbonded weak interactions between the ILs and SO2. The anionic moieties of the ILs play an important role in SO2 capture on the basis of the consistently experimental and computational results.

Airborne Systems Course Textbook. Electro-Optical Systems Test and Evaluation,

DTIC Science & Technology

1981-06-01

by twice the angle between the reflecting faces. The porro - prism shown in Figure 2.2.3.1(c) is used to deflect the beam by 1800. Beam Retro-Reflection...Reflection of Electromagnetic Radiation at the Interface Between Two Media 2.13 2.2 Optics 2.15 2.2.1 The Lens 2.15 2.2.2 The Mirror 2.25 2.2.3 The Prism 2.30...2.5.2 The Optical Resonator 2.77 2.5.3 Laser Implementation 2.79 2.5.4 Laser Radiation Characteristics 2.81 2.6 Electro-Optical Sensors 2.83 2.6.1

Reactions of R(2)P-P(SiMe(3))Li with [(R'(3)P)(2)PtCl(2)]. A general and efficient entry to phosphanylphosphinidene complexes of platinum. Syntheses and structures of [(eta(2)-P=(i)Pr(2))Pt(p-Tol(3)P)(2)], [(eta(2)-P=(t)Bu(2))Pt(p-Tol(3)P)(2)], [{eta(2)-P=(N(i)Pr(2))(2)}Pt(p-Tol(3)P)(2)] and [{(Et(2)PhP)(2)Pt}(2)P(2)].

PubMed

Domańska-Babul, Wioleta; Chojnacki, Jaroslaw; Matern, Eberhard; Pikies, Jerzy

2009-01-07

The reactions of lithium derivatives of diphosphanes R(2)P-P(SiMe(3))Li (R = (t)Bu, (i)Pr, Et(2)N and (i)Pr(2)N) with [(R'(3)P)(2)PtCl(2)] (R'(3)P = Et(3)P, Et(2)PhP, EtPh(2)P and p-Tol(3)P) proceed in a facile manner to afford side-on bonded phosphanylphosphinidene complexes of platinum [(eta(2)-P=R(2))Pt(PR'(3))(2)]. The related reactions of Ph(2)P-P(SiMe(3))Li with [(R'(3)P)(2)PtCl(2)] did not yield [(eta(2)-P=PPh(2))Pt(PR'(3))(2)] and resulted mainly in the formation of [{(R'(3)P)(2)Pt}(2)P(2)], Ph(2)P-PLi-PPh(2), (Me(3)Si)(2)PLi and (Me(3)Si)(3)P. Crystallographic data are reported for the compounds [(eta(2)-P=R(2))Pt(p-Tol(3)P)(2)] (R = (t)Bu, (i)Pr, ((i)Pr(2)N)(2)P) and for [{(Et(2)PhP)(2)Pt}(2)P(2)].

40 CFR 721.10408 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene...

Code of Federal Regulations, 2013 CFR

2013-07-01

...)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2,2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl)oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...

40 CFR 721.10408 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene...

Code of Federal Regulations, 2014 CFR

2014-07-01

...)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2,2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl)oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...

40 CFR 721.10408 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene...

Code of Federal Regulations, 2012 CFR

2012-07-01

...)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2,2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl) oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...-ethanediyl)], .alpha.-[2-[[2,2-dimethyl-3-[(1-oxododecyl)oxy]propylidene] amino] methylethyl]-.omega.-[2-[[2...

40 CFR 721.10326 - 2-Propenoic acid, 2-methyl-, methyl ester, polymer with butyl 2-propenoate, ethyl 2-propenoate...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false 2-Propenoic acid, 2-methyl-, methyl ester, polymer with butyl 2-propenoate, ethyl 2-propenoate, zinc 2-methyl-2-propenoate (1:2) and zinc 2-propenoate (1:2), 2,2'-(1,2-diazenediyl)bis[2-methylbutanenitrile]- and 2,2'-(1,2-diazenediyl)bis[2-methylpropanenitrile]-initiated. 721.10326...

Detecting Age in Online Chat

DTIC Science & Technology

2009-09-01

spanks 1.000 2 2 fat. 1.000 2 2 awful 1.000 3 3 parties 1.000 3 3 canada? 1.000 3 3 tail? 1.000 2 2 once 1.000 2 2 thing. 1.000 3 3 gah 1.000 2 2 will...1.000 2 2 money 1.000 2 2 minutes 1.000 8 8 hmmmmmmmm 1.000 3 3 box 1.000 8 8 tank 1.000 2 2 ks 1.000 2 2 spanks 1.000 2 2 u? 1.000 17 17 jersey...thank you lol 1.000 2 2 i have another 1.000 2 2 u have to 1.000 4 4 <post> .action spanks 1.000 2 2 yes they do 1.000 2 2 <post> it will 1.000 2 2

Semiconductor Millimeter Wavelength Electronics.

DTIC Science & Technology

1980-10-01

in whole or In part, Is permitted for any purpose of the U.S. Govenment. Contract N00014-79-C-040 N " H Contract Authority. NR SRO004 k Approved for...Muller) 2.2.1 Introduction ............................... 2-19 2.2.2 Assumptions ................................ 2-20 2.2.2.1 Wand N Treatment: List...Exact Approach ............ 2-28 2.2.3.1.2 Modified Wand N Approach ...... 2-32 2.2.3.2 The Impurity Redistribution Problem .. 2-33 2.2.3.2.1

The Terminal Interface Message Processor Program.

DTIC Science & Technology

1973-11-01

table entry for this device to one of CONECO, CONVT, CONEEE, CONESC , IBMEEE, IBMESC, IBMECO, IBMCON, BINECO, BINCON, or HUNT 8.2.2.1.1-2 8/73...transmit on EDM, goto NOPE EOMa set up counter to make buffer look full goto NOPE 8.2.2.1.1-6 8/73 A I I CONEEE call ECHO to echo characterI CONESC mask...6 82 CCHAR 8.2.2.2.2-3CCHARA 8 . 2,2 .2 .2- 3 CLKOI 8.2.2.2-1 CLOCK 8.2.2-1 CLOCK4 8.2.2-1 CLOCKA 8.2.2-2 CONEEE 8.2.2.1.1-7 CONESC 8.2.2.1.1-7

40 CFR 721.10326 - 2-Propenoic acid, 2-methyl-, methyl ester, polymer with butyl 2-propenoate, ethyl 2-propenoate...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 2-Propenoic acid, 2-methyl-, methyl ester, polymer with butyl 2-propenoate, ethyl 2-propenoate, zinc 2-methyl-2-propenoate (1:2) and zinc 2-propenoate (1:2), 2,2â²-(1,2-diazenediyl)bis[2-methylbutanenitrile]- and 2,2â²-(1,2-diazenediyl)bis[2-methylpropanenitrile]-initiated. 721.10326...

40 CFR 721.10326 - 2-Propenoic acid, 2-methyl-, methyl ester, polymer with butyl 2-propenoate, ethyl 2-propenoate...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 2-Propenoic acid, 2-methyl-, methyl ester, polymer with butyl 2-propenoate, ethyl 2-propenoate, zinc 2-methyl-2-propenoate (1:2) and zinc 2-propenoate (1:2), 2,2â²-(1,2-diazenediyl)bis[2-methylbutanenitrile]- and 2,2â²-(1,2-diazenediyl)bis[2-methylpropanenitrile]-initiated. 721.10326...

Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

NASA Astrophysics Data System (ADS)

Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

1996-11-01

The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

Fast Collaborative Filtering from Implicit Feedback withProvable Guarantees

DTIC Science & Technology

2016-11-22

n2 = Ω (( ε d̃2sσK(M2) )2) • n3 = Ω ( K2 ( 10 d̃2sσK(M2)5/2 + 2 √ 2 d̃3sσK(M2)3/2 )2 ε2 ) 212 Fast Collaborative Filtering for some constants c1 and c2...drawback of Method of Moments is that it will not work when there are only a few users available such that N < Θ( K2 ). However, modern recommendation systems...2 √ 2 d̃3sσK(M2)3/2 ) 2ε√ N ≤ c1 1 K √ πmax Since πmax ≤ 1, we need N ≥ Ω ( K2 ( 10 d̃2sσK(M2)5/2 + 2 √ 2 d̃3sσK(M2)3/2 )2 ε2 ) . This con- tributes

Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex

NASA Astrophysics Data System (ADS)

Qian, Cheng; Kong, Fang; Mao, Jiang-Gao

2016-06-01

A series of vanadium selenites covalently bonded with metal-organic complex, namely, Ni(2,2-bipy)2V2O4(SeO3)2 (1), Cu(2,2-bipy)V2O4(SeO3)2·0.5H2O (2) and Cu2(2,2-bipy)2V5O12(SeO3)2 (3) (2,2-bipy=2,2-bipyridine) have been hydrothermally synthesized and structurally characterized. They exhibit three different structural dimensions, from 0D cluster, 1D chain to 2D layer. Compound 1 features a 0D {Ni(2,2-bipy)2V2O4(SeO3)2}2 dimeric cluster composed of two {Ni(2,2-bipy)2}2+ moieties connected by the {V4O8(SeO3)4}4- cluster. Compound 2 shows a 1D {Cu(2,2-bipy)V2O4(SeO3)2}n chain in which the {Cu2(2,2-bipy)2}4+ moieties are bridged by the {V4O8(SeO3)4}4- clusters. Compound 3 displays a 2D structure consisted of mixed valence vanadium selenites layers {VIVVV4SeIV2O18}n4- and {Cu(2,2-bipy)}2+ complex moieties. The adjacent layers are further interconnected via π-π interactions between the 2,2-bipy ligands exhibiting an interesting 3D supramolecular architecture. Both compound 1 and 2 contain a new {V4O8(SeO3)4}4- cluster and compound 3 exhibits the first 2D vanadate polyhedral layer in vanadium selenites/tellurites with organic moieties.

NASA TEERM Hexavalent Chrome Alternatives Projects

DTIC Science & Technology

2011-08-18

1 N2-2 N3-2 N4-2 N5-2 N6-2 N7-2 N8-2 N9-2 N10-2 N11-2 N12-2 N13-2 H H2-1 H3-1 H4-1 H5-1 H6-1 H7-1 H8-1 H9-1 H10-1 H11-1 H12-1 H13 -1 H2-2 H3-2 H4-2...H5-2 H6-2 H7-2 H8-2 H9-2 H10-2 H11-2 H12-2 H13 -2 D D2-1 D3-1 D4-1 D5-1 D6-1 D7-1 D8-1 D9-1 D10-1 D11-1 D12-1 D13-1 D2-2 D3-2 D4-2 D5-2 D6-2 D7-2...Color, Adhesion, Impact , Flexibility, Fluid Resistance, Filiform Corrosion, Salt-Spray Corrosion, Artificial Weathering, Stripability, Restoration

Software Design Document PVD CSCI (3). Volume 2, Appendices

DTIC Science & Technology

1991-06-01

FUNCTION: Igeneric -type(Type, Overline) called~y: show Ioverline in overlineif.c, (null) boundary-action in ovline-func.c, (null) Ideparture-action in...2.8.2.2-22 Ideparture-action 2.8.2.2-28 ldeparturejabel 2.8.2.2-27 idone__create_action 2.8.2.2-39 igeneric -size 2.8.2.2-17 lgeneric-type, 2.8.2.2-24

Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C-H Activation.

PubMed

Handford, Rex C; Wakeham, Russell J; Patrick, Brian O; Legzdins, Peter

2017-03-20

Treatment of CH 2 Cl 2 solutions of Cp*M(NO)Cl 2 (Cp* = η 5 -C 5 (CH 3 ) 5 ; M = Mo, W) first with 2 equiv of AgSbF 6 in the presence of PhCN and then with 1 equiv of Ph 2 PCH 2 CH 2 PPh 2 affords the yellow-orange salts [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 in good yields (M = Mo, W). Reduction of [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 with 2 equiv of Cp 2 Co in C 6 H 6 at 80 °C produces the corresponding 18e neutral compounds, Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) which have been isolated as analytically pure orange-red solids. The addition of 1 equiv of the Lewis acid, Sc(OTf) 3 , to solutions of Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) at room temperature results in the immediate formation of thermally stable Cp*M(NO→Sc(OTf) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes in which one of the phenyl substituents of the Ph 2 PCH 2 CH 2 PPh 2 ligands has undergone intramolecular orthometalation. In a similar manner, addition of BF 3 produces the analogous Cp*M(NO→BF 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes. In contrast, B(C 6 F 5 ) 3 forms the 1:1 Lewis acid-base adducts, Cp*M(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) in CH 2 Cl 2 at room temperature. Upon warming to 80 °C, Cp*Mo(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) converts cleanly to the orthometalated product Cp*Mo(NO→B(C 6 F 5 ) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ), but Cp*W(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) generates a mixture of products whose identities remain to be ascertained. Attempts to extend this chemistry to include related Ph 2 PCH 2 PPh 2 compounds have had only limited success. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

Orthopalladation of iminophosphoranes: synthesis, structure and study of stability.

PubMed

Bielsa, Raquel; Navarro, Rafael; Soler, Tatiana; Urriolabeitia, Esteban P

2008-03-07

The reaction of Pd(OAc)(2) with polyfunctional iminophosphoranes Ph(3)P=NCH(2)CO(2)Me (1a), Ph(3)P=NCH(2)C(O)NMe(2) (1b), Ph(3)P=NCH(2)CH(2)SMe (1c) and Ph(3)P=NCH(2)-2-NC(5)H(4) (1d), gives the orthopalladated dinuclear complex [Pd(mu-Cl){C(6)H(4)(PPh(2)=NCH(2)CO(2)Me-kappa-C,N)-2}](2) (2a) and the mononuclear derivatives [PdCl{C(6)H(4)(PPh(2)=NCH(2)CONMe(2)-kappa-C,N,O)-2}] (2b), [PdCl{C(6)H(4)(PPh(2)=NCH(2)CH(2)SMe-kappa-C,N,S)-2}] (2c) and [PdCl{C(6)H(4)(PPh(2)=NCH(2)-2-NC(5)H(4)-kappa-C,N,N)-2}] (2d). The reaction implies the activation of a C-H bond in a phenyl ring of the phosphonium group, this fact being worthy of note due to the strongly deactivating nature of the phosphonium unit. The palladacycle containing the metallated carbon atom is remarkably stable toward the coordination of incoming ligands, while that formed by the iminic N atom and another heteroatom (O, 2a and 2b; S, 2c; N, 2d) is less stable and the resulting complexes can be considered as hemilabile. The X-ray crystal structures of the cyclopalladated [Pd(mu-Cl){C(6)H(4)(PPh(2)=NCH(2)CO(2)Me-kappa-C,N)-2}](2) (2a), [PdCl{C(6)H(4)(PPh(2)=NCH(2)-2-NC(5)H(4)-kappa-C,N,N)-2}] (2d), [Pd{C(6)H(4)(PPh(2)=NCH(2)CONMe(2)-kappa-C,N,O)-2}(NCMe)](ClO(4)) (7b) and [Pd{C(6)H(4)(PPh(2)NCH(2)CONMe(2)-kappa-C,N,O)-2}(py)](ClO(4)) (3b), and the coordination compound cis-[Pd(Cl)(2)(Ph(3)P=NCH(2)CH(2)SMe-kappa-N,S)] (8) are also reported.

Synthesis, Crystal Chemistry, and Physical Properties of Ternary Intermetallic Compounds An2T2X( An=Pu, Am; X=ln, Sn; T=Co, Ir, Ni, Pd, Pt, Rh)

NASA Astrophysics Data System (ADS)

Pereira, L. C. J.; Wastin, F.; Winand, J. M.; Kanellakopoulos, B.; Rebizant, J.; Spirlet, J. C.; Almeida, M.

1997-11-01

The synthesis, structural, and physical characterization of nine new ternary intermetallic compounds belonging to the isostructural An2T2Xfamily with the transuranium Pu and Am elements, namely, Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, are reported. From these compounds only Pu 2Rh 2In, Am 2Ni 2Sn, and Am 2Pd 2Sn melt incongruently. All of these compounds crystallize in a tetragonal U 3Si 2-type structure, with the space group P4/ mbm, ( Z=2) as most of the U and Np 2-2-1 compounds already found. In this structure, Anatoms occupy the 4 h( x1, x1+0.5, 0.5), Tthe 4 g( x2, x2+0.5, 0), and Xthe 2 a(0, 0, 0) positions. The average values of x1and x2are, respectively, 0.17 and 0.37. Single-crystal X-ray data were refined to R/ RW=0.045/0.066, 0.043/0.072, 0.066/0.080, 0.070/0.098, 0.029/0.048, 0.055/0.080, 0.073/0.096, 0.048/0.086, 0.048/0.065 for Pu 2Ni 2In, Pu 2Pd 2In, Pu 2Pt 2In, Pu 2Rh 2In, Pu 2Ni 2Sn, Pu 2Pd 2Sn, Pu 2Pt 2Sn, Am 2Ni 2Sn, and Am 2Pd 2Sn, respectively, for seven variables. The variation of the lattice parameters and the range of stability of the 2-2-1 phase are discussed in terms of the substitution of different An(actinide), T(transition metal), and X( p-electron) elements in their crystal structure. The possible role of spin fluctuations in the low-temperature behavior of the Pu samples is indicated by magnetic and electrical resistivity measurements.

Design and syntheses of hybrid metal-organic materials based on K3[M(C2O4)3]·3H2O [M(III)=Fe, Al, Cr] metallotectons

NASA Astrophysics Data System (ADS)

Sun, Yayong; Zong, Yingxia; Ma, Haoran; Zhang, Ao; Liu, Kang; Wang, Debao; Wang, Wenqiang; Wang, Lei

2016-05-01

By using K3[M(C2O4)3]·3H2O [M(III)=Fe, Al, Cr] (C2O42-=oxalate) metallotectons as the starting material, we have synthesized eight novel complexes with formulas [{Fe(C2O4)2(H2O)2}2]·(H-L1)2·H2O 1, [Fe(C2O4)Cl2]·(H2-L2)0.5·(L2)0.5·H2O 2, [{Fe(C2O4)1.5Cl2}2]·(H-L3)43, [Fe2(C2O4)Cl8]·(H2-L4)2·2H2O 4, K[Al(C2O4)3]·(H2-L5)·2H2O 5, K[Al(C2O4)3]·(H-L6)2·2H2O 6, K[Cr(C2O4)3]·2H2O 7, Na[Fe(C2O4)3]·(H-L6)2·2H2O 8 (with L1=4-dimethylaminopyridine, L2=2,3,5,6-tetramethylpyrazine, L3=2-aminobenzimidazole, L4=1,4-bis-(1H-imidazol-1-yl)benzene, L5=1,4-bis((2-methylimidazol-1-yl)methyl)benzene, L6=2-methylbenzimidazole). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra and thermogravimetric analyses. Compound 3 is a 2D H-bonded supramolecular architecture. Others are 3D supramolecular structures. Compound 1 shows a [Fe(C2O4)2(H2O)2]- unit and 3D antionic H-bonded framework. Compound 2 features a [Fe(C2O4)Cl2]- anion and 1D iron-oxalate-iron chain. Compound 3 features a [Fe2(C2O4)3Cl4]4- unit. Compound 4 features distinct [Fe2(C2O4)Cl8]4- units, which are mutual linked by water molecules to generated a 2D H-bonded network. Compound 5 features infinite ladder-like chains constructed by [Al(C2O4)3]3- units and K+ cations. The 1D chains are further extended into 3D antionic H-bonded framework through O-H···O H-bonds. Compounds 6-8 show 2D [KAl(C2O4)3]2- layer, [KCr(C2O4)3]2- layer and [NaFe(C2O4)3]2- layer, respectively.

Self-encapsulation of [MII(phen)2(H2O)2]2+ (M=Co, Zn) in one-dimensional nanochannels of [MII(H2O)6(BTC)2]4- (M=Co, Cu, Mn): a high HQ/CAT ratio catalyst for hydroxylation of phenols.

PubMed

Bi, Jianhong; Kong, Lingtao; Huang, Zixiang; Liu, Jinhuai

2008-06-02

Four novel three-dimensional (3D) microporous supramolecular compounds containing nanosized channels, namely, [Co(phen)2(H2O)2]2[Co(H2O)6].2BTC.21.5H2O (1), [Co(phen)2(H2O)2]2[Cu(H2O)6].2BTC.21.5H2O (2), [Co(phen)2(H2O)2]2[Mn(H2O)6].2BTC.18H2O (3), and [Zn(phen)2(H2O)2]2[Mn(H2O)6].2BTC.22.5H2O (4), were synthesized from 1,3,5-benzenetricarboxylate (BTC), 1,10-phenanthroline (phen), and the transition-metal salt(s) by self-assembly. Single-crystal X-ray structural analysis showed that the resulting 3D microporous supramolecular frameworks consist of a two-dimensional (2D) hydrogen-bonded host framework of [MII(H2O)6(BTC)2]4- (M=Co for 1, Cu for 2, Mn for 3, 4) with rectangular-shaped cavities containing [MII(phen)2(H2O)2]2+ (M=Co for 1-3, Zn for 4) guests. The guest complex is encapsulated in the 2D hydrogen-bonded host framework by hydrogen bonding and aromatic pi-pi stacking interactions, forming the 3D hydrogen-bonded framework. The catalytic activities of 1, 2, 3, and 4 were studied using hydroxylation of phenols with 30% aqueous H2O2 as a test reaction. The compounds displayed a good phenol conversion ratio and excellent channel selectivity in the hydroxylation reaction, with a maximum hydroquinone (HQ)/catechol (CAT) ratio of 3.9.

AQUO-OXALATO-SULFATE COMPOUNDS OF URANIUM (in Russian)

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

Chernyaev, I.I.; Golovnya, V.A.; Shchelokov, R.N.

1960-07-01

The following mixed aquo-acido complex uranyl compounds containing an oxalate and a sulfate group were synthesized for the first time: K/sub 2/STAUO/ sub 2/(C/sub 2/O/sub 4/) (SO/sub 4/ (H/sub 2/O)/sub 2/!. H/sub 2/O, Rb/sub 2/ STAUO/sub 2/(C/sub 2/O/sub 4/)(SO/sub 4/)(H/sub 2/O)/sub 2/!, Cs/sub 2/STAUO/sub 2/(C/sub 2/O/sub 4/)(SO/sub 4/)(H/sub 2/O)/sub 2/)!, and Cs(NH/sub 4/) (UO/sub 2/ (C/sub 2/O/sub 4/) (SO/sub 4/)(H/sub 2/O)/sub 2/!. T he molecular conductivity and pH were determined in dilute solutions, and it was concluded that the decrease in stability of these complexes in aqueous solution is as follows: STAUO/ sub 2/(C/sub 2/O/sub 4/)/sub 2/(H/sub 2/O)/sub 2/!/sup 2-/more » > STAUO/sub 2/(C/su b 2/O/sub 4/)(SO/sub 4)(H/sub 2/O)/sub 2/!/sup 2-/ > STAUO/sub 2/(SO/sub 4/)/sub 2/ (H/sub 2O)/sub 2/!/sup 2-. (TTT)« less

Laser gain on 3p-3d and 3s-3p transitions and X-ray line ratios for the nitrogen isoelectronic sequence

NASA Technical Reports Server (NTRS)

Feldman, U.; Seely, J. F.; Bhatia, A. K.

1989-01-01

Results are presented on calculations of the 72 levels belonging to the 2s(2)2p(3), 2s2p(4), 2p(5), 2s(2)2p(2)3s, 2s(2)2p(2)3p, and 2s(2)2p(2)3d configurations of the N I isoelectronic sequence for the ions Ar XII, Ti XVI, Fe XX, Zn XXIV, and Kr XXX, for electron densities up to 10 to the 24th/cu cm. It was found that large population inversions and gain occur between levels in the 2s(2)2p(2)3p configuration and levels in the 2s(2)2p(2)3d configuration that cannot decay to the ground configuration by an electric dipole transition. For increasing electron densities, the intensities of the X-ray transitions from the 2s(2)2p(2)3p configuration to the ground configuration decrease relative to the transitions from the 2s(2)2p(2)3s and 2s(2)2p(2)3d configurations to the ground configuration. The density dependence of these X-ray line ratios is presented.

Effect of persulfate and persulfate/H₂O₂ on biodegradability of an anaerobic stabilized landfill leachate.

PubMed

Hilles, Ahmed H; Abu Amr, Salem S; Hussein, Rim A; Arafa, Anwar I; El-Sebaie, Olfat D

2015-10-01

The current study investigated the effects of S2O8(2-) and S2O8(2-)/H2O2 oxidation processes on the biodegradable characteristics of an anaerobic stabilized leachate. Total COD removal efficiency was found to be 46% after S2O8(2-) oxidation (using 4.2 g S2O8(2-)/1g COD0, at pH 7, for 60 min reaction time and at 350 rpm shaking speed), and improved to 81% following S2O8(2-)/H2O2 oxidation process (using 5.88 g S2O8(2-) dosage, 8.63 g H2O2 dosage, at pH 11 and for 120 min reaction time at 350 rpm). Biodegradability in terms of BOD5/COD ratio of the leachate enhanced from 0.09 to 0.1 and to 0.17 following S2O8(2-) and S2O8(2-)/H2O2 oxidation processes, respectively. The fractions of COD were determined before and after each oxidation processes (S2O8(2-) and S2O8(2-)/H2O2). The fraction of biodegradable COD(bi) increased from 36% in raw leachate to 57% and 68% after applying S2O8(2-) and S2O8(2-)/H2O2 oxidation, respectively. As for soluble COD(s), its removal efficiency was 39% and 78% following S2O8(2-) and S2O8(2-)/H2O2 oxidation, respectively. The maximum removal for particulate COD was 94% and was obtained after 120 min of S2O8(2-)/H2O2 oxidation. As a conclusion, S2O8(2-)/H2O2 oxidation could be an efficient method for improving the biodegradability of anaerobic stabilized leachate. Copyright © 2015 Elsevier Ltd. All rights reserved.

Rigid 2D networks of copper(II) complexes containing diallylbis(pyridin-3-yl)silane: Insight into anion and media effects on catechol oxidation catalysis

NASA Astrophysics Data System (ADS)

Ryu, Minjoo; Lee, Young-A.; Jung, Ok-Sang

2018-01-01

The self-assembly of CuX2 (X- = Cl-, Br-, NO3-, ClO4-, and BF4-) with a new diallylbis(pyridin-3-yl)silane ligand (L) gives rise to the similar 2D coordination networks with composition of Cu(II) and L of 1: 2 irrespective of anions and solvents. The 2D networks of [CuCl2L2]·2H2O, [CuBr2L2]·2H2O, and [Cu(H2O)2L2]·(NO3)2 are packed in a staggered mode while the similar networks of [Cu(BF4)2L2] and [Cu(ClO4)2L2] are arrayed in a eclipsed fashion. These crystals of all 2D networks have been employed as catalysts for 3,5-di-tert-butylcatechol (3,5-DBCat) oxidation, showing the catalytic effects in the order of [CuCl2L2]·2H2O > [CuBr2L2]·2H2O > [Cu(H2O)2L2]·(NO3)2 > [Cu(ClO4)2L2] > [Cu(BF4)2L2] in chloroform and exhibiting the catalytic effects of only [Cu(H2O)2L2]·(NO3)2 in acetone. Thus, the catalytic effect on catechol oxidation is strongly dependent on anions and media.

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2 }2 {μ-η2 :η2 -B2 H4 }] and [{Cp*M(CO)2 }2 B2 H2 M(CO)4 ], M=Mo,W.

PubMed

Mondal, Bijan; Bag, Ranjit; Ghorai, Sagar; Bakthavachalam, K; Jemmis, Eluvathingal D; Ghosh, Sundargopal

2018-07-02

The reaction of [(Cp*Mo) 2 (μ-Cl) 2 B 2 H 6 ] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged C s structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum-alkyne complex [{CpMo(CO) 2 } 2 C 2 H 2 ]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO) 4 ] fragment, [{Cp*Mo(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (3) was isolated upon treatment with [W(CO) 5 ⋅thf]. Compound 3 shows the intriguing presence of [B 2 H 2 ] with a short B-B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (4) and [{Cp*W(CO) 2 } 2 B 2 H 2 Mo(CO) 4 ] (5), which provided direct proof of the existence of the tungsten analogue of 2. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of the (N2)3- radical from Y2+ and its protonolysis reactivity to form (N2H2)2- via the Y[N(SiMe3)2]3/KC8 reduction system.

PubMed

Fang, Ming; Lee, David S; Ziller, Joseph W; Doedens, Robert J; Bates, Jefferson E; Furche, Filipp; Evans, William J

2011-03-23

Examination of the Y[N(SiMe(3))(2)](3)/KC(8) reduction system that allowed isolation of the (N(2))(3-) radical has led to the first evidence of Y(2+) in solution. The deep-blue solutions obtained from Y[N(SiMe(3))(2)](3) and KC(8) in THF at -35 °C under argon have EPR spectra containing a doublet at g(iso) = 1.976 with a 110 G hyperfine coupling constant. The solutions react with N(2) to generate (N(2))(2-) and (N(2))(3-) complexes {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2)) (1) and {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2))[K(THF)(6)] (2), respectively, and demonstrate that the Y[N(SiMe(3))(2)](3)/KC(8) reaction can proceed through an Y(2+) intermediate. The reactivity of (N(2))(3-) radical with proton sources was probed for the first time for comparison with the (N(2))(2-) and (N(2))(4-) chemistry. Complex 2 reacts with [Et(3)NH][BPh(4)] to form {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-N(2)H(2)), the first lanthanide (N(2)H(2))(2-) complex derived from dinitrogen, as well as 1 as a byproduct, consistent with radical disproportionation reactivity.

Postfunctionalization of periodic mesoporous silica SBA-1 with magnesium(II) and iron(II) silylamides.

PubMed

Deschner, Thomas; Klimpel, Michael; Tafipolsky, Maxim; Scherer, Wolfgang; Törnroos, Karl W; Anwander, Reiner

2012-06-28

Magnesium silylamide complexes Mg[N(SiHMe(2))(2)](2)(THF)(2) and Mg[N(SiPhMe(2))(2)](2) were synthesized according to transsilylamination and alkane elimination protocols, respectively, utilizing Mg[N(SiMe(3))(2)](2)(THF)(2) and [Mg(n-Bu)](2) as precursors. Cage-like periodic mesoporous silica SBA-1 was treated with donor solvent-free dimeric [Mg{N(SiHMe(2))(2)}(2)](2), [Mg{N(SiMe(3))(2)}(2)](2) and monomeric Mg[N(SiPhMe(2))(2)](2), producing hybrid materials [Mg(NR(2))(2)]@SBA-1 with magnesium located mainly at the external surface. Consecutive grafting of [Mg{N(SiHMe(2))(2)}(2)](2) and [Fe(II){N(SiHMe(2))(2)}(2)](2) onto SBA-1 led to heterobimetallic hybrid materials which exhibit complete consumption of the isolated surface silanol groups, evidencing intra-cage surface functionalization. All materials were characterized by DRIFT spectroscopy, nitrogen physisorption and elemental analysis.

10 CFR 2.1000 - Scope of subpart J.

Code of Federal Regulations, 2012 CFR

2012-01-01

....309; 2.312; 2.313; 2.314; 2.315; 2.316; 2.317(a); 2.318; 2.319; 2.320; 2.321; 2.322; 2.323; 2.324; 2...(f)(8) or 2.105(a)(5), and for an application for a license to receive and possess high level...

10 CFR 2.1000 - Scope of subpart J.

Code of Federal Regulations, 2010 CFR

2010-01-01

....309; 2.312; 2.313; 2.314; 2.315; 2.316; 2.317(a); 2.318; 2.319; 2.320; 2.321; 2.322; 2.323; 2.324; 2...(f)(8) or 2.105(a)(5), and for an application for a license to receive and possess high level...

10 CFR 2.1000 - Scope of subpart J.

Code of Federal Regulations, 2011 CFR

2011-01-01

....309; 2.312; 2.313; 2.314; 2.315; 2.316; 2.317(a); 2.318; 2.319; 2.320; 2.321; 2.322; 2.323; 2.324; 2...(f)(8) or 2.105(a)(5), and for an application for a license to receive and possess high level...

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

Uemura, Kazuhiro, E-mail: k_uemura@gifu-u.ac.j; Onishi, Fumiaki; Yamasaki, Yukari

NO{sub 2} containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO{sub 2}) and 2,5-dinitroterephthalate (bdc-(NO{sub 2}){sub 2}), afford porous coordination polymers, {l_brace}[Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)].solvents{r_brace}{sub n} (2 contains solvents) and {l_brace}[Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)].solvents{r_brace}{sub n} (3 contains solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn{sub 2} units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2 contains solvents and 3 contains solvents, a rectangle pore surrounded by eight Zn{sub 2} corners contains two and four NO{sub 2} moieties, respectively. Thermal gravimetry (TG) and X-ray powdermore » diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me{sub 2}CO. Adsorption measurements reveal that dried 2 and 3 adsorb H{sub 2}O molecules to be {l_brace}[Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)].4H{sub 2}O{r_brace}{sub n} (2 contains 4H{sub 2}O) and {l_brace}[Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)].6H{sub 2}O{r_brace}{sub n} (3 contains 6H{sub 2}O), showing the pore hydrophilicity enhancement caused by NO{sub 2} group introduction. - Graphical abstract: Two hydrophilic porous coordination polymers, [Zn{sub 2}(bdc-NO{sub 2}){sub 2}(dabco)]{sub n} (2, bdc-NO{sub 2}=nitroterephthalate, dabco=1,4-diazabicyclo[2.2.2]octane) and [Zn{sub 2}(bdc-(NO{sub 2}){sub 2}){sub 2}(dabco)]{sub n} (3, bdc-(NO{sub 2}){sub 2}=2,5-dinitroterephthalate), have been synthesized and characterized by single X-ray analyses, thermal gravimetry, and adsorption measurements.« less

A Limited Antiballistic Missile System

DTIC Science & Technology

1990-12-01

2.2 ABM Philosophy. .. .. .. .. ... ... ... ...... 2-1 2.3 Ballistic Missile Flight Phases .. .. .. .... ....... 2-3 2.4 Past US Systems...2-7 iii Page 2.4.4 SAFEGUARD .. .. .. .. .. ... ... ..... 2-8 2.4.5 Other Programs. .. .. .. .. ... ... ..... 2-9 2.5 Current ABM ...2.5.6 Summary of ABM Characteristics. .. .. ..... 2-11 2.6 The Threat .. .. .. .. ... ... ... ... ... ... 2-12 2.6.1 The Middle East

Isolation of (CO)1- and (CO2)1- radical complexes of rare earths via Ln(NR2)3/K reduction and [K2(18-crown-6)2]2+ oligomerization.

PubMed

Fang, Ming; Farnaby, Joy H; Ziller, Joseph W; Bates, Jefferson E; Furche, Filipp; Evans, William J

2012-04-11

Deep-blue solutions of Y(2+) formed from Y(NR(2))(3) (R = SiMe(3)) and excess potassium in the presence of 18-crown-6 at -45 °C under vacuum in diethyl ether react with CO at -78 °C to form colorless crystals of the (CO)(1-) radical complex, {[(R(2)N)(3)Y(μ-CO)(2)][K(2)(18-crown-6)(2)]}(n), 1. The polymeric structure contains trigonal bipyramidal [(R(2)N)(3)Y(μ-CO)(2)](2-) units with axial (CO)(1-) ligands linked by [K(2)(18-crown-6)(2)](2+) dications. Byproducts such as the ynediolate, [(R(2)N)(3)Y](2)(μ-OC≡CO){[K(18-crown-6)](2)(18-crown-6)}, 2, in which two (CO)(1-) anions are coupled to form (OC≡CO)(2-), and the insertion/rearrangement product, {(R(2)N)(2)Y[OC(═CH(2))Si(Me(2))NSiMe(3)]}[K(18-crown-6)], 3, are common in these reactions that give variable results depending on the specific reaction conditions. The CO reduction in the presence of THF forms a solvated variant of 2, the ynediolate [(R(2)N)(3)Y](2)(μ-OC≡CO)[K(18-crown-6)(THF)(2)](2), 2a. CO(2) reacts analogously with Y(2+) to form the (CO(2))(1-) radical complex, {[(R(2)N)(3)Y(μ-CO(2))(2)][K(2)(18-crown-6)(2)]}(n), 4, that has a structure similar to that of 1. Analogous (CO)(1-) and (OC≡CO)(2-) complexes of lutetium were isolated using Lu(NR(2))(3)/K/18-crown-6: {[(R(2)N)(3)Lu(μ-CO)(2)][K(2)(18-crown-6)(2)]}(n), 5, [(R(2)N)(3)Lu](2)(μ-OC≡CO){[K(18-crown-6)](2)(18-crown-6)}, 6, and [(R(2)N)(3)Lu](2)(μ-OC≡CO)[K(18-crown-6)(Et(2)O)(2)](2), 6a. © 2012 American Chemical Society

On the role of the termolecular reactions 2O2 + H2 → 2HO2 and 2O2 + H2 → H + HO2 + O2 in formation of the first radicals in hydrogen combustion: ab initio predictions of energy barriers.

PubMed

Monge-Palacios, M; Rafatijo, Homayoon

2017-01-18

We have investigated the role of termolecular reactions in the early chemistry of hydrogen combustion. We performed molecular chemical dynamics simulations using ReaxFF in LAMMPS to identify potential initial reactions for a 1 : 4 mixture of H 2  : O 2 in the NVT ensemble at density 276.3 kg m -3 and ∼3000 K (∼4000 atm) and ∼4000 K (∼5000 atm), and then characterized the saddle points for those reactions using ab initio methods: CCSD(T) = FC/cc-pVTZ//MP2/6-31G, CCSD(T) = FULL/aug-cc-pVTZ//CCSD = FC/cc-pVTZ and CASSCF MP2/6-31G//MP2/6-31G. The main initial reaction is H 2 + O 2 → H + HO 2 , frequently occurring in the presence of a second O 2 as a third body; that is, 2O 2 + H 2 → H + HO 2 + O 2 . The second most frequent reaction is 2O 2 + H 2 → 2HO 2 . We found three saddle points on the triplet PES of these termolecular reactions: one for 2O 2 + H 2 → H + HO 2 + O 2 and two for 2O 2 + H 2 → 2HO 2 . In the latter case, one has a symmetric structure consistent with simultaneous formation of two HO 2 and the other corresponds to a bimolecular reaction between O 2 and H 2 that is "interrupted" by a second O 2 before going to completion. The classical barrier height of the symmetric saddle point for 2O 2 + H 2 → 2HO 2 is 49.8 kcal mol -1 . The barrier to H 2 + O 2 → H + HO 2 is 58.9 kcal mol -1 . The termolecular reaction will be competitive with H 2 + O 2 → H + HO 2 only at sufficiently high pressures.

Binding Energy of Quantum Bound States in X-shaped Nanowire Intersection

DTIC Science & Technology

2014-01-01

α0)〉 = 3~2 mb2 ( 2α0 + 2 11 ) = 6~2 mb2 ( α0 + 1 11 ) = 1.058 ~2 ma2 ∆2 (111) The threshold energy is found to be Et = π2~2 2mw2 (112) Since the...energy (Eb) of the electron taking the threshold energy as zero level is given by Eb = −Emin = −1.058 ~2 ma2 ∆2 = −4.232 ~ 2 mw2 cos2(θ1 − θ2

The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4](2-) (M=Mo, W).

PubMed

Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

2015-08-10

Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2'-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4](2-) were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Free-Surface Flow Over Curved Surfaces

DTIC Science & Technology

1993-08-01

method to the shallow water equations some deficiencies are apparent. The primary problem, for the hydrodynamic conditions we wish to simulate, is that... tK2 K•2 a9 I.- 2 K2h3 13 6 all I -h -I 2 h 4 6 1-2 K2h + f2 (h) log f2 (h)=22- K2 2 hf 2 (h/2) f,(h)logf 2(h) K2 2 K2 3 aK1 2 h + f2 (h/2) log f2 (h

Environmental Impact of Munition and Propellant Disposal (Impact Environnemental de l’Elimination des Munitions et des Combustibles)

DTIC Science & Technology

2010-02-01

Territory of Republic of Bulgaria 2.2.3 Quantity of Conventional Ammunition in the Expired Term 2-3 2.2.4 Technological Possibilities for...Utilization of Life Expired Conventional Ammunition 2-4 2.2.4.1 ‘VMZ’ Co., Sopot 2-4 2.2.4.2 ‘Trema’ Co., Tryavna 2-5 2.2.4.3 ‘Arcus’ Co., Lyaskovetz 2-5...Technology and Process Equipment 2-7 2.2.5 Acts on Environment Preservation in Utilization of Conventional Ammunition in 2-8 the Expired Term 2.2.6

The Synthesis, Characterization and Dehydrogenation of Sigma‐Complexes of BN‐Cyclohexanes

PubMed Central

Kumar, Amit; Ishibashi, Jacob S. A.; Hooper, Thomas N.; Mikulas, Tanya C.; Dixon, David A.

2015-01-01

Abstract The coordination chemistry of the 1,2‐BN‐cyclohexanes 2,2‐R2‐1,2‐B,N‐C4H10 (R2=HH, MeH, Me2) with Ir and Rh metal fragments has been studied. This led to the solution (NMR spectroscopy) and solid‐state (X‐ray diffraction) characterization of [Ir(PCy3)2(H)2(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH) and [Rh(iPr2PCH2CH2CH2PiPr2)(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH, NMe2). For NR2=NH2 subsequent metal‐promoted, dehydrocoupling shows the eventual formation of the cyclic tricyclic borazine [BNC4H8]3, via amino‐borane and, tentatively characterized using DFT/GIAO chemical shift calculations, cycloborazane intermediates. For NR2=NMeH the final product is the cyclic amino‐borane HBNMeC4H8. The mechanism of dehydrogenation of 2,2‐H,Me‐1,2‐B,N‐C4H10 using the {Rh(iPr2PCH2CH2CH2PiPr2)}+ catalyst has been probed. Catalytic experiments indicate the rapid formation of a dimeric species, [Rh2(iPr2PCH2CH2CH2PiPr2)2H5][BArF 4]. Using the initial rate method starting from this dimer, a first‐order relationship to [amine‐borane], but half‐order to [Rh] is established, which is suggested to be due to a rapid dimer–monomer equilibrium operating. PMID:26602704

The Synthesis, Characterization and Dehydrogenation of Sigma-Complexes of BN-Cyclohexanes

DOE PAGES

Kumar, Amit; Ishibashi, Jacob S. A.; Hooper, Thomas N.; ...

2015-11-25

The coordination chemistry of the 1,2-BN-cyclohexanes 2,2-R 2-1,2-B,N-C 4H 10 (R 2=HH, MeH, Me 2) with Ir and Rh metal fragments has been studied. This led to the solution (NMR spectroscopy) and solid-state (X-ray diffraction) characterization of [Ir(PCy 3) 2(H) 2(η 2η 2-H 2BNR 2C 4H 8)][BAr F 4] (NR 2=NH 2, NMeH) and [Rh( iPr 2PCH 2CH 2CH 2P iPr 2)(η 2η 2-H 2BNR 2C 4H 8)][BAr F 4] (NR 2=NH 2, NMeH, NMe 2). For NR 2=NH 2 subsequent metal-promoted, dehydrocoupling shows the eventual formation of the cyclic tricyclic borazine [BNC 4H 8] 3, via amino-borane and, tentativelymore » characterized using DFT/GIAO chemical shift calculations, cycloborazane intermediates. For NR 2=NMeH the final product is the cyclic amino-borane HBNMeC 4H 8. The mechanism of dehydrogenation of 2,2-H,Me-1,2-B,N-C 4H 10 using the {Rh( iPr 2PCH 2CH 2CH 2P iPr 2)} + catalyst has been probed. Catalytic experiments indicate the rapid formation of a dimeric species, [Rh 2( iPr 2PCH 2CH 2CH 2P iPr 2) 2H 5][BAr F 4]. Using the initial rate method starting from this dimer, a first-order relationship to [amine-borane], but half-order to [Rh] is established, which is suggested to be due to a rapid dimer–monomer equilibrium operating.« less

Unsaturated Mn complex decorated hybrid thioarsenates: Syntheses, crystal structures and physical properties

NASA Astrophysics Data System (ADS)

Yue, Cheng-Yang; Lei, Xiao-Wu; Tian, Ya-Wei; Xu, Jing; Bai, Yi-Qun; Wang, Fei; Zhou, Peng-Fei; Liu, Xiao-Fan; Yi, Fei-Yan

2016-03-01

The incorporation of unsaturated [Mn(1,2-dap)]2+, [Mn(1,2-dap)2]2+, [Mn(2,2-bipy)]2+ (1,2-dap=1,2-diaminopropane) complex cations with thioarsenate anions of [AsIIIS3]3- and [AsVS4]3- led to three new hybrid manganese thioarsenates, namely, [Mn(1,2-dap)]2MnAs2S6 (1), [Mn(1,2-dap)2]{[Mn(1,2-dap)]2As2S8} (2) and (NH4)[Mn(2,2-bipy)2]AsS4 (3). In compound 1, the unsaturated [Mn(1,2-dap)]2+ complexes, [MnS4]6- tetrahedra and [AsIIIS3]3- trigonal-pyramids are condensed to form the 1D [Mn(1,2-dap)]2MnAs2S6 chain, whereas compound 2 features 2D layer composed of [Mn(1,2-dap)]2+ and [Mn(1,2-dap)2]2+ complexes as well as [AsVS4]3- tetrahedral units. For compound 3, two [AsVS4]3- anions bridge two [Mn(2,2-bipy)]2+ complex cations into a butterfly like {[Mn(2,2-bipy)]2As2S8}2- anionic unit. Magnetic measurements indicate the ferrimagnetic behavior for compound 1 and antiferromagnetic (AF) behaviors for compounds 2-3. The UV-vis diffuse-reflectance measurements and electronic structural calculations based on density functional theory (DFT) revealed the title compounds belong to semiconductors with band gaps of 2.63, 2.21, and 1.97 eV, respectively. The narrow band-gap of compound 3 led to the efficient and stable photocatalytic degradation activity over organic pollutant than N-doped P25 under visible light irradiation.

Word Criticality Analysis MOS: 15D. Skill Levels 1 & 2.

DTIC Science & Technology

1981-09-01

0p -o1 2-91D1 2-290,1 -2- 27002 -2-245,1 2-12101 apcisoti 2-140,2 "P nSNPG2-155,1 ’ 2 PL~1%UNOI:S 2:146,#2 I POSITLIW 2 264,1I __...POSS IALr . ___2*2...UUALLY _ 2-224,1 2 T1,1 - 91,2 2- 92.2 2- 91.1 3 15.1 A- 17s1 3- 16#1 3- 44.2 1- 7201 3- ISO [ 1- I0,i Z TLZ - 94,1 3- 14,1 3- 1.. 3- 12.1 3- 11.1 2- 90,1

An Estimation Theory Approach to Detection and Ranging of Obscured Targets in 3-D LADAR Data

DTIC Science & Technology

2006-03-01

Bmat = [sum(Bsim*(1-(x-m1).^2/w^2).*rect_f(M1,:))-sum(simdat.*(1-(x- m1).^2/w^2).*rect_f(M1,:)); sum(Bsim*(1-(x-m2...2/w^2).*rect_f(M2,:))-sum(simdat.*(1-(x- m2).^2/w^2).*rect_f(M2,:))]; Xmat(2*M1-1:2*M1,M2) = inv(Amat)* Bmat ; %I=I+1; Est...1-(x-m2).^2/w^2).^2.*rect_f(M2,:))]; Bmat = [sum(Bsim.*(1-(x-m1).^2/w^2).*rect_f(M1,:))-sum(simdat’.*(1-(x- m1).^2/w^2).*rect_f

Vapochromic Behaviour of M[Au(CN)2]2-Based Coordination Polymers (M = Co, Ni)

PubMed Central

Lefebvre, Julie; Korčok, Jasmine L.; Katz, Michael J.; Leznoff, Daniel B.

2012-01-01

A series of M[Au(CN)2]2(analyte)x coordination polymers (M = Co, Ni; analyte = dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), pyridine; x = 2 or 4) was prepared and characterized. Addition of analyte vapours to solid M(μ-OH2)[Au(CN)2]2 yielded visible vapochromic responses for M = Co but not M = Ni; the IR νCN spectral region changed in every case. A single crystal structure of Zn[Au(CN)2]2(DMSO)2 revealed a corrugated 2-D layer structure with cis-DMSO units. Reacting a Ni(II) salt and K[Au(CN)2] in DMSO yielded the isostructural Ni[Au(CN)2]2(DMSO)2 product. Co[Au(CN)2]2(DMSO)2 and M[Au(CN)2]2(DMF)2 (M = Co, Ni) complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH2)[Au(CN)2]2 and from DMSO or DMF solution synthesis. Co[Au(CN)2]2(pyridine)4 is generated via vapour absorption by Co(μ-OH2)[Au(CN)2]2; the analogous Ni complex is synthesized by immersion of Ni(μ-OH2)[Au(CN)2]2 in 4% aqueous pyridine. Similar immersion of Co(μ-OH2)[Au(CN)2]2 yielded Co[Au(CN)2]2(pyridine)2, which has a flat 2-D square-grid structure with trans-pyridine units. Absorption of pyridine vapour by solid Ni(μ-OH2)[Au(CN)2]2 was incomplete, generating a mixture of pyridine-bound complexes. Analyte-free Co[Au(CN)2]2 was prepared by dehydration of Co(μ-OH2)[Au(CN)2]2 at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate. PMID:22737031

Luminescence and Site Occupancy of Eu2+ in Ba2 Ca(BO3)2

NASA Astrophysics Data System (ADS)

Li, Pan-Lai; Wang, Zhi-Jun; Yang, Zhi-Ping; Guo, Qing-Lin

2011-01-01

A green phosphor Ba2Ca(BO3)2:Eu2+ was synthesized by a high temperature solid-state reaction method under a reductive atmosphere. The luminescence and site occupancy of Eu2+ in Ba2Ca(BO3)2 are investigated. Ba2Ca(BO3)2:Eu2+ shows one green band (537 nm) under 400 nm near ultraviolet excitation which is suitable for UV LED. Ca2+ and Ba2+ ions in Ba2Ca(BO3)2 are replaced by Eu2+ ions, the Ba2Ca(BO3)2:Eu2+ shows a dissymmetrical emission band. The influence of Eu2+ doping concentrations on the emission intensity of Ba2Ca(BO3)2:Eu2+ is studied. It is found that the emission intensity is influenced by the Eu2+ concentration and reaches the maximum value at 2% Eu2+. According to the Dexter theory, the concentration quenching mechanisms of Eu2+ in Ba2Ca(BO3)2 are the d-dinteraction.

Controlled synthesis of racemic indenyl rare-earth metal complexes via the cooperation between the intramolecular coordination of donor atoms and a bridge.

PubMed

Zhou, Shuangliu; Wu, Zhangshuan; Zhou, Lingmin; Wang, Shaowu; Zhang, Lijun; Zhu, Xiancui; Wei, Yun; Zhai, Jinhua; Wu, Jie

2013-06-03

The reactions of Me2Si(C9H6CH2CH2-DG)2 (DG = NMe2 (1), CH2NMe2 (2), OMe (3), and N(CH2CH2)2O (4)) with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 in toluene afforded a series of racemic divalent rare-earth metal complexes: {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2-DG)2}RE (DG = NMe2, RE = Yb (6) and Eu (7); DG = CH2NMe2, RE = Yb (8), Eu (9), and Sm (10); DG = OMe, RE = Yb (11) and Eu (12); DG = N(CH2CH2)2O, RE = Yb (13) and Eu (14)). Similarly, the racemic divalent rare-earth metal complexes {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2CH2NMe2)(C9H5CH2CH2OMe)}RE (RE = Yb (15) and Eu (16)) were also obtained. The reaction of Me2Si(C9H5CH2CH2OMe)2Li2 with NdCl3 gave a racemic dimeric neodymium chloride {η(5):η(1):η(5)-Me2Si(C9H5CH2CH2OMe)2NdCl}2 (17), whereas the reaction of Me2Si(C9H5CH2CH2NMe2)2Li2 with SmCl3 afforded a racemic dinuclear samarium chloride bridged by lithium chloride {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2NMe2)2SmCl}2(μ-LiCl) (18). Further reaction of complex 18 with LiCH2SiMe3 provided an unexpected rare-earth metal alkyl complex {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Sm (19) through the activation of an sp(3) C-H bond α-adjacent to the nitrogen atom. Complexes 19 and {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Y (20) were also obtained by one-pot reactions of Me2Si(C9H5CH2CH2NMe2)2Li2 with RECl3 followed by treatment with LiCH2SiMe3. All compounds were fully characterized by spectroscopic methods and elemental analysis. Complexes 6-10 and 14-20 were further characterized by single-crystal X-ray diffraction analysis. All of the prepared rare-earth metal complexes were racemic, suggesting that racemic organo rare-earth metal complexes could be controllably synthesized by the cooperation between a bridge and the intramolecular coordination of donor atoms.

New superhindered polydentate polyphosphine ligands P(CH2CH2P(t)Bu2)3, PhP(CH2CH2P(t)Bu2)2, P(CH2CH2CH2P(t)Bu2)3, and their ruthenium(II) chloride complexes.

PubMed

Gilbert-Wilson, Ryan; Field, Leslie D; Bhadbhade, Mohan M

2012-03-05

The synthesis and characterization of the extremely hindered phosphine ligands, P(CH(2)CH(2)P(t)Bu(2))(3) (P(2)P(3)(tBu), 1), PhP(CH(2)CH(2)P(t)Bu(2))(2) (PhP(2)P(2)(tBu), 2), and P(CH(2)CH(2)CH(2)P(t)Bu(2))(3) (P(3)P(3)(tBu), 3) are reported, along with the synthesis and characterization of ruthenium chloro complexes RuCl(2)(P(2)P(3)(tBu)) (4), RuCl(2)(PhP(2)P(2)(tBu)) (5), and RuCl(2)(P(3)P(3)(tBu)) (6). The bulky P(2)P(3)(tBu) (1) and P(3)P(3)(tBu) (3) ligands are the most sterically encumbered PP(3)-type ligands so far synthesized, and in all cases, only three phosphorus donors are able to bind to the metal center. Complexes RuCl(2)(PhP(2)P(2)(tBu)) (5) and RuCl(2)(P(3)P(3)(tBu)) (6) were characterized by crystallography. Low temperature solution and solid state (31)P{(1)H} NMR were used to demonstrate that the structure of RuCl(2)(P(2)P(3)(tBu)) (4) is probably analogous to that of RuCl(2)(PhP(2)P(2)(tBu)) (5) which had been structurally characterized.

Synthesis, characterization and biological study on Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide and bis(3-hydroxyimino)butan-2-ylidene)-oxalohydrazide.

PubMed

El-Asmy, A A; El-Gammal, O A; Radwan, H A

2010-09-01

Cr(3+), ZrO(2+), HfO(2+) and UO(2)(2+) complexes of oxalohydrazide (H(2)L(1)) and oxalyl bis(diacetylmonoxime hydrazone) [its IUPAC name is oxalyl bis(3-hydroxyimino)butan-2-ylidene)oxalohydrazide] (H(4)L(2)) have been synthesized and characterized by partial elemental analysis, spectral (IR; electronic), thermal and magnetic measurements. [Cr(L(1))(H(2)O)(3)(Cl)].H(2)O, [ZrO(HL(1))(2)].C(2)H(5)OH, [UO(2)(L(1))(H(2)O)(2)] [ZrO(H(3)L(2))(Cl)](2).2H(2)O, [HfO(H(3)L(2))(Cl)](2).2H(2)O and [UO(2)(H(2)L(2))].2H(2)O have been suggested. H(2)L(1) behaves as a monobasic or dibasic bidentate ligand while H(4)L(2) acts as a tetrabasic octadentate with the two metal centers. The molecular modeling of the two ligands have been drawn and their molecular parameters were calculated. Examination of the DNA degradation of H(2)L(1) and H(4)L(2) as well as their complexes revealed that direct contact of [ZrO(H(3)L(2))(Cl)](2).2H(2)O or [HfO(H(3)L(2))(Cl)](2).2H(2)O degrading the DNA of Eukaryotic subject. The ligands and their metal complexes were tested against Gram's positive Bacillus thuringiensis (BT) and Gram's negative (Escherichia coli) bacteria. All compounds have small inhibitory effects. Copyright 2010 Elsevier B.V. All rights reserved.

Does dinitrogen hydrogenation follow different mechanisms for [(eta5-C5Me4H)2Zr]2(mu2,eta2,eta2-N2) and {[PhP(CH2SiMe2NSiMe2CH2)PPh]Zr}2(mu2,eta2,eta2-N2) complexes? A computational study.

PubMed

Bobadova-Parvanova, Petia; Wang, Qingfang; Quinonero-Santiago, David; Morokuma, Keiji; Musaev, Djamaladdin G

2006-09-06

The mechanisms of dinitrogen hydrogenation by two different complexes--[(eta(5)-C(5)Me(4)H)(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)), synthesized by Chirik and co-workers [Nature 2004, 427, 527], and {[P(2)N(2)]Zr}(2)(mu(2),eta(2),eta(2)-N(2)), where P(2)N(2) = PhP(CH(2)SiMe(2)NSiMe(2)CH(2))(2)PPh, synthesized by Fryzuk and co-workers [Science 1997, 275, 1445]--are compared with density functional theory calculations. The former complex is experimentally known to be capable of adding more than one H(2) molecule to the side-on coordinated N(2) molecule, while the latter does not add more than one H(2). We have shown that the observed difference in the reactivity of these dizirconium complexes is caused by the fact that the former ligand environment is more rigid than the latter. As a result, the addition of the first H(2) molecule leads to two different products: a non-H-bridged intermediate for the Chirik-type complex and a H-bridged intermediate for the Fryzuk-type complex. The non-H-bridged intermediate requires a smaller energy barrier for the second H(2) addition than the H-bridged intermediate. We have also examined the effect of different numbers of methyl substituents in [(eta(5)-C(5)Me(n)H(5)(-)(n))(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)) for n = 0, 4, and 5 (n = 5 is hypothetical) and [(eta(5)-C(5)H(2)-1,2,4-Me(3))(eta(5)-C(5)Me(5))(2)Zr](2)(mu(2),eta(2),eta(2)-N(2)) and have shown that all complexes of this type would follow a similar H(2) addition mechanism. We have also performed an extensive analysis on the factors (side-on coordination of N(2) to two Zr centers, availability of the frontier orbitals with appropriate symmetry, and inflexibility of the catalyst ligand environment) that are required for successful hydrogenation of the coordinated dinitrogen.

Syntheses, structures and characterizations of three novel vanadium selenites with organically bonded copper/nickel complex

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

Qian, Cheng; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002; Kong, Fang

2016-06-15

A series of vanadium selenites covalently bonded with metal-organic complex, namely, Ni(2,2-bipy){sub 2}V{sub 2}O{sub 4}(SeO{sub 3}){sub 2} (1), Cu(2,2-bipy)V{sub 2}O{sub 4}(SeO{sub 3}){sub 2}·0.5H{sub 2}O (2) and Cu{sub 2}(2,2-bipy){sub 2}V{sub 5}O{sub 12}(SeO{sub 3}){sub 2} (3) (2,2-bipy=2,2-bipyridine) have been hydrothermally synthesized and structurally characterized. They exhibit three different structural dimensions, from 0D cluster, 1D chain to 2D layer. Compound 1 features a 0D {Ni(2,2-bipy)_2V_2O_4(SeO_3)_2}{sub 2} dimeric cluster composed of two {Ni(2,2-bipy)_2}{sup 2+} moieties connected by the {V_4O_8(SeO_3)_4}{sup 4-} cluster. Compound 2 shows a 1D {Cu(2,2-bipy)V_2O_4(SeO_3)_2}{sub n} chain in which the {Cu_2(2,2-bipy)_2}{sup 4+} moieties are bridged by the {V_4O_8(SeO_3)_4}{sup 4−} clusters. Compound 3more » displays a 2D structure consisted of mixed valence vanadium selenites layers {V"I"VV"V_4Se"I"V_2O_1_8}{sub n}{sup 4−} and {Cu(2,2-bipy)}{sup 2+} complex moieties. The adjacent layers are further interconnected via π-π interactions between the 2,2-bipy ligands exhibiting an interesting 3D supramolecular architecture. Both compound 1 and 2 contain a new {V_4O_8(SeO_3)_4}{sup 4−} cluster and compound 3 exhibits the first 2D vanadate polyhedral layer in vanadium selenites/tellurites with organic moieties. - Graphical abstract: We got three new vanadium selenites with organically linked copper/nickel complex, namely, Ni(2,2-bipy){sub 2}V{sub 2}O{sub 4}(SeO{sub 3}){sub 2} (1), Cu(2,2-bipy)V{sub 2}O{sub 4}(SeO{sub 3}){sub 2}·0.5H{sub 2}O (2) and Cu{sub 2}(2,2-bipy){sub 2}V{sub 5}O{sub 12}(SeO{sub 3}){sub 2} (3) by hydrothermally syntheses. They display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. Display Omitted - Highlights: • Three new compounds display three different structural dimensions, from 0D cluster, to 1D chain and 2D layer. • The Tetranuclear {V_4O_8(SeO_3)_4}{sup 4−} cluster and the vanadate {V_5O_1_7}{sub n} 2D layer are observed firstly. • Optical Properties and Magnetic Properties of three compounds are reported.« less

40 CFR 721.9790 - Benzenesulfonic acid, 2,2′-(1,2-ethenediyl)bis[5-[[4-[bis(2-hydroxypropyl) amino]- 6-[(3...

Code of Federal Regulations, 2012 CFR

2012-07-01

...]-, disodium salt, compd. with 2,2â²,2â³-nitrilo-tris[ethanol] (1:2); Benzenesulfonic acid, 5-[[4-[bis(2.... with 2,2â²,2â³-nitrilotris[ethanol] (1:2). 721.9790 Section 721.9790 Protection of Environment...]-, disodium salt, compd. with 2,2′,2″-nitrilo-tris[ethanol] (1:2); Benzenesulfonic acid, 5-[[4-[bis(2...

40 CFR 721.9790 - Benzenesulfonic acid, 2,2′-(1,2-ethenediyl)bis[5-[[4-[bis(2-hydroxypropyl) amino]- 6-[(3...

Code of Federal Regulations, 2014 CFR

2014-07-01

...]-, disodium salt, compd. with 2,2â²,2â³-nitrilo-tris[ethanol] (1:2); Benzenesulfonic acid, 5-[[4-[bis(2.... with 2,2â²,2â³-nitrilotris[ethanol] (1:2). 721.9790 Section 721.9790 Protection of Environment...]-, disodium salt, compd. with 2,2′,2″-nitrilo-tris[ethanol] (1:2); Benzenesulfonic acid, 5-[[4-[bis(2...

40 CFR 721.9790 - Benzenesulfonic acid, 2,2′-(1,2-ethenediyl)bis[5-[[4-[bis(2-hydroxypropyl) amino]- 6-[(3...

Code of Federal Regulations, 2013 CFR

2013-07-01

...]-, disodium salt, compd. with 2,2â²,2â³-nitrilo-tris[ethanol] (1:2); Benzenesulfonic acid, 5-[[4-[bis(2.... with 2,2â²,2â³-nitrilotris[ethanol] (1:2). 721.9790 Section 721.9790 Protection of Environment...]-, disodium salt, compd. with 2,2′,2″-nitrilo-tris[ethanol] (1:2); Benzenesulfonic acid, 5-[[4-[bis(2...

An Investigation of the Thermal Decomposition of 1, 4-Butanediammonium Dinitrate and Selected Composites with Ammonium and Potassium Nitrates

DTIC Science & Technology

1989-02-01

Reference 20. (8) PN H dCHCHCHH 2T NO2 + H20 PNA (9) PNA - 2C H2CH 2 CH2 NNO + other products PNSA (10) BDD . 02 NNH(CH2 )4 NHNO 2 + 2H2 0 BONA (11) BDNA ...ONNH(CH2 )4 NHNO + other products BONSA 2H+ (12) BDNA --> ý4-CH2CH2 -N=N=0+] 2 + 2H2 0 (a) (13) (a) --- 4 [(CH2 )4 ]++ + 2N2 0 (b) (14) (b) --- H2 C

Intramolecular B/N frustrated Lewis pairs and the hydrogenation of carbon dioxide.

PubMed

Courtemanche, Marc-André; Pulis, Alexander P; Rochette, Étienne; Légaré, Marc-André; Stephan, Douglas W; Fontaine, Frédéric-Georges

2015-06-18

The FLP species 1-BR2-2-NMe2-C6H4 (R = 2,4,6-Me3C6H2, 2,4,5-Me3C6H2) reacts with H2 in sequential hydrogen activation and protodeborylation reactions to give (1-BH2-2-NMe2-C6H4)2. While reacts with H2/CO2 to give formyl, acetal and methoxy-derivatives, reacts with H2/CO2 to give C6H4(NMe2)(B(2,4,5-Me3C6H2)O)2CH2. The mechanism of CO2 reduction is considered.

Establishment of a Rotor Model Basis.

DTIC Science & Technology

1982-06-01

2 FC = J r2 dr = (r r3) W) rA Defining b, = 1 (r2 - N =(A3) b2= r the segment extremities are given by equations (87) as rn(+) = ( nbl + b2 )I1/2 (A...rn(_)] - FC n= 1 N 2 ((2n - 1)b I + 2b2 ][vnb + b2 - .(n - l)bj + b2 -F Cn= 1 S11N-i [(2N - l)bj + 2b2]rT - (b, + 2 b2)rA - b I / nbl + b- FC n=1...EEM = 4 [rn(+) + rn(-)]2[rn(+) - rn(-)] - FC n= 1 N 2 2 4 [rn(+) - rn(_)J[rn(+) + rn(_ )] - FC n= 1 = b (/I + b 2 + bI2+2 E nbl + b2 - FC 4 bj + b 2

From Layered Structures to Cubic Frameworks. Expanding the Structural Diversity of Uranyl Carboxyphosphonates via the Incorporation of Cobalt

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

Alsobrook, Andrea N.; Hauser, Brad G.; Hupp, Joseph T.

2011-02-08

Five heterobimetallic U(VI)/Co(II) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO 3, Co(CH 3CO 2) 2·4H 2O, and triethyl phosphonoacetate. These compounds, Co(H 2O) 4[(UO 2) 2(PO 3CH 2CO 2) 2(H 2O) 2] (CoUPAA-1), [Co(H 2O) 6][UO 2(PO 3CH 2CO 2)] 2·8H 2O (CoUPAA-2), Co(H 2O) 4[UO 2(PO 3CH 2CO 2)] 2·4H 2O (CoUPAA-3), Co(H 2O) 4[(UO 2) 62CH 2CO 2) 2O 2(OH) 3(H 2O) 3] 2·3H 2O (CoUPAA-4), and Co 2(UO 2) 6(PO 3CH 2CO 2) 3O 3(OH)(H 2O) 2·16H 2O (CoUPAA-5), range from two- to three-dimensional structures. CoUPAA-1 to CoUPAA-3 all possess uranyl carboxyphosphonate layersmore » that are separated by the Co(II) cation with varying degrees of hydration. CoUPAA-4 contains both UO 7 pentagonal bipyramids and UO 8 hexagonal bipyramids within the uranyl carboxyphosphonate plane. Unlike the first four low-symmetry compounds, CoUPAA-5 is a cubic, three-dimensional network with large cavities approximately 16 Å in diameter that are filled with cocrystallized water molecules. Differential gas absorption measurements performed on CoUPAA-5 displayed a surface area uptake for CO 2 of 40 m 2 g -1 at 273 K, and no uptake for N 2 at 77 K.« less

Comparison of [Ni(PPh2NPh2)2(CH3CN)]2+ and [Pd(PPh2NPh2)2]2+ as Electrocatalysts for H2 Production

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

Wiedner, Eric S.; Helm, Monte L.

The complexes [Ni(PPh2NPh2)2(CH3CN)]2+ and [Pd(PPh2NPh2)2]2+, where PPh2NPh2 is 1,5-diphenyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane, are compared as electrocatalysts for H2 production under identical experimental conditions. With [(DMF)H]+ as the acid in acetonitrile solution, [Pd(PPh2NPh2)2]2+ afforded a turnover frequency (TOF) of 230 s-1 for formation of H2 under dry conditions and a TOF of 640 s-1 when H2O was added. These rates are similar to the TOF’s of 590 s-1 (dry) and 720 s-1 (wet) that were previously measured for [Ni(PPh2NPh2)2(CH3CN)]2+ using [(DMF)H]+. The [Ni(PPh2NPh2)2(CH3CN)]2+ and [Pd(PPh2NPh2)2]2+ complexes both exhibited large current enhancements when treated with trifluoroacetic acid (TFA). At a TFA concentration of 1.8 M,more » TOF values of 5670 s-1 and 2060 s-1 were measured for [Ni(PPh2NPh2)2(CH3CN)]2+ and [Pd(PPh2NPh2)2]2+, respectively. The fast rates observed using TFA are, in part, attributed to homoconjugation of TFA in acetonitrile solutions, which decreases the effective pKa of the acid. In support of this hypothesis, dramatically lower rates of H2 production were observed using p anisidinium, which has a pKa comparable to TFA but does not homoconjugate significantly in acetonitrile solutions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is oper-ated by Battelle for the U.S. Department of Energy.« less

A Series of Lanthanide Selenidogermanates: The First Coexistence of Three Types of Selenidogermanate Units in the Same Architecture.

PubMed

Tang, Shimei; Zhou, Jian; Zou, Hua-Hong; Liu, Xing; Zhang, Li

2018-02-05

A series of lanthanide selenidogermanates, (H 2 peha)[Ln 2 (μ-OH) 2 (tepa) 2 Cl 2 ]{[Ln 2 (μ-OH) 2 (tepa) 2 Cl] 2 (μ-Ge 2 Se 6 )}[Ge 2 Se 6 ]Cl 2 [Ln = Y (1a) and Er (1b); peha = pentaethylenexamine, tepa = tetraethylenepentamine], [Sm 2 (μ-OH) 2 (tepa) 2 (μ-Ge 2 Se 6 )] n (2), [Ho 2 (μ-OH) 2 (tepa) 2 (μ-Ge 2 Se 6 )] n (3), and [Ce 4 (tepa) 4 (μ-GeSe 4 )(μ-GeSe 5 )(μ-Ge 2 Se 6 )] n (4), were made under solvothermal conditions. Compounds 1a and 1b contain a protonated H 2 peha 2+ ion, the complex cation [Ln 2 (μ-OH) 2 (tepa) 2 Cl 2 ] 2+ , a [Ge 2 Se 6 ] 4- anion, free Cl - ions, and a {[Ln 2 (μ-OH) 2 (tepa) 2 Cl] 2 (μ-Ge 2 Se 6 )} 2+ cation constructed by two unsaturated [Ln 2 (μ-OH) 2 (tepa) 2 Cl] 3+ groups connecting via the trans terminal Se atoms of the [Ge 2 Se 6 ] 4- anion, which provides the first example of an organic decorated lanthanide selenidogermanate cation. Both compounds 2 and 3 contain one-dimensional chains [Ln 2 (μ-OH) 2 (tepa) 2 (μ-Ge 2 Se 6 )] n constructed by a combination of unsaturated complex cations [Ln 2 (μ-OH) 2 (tepa) 2 ] 4+ and [Ge 2 Se 6 ] 4- anions, but their stacking patterns of neutral chains are different. Compound 4 contains one-dimensional chain [Ce 4 (tepa) 4 (μ-GeSe 4 )(μ-GeSe 5 )(μ-Ge 2 Se 6 )] n , where three different selenidogermanate units acting as bridging ligands connect unsaturated [Ce(tepa)] 3+ ions. Compound 4 represents the first example of the coexistence of three different selenidogermanate anions in the same architecture. Their optical properties are studied, and the magnetic properties of compounds 1b and 2-4 are also investigated.

Synthesis, characterization and some properties of mononuclear Ni and trinuclear NiFe2 complexes related to the active site of [NiFe]-hydrogenases.

PubMed

Song, Li-Cheng; Sun, Xiao-Jing; Zhao, Pei-Hua; Li, Jia-Peng; Song, Hai-Bin

2012-08-07

The [N(2)S(2)]-type ligand 1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4) (L) is prepared in 84% yield by a new method and its structure has been confirmed by X-ray crystallography. The new synthetic method involves sequential reaction of 1,2-phenylenedithiol with EtONa followed by treatment of the resulting disodium salt of 1,2-phenylenedithiol with in situ generated 2-(chloromethyl)pyridine from its HCl salt. Further treatment of ligand L with NiCl(2)·6H(2)O or NiI(2) affords the expected new mononuclear Ni complexes Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Cl(2) (1) and Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]I(2) (3) in 87-88% yields, whereas reaction of L with NiBr(2) under similar conditions results in formation of the expected new mononuclear complex Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Br(2) (2) and one unexpected new mononuclear complex Ni[1-(2-C(5)H(4)NCH(2)S)-2-(2-C(5)H(4)NCH(2)SC(6)H(4)S)C(6)H(4)]Br(2) (2*) in 82% and 5% yields, respectively. More interestingly, the ligand L-containing novel trinuclear NiFe(2) complex Ni{[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)}Fe(2)(CO)(6)(μ(3)-S)(2) (4) is found to be prepared by sequential reaction of (μ-S(2))Fe(2)(CO)(6) with Et(3)BHLi, followed by treatment of the resulting (μ-LiS)(2)Fe(2)(CO)(6) with mononuclear complex 1, 2, or 3 in 12-20% yields. The new complexes 1-4 and 2* are fully characterized by elemental analysis and various spectroscopies, and the crystal structures of 1, 2* and 3 as well as some electrochemical properties of 1-4 are also reported.

Crystal structure, complexation, spectroscopic characterization and antimicrobial evaluation of 3,4-dihydroxybenzylidene isonicotinyl-hydrazone

NASA Astrophysics Data System (ADS)

Jeragh, Bakir; Ali, Mayada S.; El-Asmy, Ahmed A.

2015-06-01

A single crystal of 3,4-dihydroxybenzylidene isonicotinylhydrazone, HBINH, has been grown and solved by X-ray crystallography. The VO2+, Zr4+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+ and Pd2+ complexes of HBINH have been prepared and spectroscopically characterized. The data confirmed the formulae [Co(HBINH)(H2O)Cl]Cl·H2O, [Pd(HBINH)Cl2], [Zn(HBINH)2Cl2], [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)], [Ni2(HBINH)(H2O)6Cl2]Cl2, [Cu2(HBINH-3H)(H2O)2(OAc)]·3H2O, [Zr2(HBINH-3H)Cl4]Cl, [Hg2(HBINH)Cl4] and the dimer {[Cu(HBINH)Cl]Cl}2. Most of the complexes have intense colors and high melting points and some are electrolytes in DMSO solution. The ligand behaves as a neutral bidentate in the Co(II), Cu(II), Pd(II), Zn(II) and Cd(II) complexes; dibasic tetradentate in [Ni2(HBINH)(H2O)6Cl2]Cl2 and tribasic tetradentate in [Cu2(HBINH-3H)(OAc)]·5H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Zr2(HBINH-3H)Cl4]Cl by the loss of 3H+ due to the deprotonation of the two hydroxyl groups and the enolization of the amide (Odbnd CNH) group. A tetrahedral geometry was proposed for the Co(II), Cu(II), Zn(II) and Hg(II) complexes; square-planar for the Pd(II) complex; square-pyramid for the VO2+ complex and octahedral for the Ni(II) and Cd(II) complexes. The complexes [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Cu2(HBINH-3H)-(H2O)2(OAc)]·3H2O have activities against Bacillus sp. M3010, Candida albicans, Escherichia coli, Staphylococcus aureus and Slamonella sp. PA393.

Modulation of Cardiac Ryanodine Receptor Channels by Alkaline Earth Cations

PubMed Central

Diaz-Sylvester, Paula L.; Porta, Maura; Copello, Julio A.

2011-01-01

Cardiac ryanodine receptor (RyR2) function is modulated by Ca2+ and Mg2+. To better characterize Ca2+ and Mg2+ binding sites involved in RyR2 regulation, the effects of cytosolic and luminal earth alkaline divalent cations (M2+: Mg2+, Ca2+, Sr2+, Ba2+) were studied on RyR2 from pig ventricle reconstituted in bilayers. RyR2 were activated by M2+ binding to high affinity activating sites at the cytosolic channel surface, specific for Ca2+ or Sr2+. This activation was interfered by Mg2+ and Ba2+ acting at low affinity M2+-unspecific binding sites. When testing the effects of luminal M2+ as current carriers, all M2+ increased maximal RyR2 open probability (compared to Cs+), suggesting the existence of low affinity activating M2+-unspecific sites at the luminal surface. Responses to M2+ vary from channel to channel (heterogeneity). However, with luminal Ba2+or Mg2+, RyR2 were less sensitive to cytosolic Ca2+ and caffeine-mediated activation, openings were shorter and voltage-dependence was more marked (compared to RyR2 with luminal Ca2+or Sr2+). Kinetics of RyR2 with mixtures of luminal Ba2+/Ca2+ and additive action of luminal plus cytosolic Ba2+ or Mg2+ suggest luminal M2+ differentially act on luminal sites rather than accessing cytosolic sites through the pore. This suggests the presence of additional luminal activating Ca2+/Sr2+-specific sites, which stabilize high Po mode (less voltage-dependent) and increase RyR2 sensitivity to cytosolic Ca2+ activation. In summary, RyR2 luminal and cytosolic surfaces have at least two sets of M2+ binding sites (specific for Ca2+ and unspecific for Ca2+/Mg2+) that dynamically modulate channel activity and gating status, depending on SR voltage. PMID:22039534

Half a grid is better than no grid: competition between 2,2':6',2''-terpyridine and 3,6-di(pyrid-2-yl)pyridazine for copper(II).

PubMed

Constable, Edwin C; Decurtins, Silvio; Housecroft, Catherine E; Keene, Tony D; Palivan, Cornelia G; Price, Jason R; Zampese, Jennifer A

2010-03-07

The reaction between Cu(NO(3))(2).3H(2)O, 2,2':6',2''-terpyridine (tpy) and 3,6-di(pyrid-2-yl)pyridazine (1) in a 2 : 2 : 1 molar equivalent ratio in aqueous MeCN in the presence of excess NH(4)PF(6) leads to competition between the assembly of the dinuclear half-grid [Cu(2)(1)(tpy)(2)][PF(6)](4).2H(2)O and the mononuclear complex [Cu(1)(2)(OH(2))][PF(6)](2). The yield of [Cu(2)(1)(tpy)(2)][PF(6)](4).2H(2)O has been optimized using microwave conditions. [Cu(1)(2)(OH(2))][PF(6)](2) can be selectively produced by treating Cu(NO(3))(2).3H(2)O with 1 (1 : 2 molar equivalents) in aqueous MeCN in the presence of NH(4)PF(6). The single crystal structures of [Cu(2)(1)(tpy)(2)][PF(6)](4).4MeNO(2) and [Cu(1)(2)(OH(2))][PF(6)](2) are presented. In the [Cu(2)(1)(tpy)(2)](4+) cation, ligand 1 bridges the two copper(II) centres, each of which is further coordinated by a tpy ligand. The copper(II) coordination geometry is closely associated with the arrangement of the two tpy ligands which engage in efficient face-to-face pi-stacking. Magnetic data for crystalline [Cu(2)(1)(tpy)(2)][PF(6)](4).4MeNO(2) are consistent with a weak antiferromagnetic interaction between the two copper(II) centres. EPR spectroscopic data for a powder sample of [Cu(2)(1)(tpy)(2)][PF(6)](4).2H(2)O are consistent with the dinuclear structure, but in frozen DMF and DMSO solutions, the data indicate that the dinuclear structure of [Cu(2)(1)(tpy)(2)](4+) is not preserved.

Studies on the Condensation Pathway to and Properties of Diiron Azadithiolate Carbonyls

PubMed Central

Stanley, Jane L.; Rauchfuss, Thomas B.; Wilson, Scott R.

2008-01-01

Reaction of Fe2(SH)2(CO)6 and HCHO, which gives Fe2[(SCH2)2NH](CO)6 in the presence of NH3, affords the possible intermediate Fe2(SCH2OH)2(CO)6, which has been characterized crystallographically as its axial–equatorial isomer. Fe2(SCH2OH)2(CO)6 was shown to react with ammonia and amines to give Fe2[(SCH2)2NR](CO)6 (R = H, alkyl). Related hemithioacetal intermediates were generated by treatment of Fe2(SH)2(CO)6 with RC(O)C(O)R (R = H, Ph, 4-F-C6H4) to give cycloadducts. The benzil derivative Fe2[S2C2(OH)2Ph2](CO)6, a C2-symmetric species, was also characterized crystallographically. The acylated azadithiolate Fe2[(SCH2)2NAc](CO)6 was prepared by reaction of Li2Fe2S2(CO)6 with (ClCH2)2NC(O)Me. DNMR experiments show that the free energies of activation for rotation of the amide bond are the same for Fe2[(SCH2)2NAc](CO)6 and Fe2[(SCH2)2NAc](CO)4(PMe3)2, which implies that the ligands on the iron centers do not strongly affect the basicity of the nitrogen. As a control, we showed that the thioamide Fe2[(SCH2)2NC(S)Me](CO)6 does exhibit a significantly higher barrier to rotation, attributable to the increased double-bond character of the N–C(S) bond. PMID:18592045

A series of Cadmium(II) complexes with 2-substituted terephthalate building block and N-Donor co-ligands: Structural diversity and fluorescence properties

NASA Astrophysics Data System (ADS)

Ren, Yixia; Zhou, Shanhong; Wang, Zhixiang; Zhang, Meili; Wang, Jijiang; Cao, Jia

2017-11-01

Four new Cd(II) complexes have been prepared based on 1,2,4-trimellitic acid (H3tma) and monosodium 2-sulfoterephthalate (2-NaH2stp), formulated as [Cd2(Htma)2 (dpp)2(H2O)] (1), [Cd3 (tma)2 (2,4-bipy)4(H2O)2] (2), [Cd (2-Hstp) (2,2'-bipy)2]·2H2O (3) and [Cd (2-Hstp) (2,4-bipy) (H2O)2] (4) (dpp = dipyrido [3,2-a:2‧,3'-c] phenazine, 2,4-bipy = 2,4-bipyridine, 2,2'-bipy = 2,2'- bipyridine) by hydrothermal method. X-ray diffraction structural analyses show all these complexes crystallized in triclinic crystal system of Pī space group, but their structures are diverse. Complex 1 exhibits an infinite one-dimensional chain featuring the left- and right-handed stranded chains interweaved each other. For 2, the two-dimensional network is constructed by one-dimensional ladder-like chain linked by Cd2 ions. In complex 3, the cadmium ion is surrounded with one 2-Hstp2- anion and two 2,2'-bipy molecules. Complex 4 is also a discrete structure based on a metallic dimer unit. In all these complexes, the N-donor co-ligands take the important roles in the assembly of three-dimensional supramolecular structures. The fluorescence properties of complexes 1-4 could be assigned to the π - π* transition of organic ligands.

On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation

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

Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.

The mechanical properties and stability of studtite, (UO2)(O2)(H2O)2·2H2O, and metastudtite, (UO2)(O2)(H2O)2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO2)(O2)(H2O)2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO2)(O2)(H2O)2·2H2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh’s and Poisson’s ratios and the Cauchy pressure, both phases are considered ductile and shear modulus is the parameter limiting their mechanical stability. Debye temperatures of 294 and 271 K are predicted formore » polycrystalline (UO2)(O2)(H2O)2·2H2O and (UO2)(O2)(H2O)2, suggesting a lower micro-hardness of metastudtite.« less

On the mechanical stability of uranyl peroxide hydrates: Implications for nuclear fuel degradation

DOE PAGES

Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.

2015-09-11

The mechanical properties and stability of studtite, (UO 2)(O 2)(H 2O) 2·2H 2O, and metastudtite, (UO 2)(O 2)(H 2O) 2, two important corrosion phases observed on spent nuclear fuel exposed to water, have been investigated using density functional perturbation theory. While (UO 2)(O 2)(H 2O) 2 satisfies the necessary and sufficient Born criteria for mechanical stability, (UO 2)(O 2)(H 2O) 2·2H 2O is found to be mechanically metastable, which might be the underlying cause of the irreversibility of the studtite to metastudtite transformation. According to Pugh's and Poisson's ratios and the Cauchy pressure, both phases are considered ductile and shearmore » modulus is the parameter limiting their mechanical stability. Furthermore, debye temperatures of 294 and 271 K are predicted for polycrystalline (UO 2)(O 2)(H 2O) 2·2H 2O and (UO 2)(O 2)(H 2O) 2, suggesting a lower micro-hardness of metastudtite.« less

Measurement of the radiative decay and energy of the metastable $${(2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{(J=0)}$$ level in Fe XVII

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

Beiersdorfer, P.; Lopez-Urrutia, J. R. Crespo; Trabert, E.

Measurements at the Livermore electron beam ion trap have been performed in order to infer the energy and the radiative lifetime of themore » $${(1{s}^{2}2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=0}$$ level in the Fe xvii spectrum. This is the longest-lived level in the neonlike iron ion, and its radiative decay produces the Fe xvii line at 1153 Å, feeding the population of the $${(1{s}^{2}2{s}^{2}2{p}_{3/2}^{5}3{s}_{1/2})}_{J=1}$$ upper level of one of the most prominent lines in the Fe xvii L-shell X-ray spectrum, commonly dubbed $3G$. In the presence of a strong ($$\\geqslant $$ few kG) magnetic field, the $${(1{s}^{2}2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=0}$$ level has a finite probability to decay directly to the $${(1{s}^{2}2{s}^{2}2{p}^{6})}_{J=0}$$ neonlike ground level via the emission of an L-shell X-ray. Our measurements allow us to observe this X-ray line in the Fe xvii L-shell spectrum and from it to infer the radiative rate for the magnetic dipole decay of the $${(1{s}^{2}2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=0}$$ level to the $${(1{s}^{2}2{s}^{2}2{p}_{3/2}^{5}3{s}_{1/2})}_{J=1}$$. Our result of $$(1.45\\pm 0.15)\\times {10}^{4}$$ s-1 is in agreement with predictions. We have also measured the wavelength of the associated X-ray line to be 16.804 ± 0.002 Å, which means that the line is displaced 1.20 ± 0.05 eV from the neighboring $${(2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=1}\\to {(2{s}^{2}2{p}^{6})}_{J=0}$$ transition, commonly labeled $3F$. Furthermore, from our measurement, we infer 5950570 ± 710 cm-1 for the energy of the $${(1{s}^{2}2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=0}$$ level.« less

Measurement of the radiative decay and energy of the metastable $${(2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{(J=0)}$$ level in Fe XVII

DOE PAGES

Beiersdorfer, P.; Lopez-Urrutia, J. R. Crespo; Trabert, E.

2016-01-20

Measurements at the Livermore electron beam ion trap have been performed in order to infer the energy and the radiative lifetime of themore » $${(1{s}^{2}2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=0}$$ level in the Fe xvii spectrum. This is the longest-lived level in the neonlike iron ion, and its radiative decay produces the Fe xvii line at 1153 Å, feeding the population of the $${(1{s}^{2}2{s}^{2}2{p}_{3/2}^{5}3{s}_{1/2})}_{J=1}$$ upper level of one of the most prominent lines in the Fe xvii L-shell X-ray spectrum, commonly dubbed $3G$. In the presence of a strong ($$\\geqslant $$ few kG) magnetic field, the $${(1{s}^{2}2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=0}$$ level has a finite probability to decay directly to the $${(1{s}^{2}2{s}^{2}2{p}^{6})}_{J=0}$$ neonlike ground level via the emission of an L-shell X-ray. Our measurements allow us to observe this X-ray line in the Fe xvii L-shell spectrum and from it to infer the radiative rate for the magnetic dipole decay of the $${(1{s}^{2}2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=0}$$ level to the $${(1{s}^{2}2{s}^{2}2{p}_{3/2}^{5}3{s}_{1/2})}_{J=1}$$. Our result of $$(1.45\\pm 0.15)\\times {10}^{4}$$ s-1 is in agreement with predictions. We have also measured the wavelength of the associated X-ray line to be 16.804 ± 0.002 Å, which means that the line is displaced 1.20 ± 0.05 eV from the neighboring $${(2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=1}\\to {(2{s}^{2}2{p}^{6})}_{J=0}$$ transition, commonly labeled $3F$. Furthermore, from our measurement, we infer 5950570 ± 710 cm-1 for the energy of the $${(1{s}^{2}2{s}^{2}2{p}_{1/2}^{5}3{s}_{1/2})}_{J=0}$$ level.« less

State Space Methods in Multidimensional Digital Signal Processing

DTIC Science & Technology

1991-01-01

2-D finite difference equation with quarter-plane support is given by [1]. Li L-2 Ll L2 g (nln2) =E E Zb(jl,j2)f(n,-j, n 2 -j 2 ) - E a(jl,j2) g (n, - j...B2 [ g (n , n2)] = [C1 C2 1 Sq’(n nl2) ]+ D [f (ni, n 2 )] (2.2) Roesser’s state space model is based upon assigning state variables to the output of...QH(n - 1,n2) + [ B1 [f(nl,n2)]Qv(ni, n2) I A3 A411 Qv(nl, n2 -1 1 B2 [ g (n 1 ,n 2 )] = [C1 C 2] Q(n - n) + D[f(nin 2 )] (2.5) I Qv(ni,n2- 1) 1 In this

Predictions Regarding the Performance of Field Emission Cathodes in Radio Frequency Guns

DTIC Science & Technology

2010-01-01

b2b by equation 2.3. Finally, ηb = ab/fb as defined in equation 2.5. Next...2.11) with η (r, z) = √ r2 + (z − fb)2 + √ r2 + (z + fb) 2 2fb where, summarizing from above, fb = √ a2 b − b2b and ηb = ab fb = ab √ a2 b − b2b ...1 2 x, to rewrite the equations as ze ≈ ab [ 1− 1 2 ( r bb )2 ] zc ≈ cr [ 1− 1 2 ( r cr )2 ] + ab − cr. or ze ≈ ab − 1 2 abr 2 b2b zc ≈ ab − 1 2 r2

Telemetry Standards

DTIC Science & Technology

2000-01-01

07040188), Washington, DC 20603. 1. AGENCY USE ONLY (Leave blank) 2. REPORT DATE January 2000 3 . REPORT TYPE AND DATES COVERED 4. TITLE AND...2.3.1.3 1530 to 1535 MHz ’.’ 2- 3 2.3.2 Allocation of the S Band (2200 to 2300 MHz) 2- 3 2.3.2.1 2200 to 2290 MHz 2- 3 2.3.2.2 2290 to 2300 MHz 2- 3 ...2.3.3 Allocation of the Upper S Band (2310 to 2390 MHz) 2- 3 2.3.3.1 2310 to 2360 MHz 2- 3 2.3.3.2 2360 to 2390 MHz 2- 3 2.4 UHF Telemetry Transmitter

Synthesis and study of electronic state of Sr2CrO2Co2As2 with CoAs conduction layers

NASA Astrophysics Data System (ADS)

Suzuki, Atsushi; Ohta, Hiroto; Aruga Katori, Hiroko

2017-06-01

We successfully synthesized a new member of compounds with the CoAs layer, Sr2CrO2Co2As2, and its partially substituted systems Sr2CrO2(Tmx Co1- x )2As2 (Tm = Fe, Ni), and measured magnetization and electric resistivity of these polycrystalline compounds. As a result of magnetic measurement for Sr2CrO2Co2As2, magnetic moments of Co do not construct an itinerant electronic ferromagnetism unlike other compounds with the CoPn (Pn=P and As) layers. Both Sr2CrO2(Tmx Co1- x )2As2 with Tm = Fe and Ni also do not show an itinerant electronic ferromagnetism down to 2 K. For each solid solution of Sr2CrO2(Fe x Co1- x )2As2 with x > 0.0, ρ weakly increases with the decrease of T at low temperature region, indicating that the mixed occupancy of Cr and Fe within the conducting layers occurs in Sr2CrO2(Fe x Co1- x )2As2. We conclude that the absence of ferromagnetism in Sr2CrO2Co2As2 is due to the self-electron-doping from Cr to the conduction bands and the attempt to recover the ferromagnetism by the hole-doping effect is prevented by the mixed occupancy of Cr and Fe in Sr2CrO2 (Fe x Co1- x )2As2 with x > 0.0. The result of our structural analysis supports that the disappearance of itinerant electronic ferromagnetism in Sr2CrO2Co2As2 is due to the self-electron-doping from Cr.

Newly synthesized MgAl2Ge2: A first-principles comparison with its silicide and carbide counterparts

NASA Astrophysics Data System (ADS)

Tanveer Karim, A. M. M.; Hadi, M. A.; Alam, M. A.; Parvin, F.; Naqib, S. H.; Islam, A. K. M. A.

2018-06-01

Using plane-wave pseudopotential density functional theory (DFT), the first-principle calculations are performed to investigate the structural aspects, mechanical behaviors and electronic features of the newly synthesized CaAl2Si2-prototype intermetallic compound, MgAl2Ge2 for the first time and the results are compared with those calculated for its silicide and carbide counterparts MgAl2Si2 and MgAl2C2. The calculated lattice constants agree fairly well with their corresponding experimental values. The estimated elastic tensors satisfy the mechanical stability conditions for MgAl2Ge2 along with MgAl2Si2 and MgAl2C2. The level of elastic anisotropy increases following the sequence of X-elements Ge → Si → C. MgAl2Ge2 and MgAl2Si2 are expected to be ductile and damage tolerant, while MgAl2C2 is a brittle one. MgAl2Ge2 and MgAl2Si2 should exhibit better thermal shock resistance and low thermal conductivity and accordingly these can be used as thermal barrier coating (TBC) materials. The Debye temperature of MgAl2Ge2 is lowest among three intermetallic compounds. MgAl2Ge2 and MgAl2Si2 should exhibit metallic conductivity; while the dual characters of weak-metals and semiconductors are expected for MgAl2C2. The values of theoretical Vickers hardness for MgAl2Ge2, MgAl2Si2, and MgAl2C2 are 3.3, 2.7, and 7.7 GPa, respectively, indicating that these three intermetallics are soft and easily machinable.

Thermomechanical Cracking in Layered Media from Moving Friction Load,

DTIC Science & Technology

1984-07-01

Dimensionless Temperature The materials of the surface layer and the substrate are the same as Figure 1. D = Hi = 2, x = 0.01 in 61 13. Dimensionless...J 2 (j 2 M2 )] )(60) and 01) (4 ) / 2 2 2 , ")VI’ - [(i - M2 /J 2) + (U - M2 2/ ,(1) + ( - M2/12 )(I - M2/j2)V(1 ) = 0 ( 61 ) 18 .. .. mm...ii - -iii - -ml m . . . . . . . .-... -- Equation ( 61 ) has a characteristic equation x4 _ (I - M2/J2) + (1 - M2/12 )]x2 +(1 - M2/12 )(1 - M2

Excision of uranium oxide chains and ribbons in the novel one-dimensional uranyl iodates K(2)[(UO(2))3(IO(3))(4)O(2)] and Ba[(UO(2)2(IO(3))(2)O(2)](H(2)O).

PubMed

Bean, A C; Ruf, M; Albrecht-Schmitt, T E

2001-07-30

The alkali metal and alkaline-earth metal uranyl iodates K(2)[(UO(2))(3)(IO(3))(4)O(2)] and Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) have been prepared from the hydrothermal reactions of KCl or BaCl(2) with UO(3) and I(2)O(5) at 425 and 180 degrees C, respectively. While K(2)[(UO(2))(3)(IO(3))(4)O(2)] can be synthesized under both mild and supercritical conditions, the yield increases from <5% to 73% as the temperature is raised from 180 to 425 degrees C. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), however, has only been isolated from reactions performed in the mild temperature regime. Thermal measurements (DSC) indicate that K(2)[(UO(2))(3)(IO(3))(4)O(2)] is more stable than Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) and that both compounds decompose through thermal disproportionation at 579 and 575 degrees C, respectively. The difference in the thermal behavior of these compounds provides a basis for the divergence of their preparation temperatures. The structure of K(2)[(UO(2))(3)(IO(3))(4)O(2)] is composed of [(UO(2))(3)(IO(3))(4)O(2)](2)(-) chains built from the edge-sharing UO(7) pentagonal bipyramids and UO(6) octahedra. Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O) consists of one-dimensional [(UO(2))(2)(IO(3))(2)O(2)](2)(-) ribbons formed from the edge sharing of distorted UO(7) pentagonal bipyramids. In both compounds the iodate groups occur in both bridging and monodentate binding modes and further serve to terminate the edges of the uranium oxide chains. The K(+) or Ba(2+) cations separate the chains or ribbons in these compounds forming bonds with terminal oxygen atoms from the iodate ligands. Crystallographic data: K(2)[(UO(2))(3)(IO(3))(4)O(2)], triclinic, space group P_1, a = 7.0372(5) A, b = 7.7727(5) A, c = 8.9851(6) A, alpha = 93.386(1) degrees, beta = 105.668(1) degrees, gamma = 91.339(1) degrees, Z = 1; Ba[(UO(2))(2)(IO(3))(2)O(2)](H(2)O), monoclinic, space group P2(1)/c, a = 8.062(4) A, b = 6.940(3) A, c = 21.67(1), beta= 98.05(1) degrees, Z = 4.

Heterometallic and homometallic complexes containing bifunctional ligands and their application in high-temperature oxide superconductor materials

NASA Astrophysics Data System (ADS)

Breeze, Steven R.

We have been interested in the development of soluble precursors for the production of YBasb2Cusb3Osb{7-delta} and Bisb2(Ca,Sr)sbn+1CusbnOsb(2n + 4) + delta, superconductor materials. Several heterometallic and homometallic complexes containing the constituent metals of these superconductors and bifunctional ligands such as aminoalcohols, acetates and thioethers have been isolated and structurally characterized. The thermal decomposition properties and magnetic properties of some of these compounds have been investigated. The first ligand system investigated involved 1,3-bis(dimethylamino)-2-propanol (bdmapH). By varying the ratio of bdmapH, Cu(OCHsb3)sb2, and M(Osb2CCFsb3)sb2 (M = Ca, Sr) several heterometallic complexes have been obtained, including Srsb2Cusb2(bdmap)sb4(Osb2CCFsb3)sb4, CaCu(bdmap)sb2(Osb2CCFsb3)sb3(Hsb2O), Srsb2Cusb4(bdmap)sb6-(Osb2CCFsb3)sb4(musb 3-OH)sb2(THF)sb2 and SrCusb2(bdmap)sb3(Osb2CCFsb3)sb3(THF). With the exception of Srsb2Cusb4(bdmap)sb6(Osb2CCFsb3)sb4(musb 3-OH)sb2(THF)sb2, these compounds thermally decompose to form mixtures of fluorides and oxides. An analogous acetate compound SrCusb2(bdmap)sb3(Osb2CCHsb3)sb3(THF) has been produced, which forms the corresponding oxide at high temperature. A bismuth dimer, Bisb2(bdmap)sb2(Osb2CCHsb3)sb4(Hsb2O), has also been obtained. Superconducting powder of the Bisb2Srsb2CaCusb2Osb{8 + delta} and epitaxial superconducting films of the YBasb2Cusb3Osb{7-delta} superconductor have been produced using the bdmap and acetate ligands as cross-linking reagents. The second ligand system investigated involved di-2-pyridylmethanediol. Only homonuclear complexes have been obtained by using this ligand, including the mononuclear compound Cu ((2-py)sb2CO(OH)) sb2(HOsb2CCH sb3)sb2*CHsb2Clsb2, the tetranuclear compound Cusb4 ((2-py)sb2CO(OH)) sb2(Osb2CCHsb 3)sb6(Hsb2O)sb2*CHsb2Clsb2, and the bismuth dimer Bisb2 ((2-py)sb2CO(OH)) sb2(Osb 2CCFsb3)sb4*(THF)sb2. The tetranuclear Cusb4 compound was found to be dominated by ferromagnetic exchanges. The third ligand system examined involved 2,2sp'-thiodiethanol (tdeHsb2). Heterometallic complexes Prsb2Cusb4(tde)sb3(tdeH)sb2(hfacac)sb4(musb6 -O) and Basb2Cusb2(tdeH)sb4(hfacac)sb4 have been obtained using this ligand. The six metal centers in Prsb2Cusb4(tde)sb3(tdeH)sb2(hfacac)sb4(musb6-O) are arranged in a octahedron and are linked by musb6-oxide and 2,2sp'-thiodiethanolato ligands. A metallomacrocyclic Cusb4 compound, Cusb4(tde)sb2(hfacac)sb4 has been produced. Attempts have been made to produce bismuthine complexes with an amino or pyridyl functional group that can coordinate to copper. The reaction of 4-Li-Csb6Hsb4CHsb2N(2-PY)sb2 with BiClsb3 produces the compound BispIII (p-Csb6Hsb4CHsb2N(2-py)sb2rbracksb3. The ability of this compound to coordinate CuClsb2 has been investigated. The complex BispV (p-Csb6Hsb4CHsb2N(2-py)sb2rbracksb3(Osb2CCHsb3)sb2 has also been produced.

Syntheses, crystal structures, and water adsorption behaviors of jungle-gym-type porous coordination polymers containing nitro moieties

NASA Astrophysics Data System (ADS)

Uemura, Kazuhiro; Onishi, Fumiaki; Yamasaki, Yukari; Kita, Hidetoshi

2009-10-01

NO 2 containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO 2) and 2,5-dinitroterephthalate (bdc-(NO 2) 2), afford porous coordination polymers, {[Zn 2(bdc-NO 2) 2(dabco)]· solvents} n ( 2⊃ solvents) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]· solvents} n ( 3⊃ solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn 2 units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2⊃ solvents and 3⊃ solvents, a rectangle pore surrounded by eight Zn 2 corners contains two and four NO 2 moieties, respectively. Thermal gravimetry (TG) and X-ray powder diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me 2CO. Adsorption measurements reveal that dried 2 and 3 adsorb H 2O molecules to be {[Zn 2(bdc-NO 2) 2(dabco)]·4H 2O} n ( 2⊃4H 2O) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]·6H 2O} n ( 3⊃6H 2O), showing the pore hydrophilicity enhancement caused by NO 2 group introduction.

Tuning Coupling Behavior of Stacked Heterostructures Based on MoS2, WS2, and WSe2

PubMed Central

Wang, Fang; Wang, Junyong; Guo, Shuang; Zhang, Jinzhong; Hu, Zhigao; Chu, Junhao

2017-01-01

The interlayer interaction of vertically stacked heterojunctions is very sensitive to the interlayer spacing, which will affect the coupling between the monolayers and allow band structure modulation. Here, with the aid of density functional theory (DFT) calculations, an interesting phenomenon is found that MoS2-WS2, MoS2-WSe2, and WS2-WSe2 heterostructures turn into direct-gap semiconductors from indirect-gap semiconductors with increasing the interlayer space. Moreover, the electronic structure changing process with interlayer spacing of MoS2-WS2, MoS2-WSe2, and WS2-WSe2 is different from each other. With the help of variable-temperature spectral experiment, different electronic transition properties of MoS2-WS2, MoS2-WSe2, and WS2-WSe2 have been demonstrated. The transition transformation from indirect to direct can be only observed in the MoS2-WS2 heterostructure, as the valence band maximum (VBM) at the Γ point in the MoS2-WSe2 and WS2-WSe2 heterostructure is less sensitive to the interlayer spacing than those from the MoS2-WS2 heterostructure. The present work highlights the significance of the temperature tuning in interlayer coupling and advance the research of MoS2-WS2, MoS2-WSe2, and WS2-WSe2 based device applications. PMID:28303932

Alcohol and aldehyde dehydrogenase gene polymorphisms influence susceptibility to esophageal cancer in Japanese alcoholics.

PubMed

Yokoyama, A; Muramatsu, T; Omori, T; Matsushita, S; Yoshimizu, H; Higuchi, S; Yokoyama, T; Maruyama, K; Ishii, H

1999-11-01

Studies have consistently demonstrated that inactive aldehyde dehydrogenase-2 (ALDH2), encoded by ALDH2*1/2*2, is closely associated with alcohol-related carcinogenesis. Recently, the contributions of alcohol dehydrogenase-2 (ADH2) polymorphism to alcoholism, esophageal cancer, and the flushing response have also been described. To determine the effects of ALDH2 and ADH2 genotypes in genetically based cancer susceptibility, lymphocyte DNA samples from 668 Japanese alcoholic men more than 40 years of age (91 with and 577 without esophageal cancer) were genotyped and the results were expressed as odds ratios (ORs). This study also tested 82 of the alcoholics with esophageal cancer to determine whether cancer susceptibility is associated with patients' responses to simple questions about current or former flushing after drinking a glass of beer. The frequencies of ADH2*1/2*1 and ALDH2*1/2*2 were significantly higher in alcoholics with, than in those without, esophageal cancer (0.473 vs. 0.289 and 0.560 vs. 0.099, respectively). After adjustment for drinking and smoking, the analysis showed significantly increased cancer risk for alcoholics with either ADH2*1/2*I (OR = 2.03) or ALDH2*1/2*2 (OR = 12.76). For those having ADH2*1/2*1 combined with ALDH2*1/2*2, the esophageal cancer risk was enhanced in a multiplicative fashion (OR = 27.66). Responses to flushing questions showed that only 47.8% of the ALDH2*1/2*2 heterozygotes with ADH2*1/ 2*1, compared with 92.3% of those with ALDH2*1/2*2 and the ADH2*2 allele, reported current or former flushing. Genotyping showed that for alcoholics who reported ever flushing, the questionnaire was 71.4% correct in identifying ALDH2*1/2*2 and 87.9% correct in identifying ALDH2*1/2*1. Japanese alcoholics can be divided into cancer susceptibility groups on the basis of their combined ADH2 and ALDH2 genotypes. The flushing questionnaire can predict high risk ALDH2*1/2*2 fairly accurately in persons with ADH2*2 allele, but a reliable screening procedure for the highest risk gene combination (ADH2*1/2*1 and ALDH2*1/2*2) will require further investigation.

Process for the preparation of benozotriazoles and their polymers, and 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole produced thereby

DOEpatents

Vogl, Otto; Nir, Zohar

1989-03-14

The compound 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole (2H5P) is produced by azo coupling of o-nitrophenyl diazonium chloride with p-hydroxyacetophenone, subjecting the resulting isolated azo compound to reductive cyclization with zinc in the presence of sodium hydroxide at a temperature of about 50.degree.-70.degree. C., acidifying the resulting mixture so as to produce (2(2-hydroxy-5-acetylphenyl)2H-benzotriazole (2H5A), acetylating the isolated 2(2-hydroxy-5-acetylphenyl)2H-benzotriazole (2H5A), so as to produce 2(2-acetoxy-5-acetylphenyl)2H-benzotriazole (2A5A), methylating the isolated 2(2-acetoxy-5-acetylphenyl(2H-benzotriazole (2A5A) with a methyl Grignard reagent and dehydrating the isolated reaction product with potassium hydrogen sulfate so as to produce 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole (2H5P). The compound is used as a polymerizable ultra violet light stabilizer.

Near-infrared luminescence of Bi2ZnOB2O6:Nd3+/PMMA composite

NASA Astrophysics Data System (ADS)

Jaroszewski, K.; Głuchowski, P.; Chrunik, M.; Jastrząb, R.; Majchrowski, A.; Kasprowicz, D.

2018-01-01

Near-infrared luminescence of a novel polymer composite system: PMMA doped with Bi2ZnOB2O6:Nd3+ microparticles, is reported for the first time. Luminescence properties of Bi2ZnOB2O6:Nd3+/PMMA were analyzed on the basis on excitation and emission spectra as well as fluorescence decay profiles. Excitation spectra monitored at 1062 nm (4F3/2 → 4I11/2) indicate numerous bands related to the optical transition of Nd3+ ions: from the 4I9/2 ground state to the 4D3/2, 2P1/2, 2K15/2, 4G7/2 + 4G9/2, 2K13/2, 4G5/2 + 2G7/2, 2H11/2, 4F9/2, 4F7/2 + 4S3/2, 4F5/2 + 2H9/2, 4F3/2 excited states. Many of them may be utilized to excite near-infrared emission of Nd3+ ions. In particular, distinctive Nd3+ emissions of the 4F3/2 → 4I9/2 and 4F3/2 → 4I11/2 transitions were detected, under excitation at 514 nm. The fluorescence decay profiles monitored at 1062 nm, excited at 514 nm, show relatively long emission lifetime of the 4F3/2 → 4I11/2 transition equal to 85 μs. Raman spectroscopy was used to determine vibrational properties and homogeneity of Bi2ZnOB2O6:Nd3+/PMMA composites. The obtained results suggest that Bi2ZnOB2O6:Nd3+/PMMA composite may be applied as an effective source of near-infrared emission in a new integrated optoelectronic devices.

Ekectron-Impact Excitation of C+

NASA Astrophysics Data System (ADS)

Pearce, A. J.; Ballance, C. P.; Loch, S. D.; Pindzola, M. S.

2015-05-01

Electron-impact excitation cross sections are calculated for ground and excited states of C+ using the R-matrix with pseudo-states method. We used the configurations 1s2 2s2 nl (3 s <= nl <= 12 g) , 1s2 2 s 2 pnl (2 p <= nl <= 12 g) , 1s2 2p2 nl (2 p <= nl <= 12 g) , 1s2 2 s 3s2 , and 1s2 2 s 3d2 , resulting in 890 LS terms and 2048 LSJ levels. Excitation cross sections for the 1s2 2s2 2 p2 P -->4 P,2 D,2 S transitions are in good agreement with experiment. Combined with previous calculations for C and Cq+ (q = 2- 5), sufficient excitation, ionization, and recombination atomic data is now available to generate high quality collisional-radiative coefficients for the entire C isonuclear sequence. Work supported in part by grants from NASA, NSF, and DOE.

Census of U.S. Civil Aircraft, Calendar Year 1985.

DTIC Science & Technology

1985-12-31

LIMITED BN-2B-2 10 5’ 2 0 1 BN-26-21 10 51 2 0 1 1 F/W MULTI REC. ENG 51 0 2 2 TOTAL 0 2 2 . PINE AIR % SUPER V 4 51 2 0 1 F/W MULTI REC. ENG 51 0 1 1... Plymouth 32 12 15 2 2 1Pocahontas 22 7 13 1 1Polk 405 104 180 36 17 23 1 8 3 2 1 30 *Pottawatta 68 12 39 7 2 6 3 0 . Powes"In 21 7 10 2 2 Ringgold 3 2 1...2 Ballard 3 2 Barren 22 4 14 1 3 Bath 2 1 Bell 12 1 8 2 Boone 17 4 9 1 1 2 Bourbon 5 1 3 Boyd 37 8 14 6 2 2 2 Boyle 12 4 Bracken 3 2 1 Breatnitt 9

Halide anion effects on coordination polymerization of cadmium(II) halide with 1: 1 mixed ligands

NASA Astrophysics Data System (ADS)

Ryu, Minjoo; Lee, Young-A.; Jung, Ok-Sang

2018-05-01

Insight into self-assembly of CdX2 (X = Cl and Br) with a mixture of L1 and L2 (L1 = diallylbis(3-pyridyl)silane; L2 = diallylbis(4-pyridyl)silane) was carried out. The self-assembly of CdCl2 with the 1: 1 mixture of L1 and L2 produces only 2D [CdCl2(L1)(L2)] with heteroleptic ligands, whereas that of CdBr2 with the 1: 1 mixture of L1 and L2 gives rise to the statistical mixture of 2D sheet [CdBr2(L1)2]·2H2O, 1D loop-chain [CdBr2(L2)2]·2CH2Cl2, and the 2D [CdBr2(L1)(L2)] with heteroleptic ligands.

Reduced-Order Observer Model for Antiaircraft Artillery (AAA) Tracker Response

DTIC Science & Technology

1979-08-01

a22 -ka1 2) z + (a22 - ka1 2) ky + (a21 - kall ) y + (b2 - kb) uc (10) Next, the actual output of this model is expressed as the sum of the output u...a22x2 + b2u + f2eT = (a2 2 - kal2) z + (a2 2 - ka12) ky + (a21 - kall ) y + (b2 - kb l ) uc u=u +vC [Ti Y2] [y] By introducing new variables: X3 = x2...x3 [(a22- ka2)k + (a2- kall ) - (b2- kb) (YI + kY2) Y + [a22 - ka12 - (b2 - kbl) Y2] X3 + (b2 -kbl) y2 e + (2 - kbI) v + (f2 - kfl) 0 T e = (a22- ka12

Synthesis and reactivity of NHC-supported Ni2(μ(2)-η(2),η(2)-S2)-bridging disulfide and Ni2(μ-S)2-bridging sulfide complexes.

PubMed

Olechnowicz, Frank; Hillhouse, Gregory L; Jordan, Richard F

2015-03-16

The (IPr)Ni scaffold stabilizes low-coordinate, mononuclear and dinuclear complexes with a diverse range of sulfur ligands, including μ(2)-η(2),η(2)-S2, η(2)-S2, μ-S, and μ-SH motifs. The reaction of {(IPr)Ni}2(μ-Cl)2 (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with S8 yields the bridging disulfide species {(IPr)ClNi}2(μ(2)-η(2),η(2)-S2) (2). Complex 2 reacts with 2 equiv of AdNC (Ad = adamantyl) to yield a 1:1 mixture of the terminal disulfide compound (IPr)(AdNC)Ni(η(2)-S2) (3a) and trans-(IPr)(AdNC)NiCl2 (4a). 2 also reacts with KC8 to produce the Ni-Ni-bonded bridging sulfide complex {(IPr)Ni}2(μ-S)2 (6). Complex 6 reacts with H2 to yield the bridging hydrosulfide compound {(IPr)Ni}2(μ-SH)2 (7), which retains a Ni-Ni bond. 7 is converted back to 6 by hydrogen atom abstraction by 2,4,6-(t)Bu3-phenoxy radical. The 2,6-diisopropylphenyl groups of the IPr ligand provide lateral steric protection of the (IPr)Ni unit but allow for the formation of Ni-Ni-bonded dinuclear species and electronically preferred rather than sterically preferred structures.

Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation

DOE PAGES

Weck, Philippe F.; Kim, Eunja

2016-07-11

The interplay between thermodynamics and mechanical properties in the transformation of studtite, (UO 2)(O 2)(H 2O) 2·2H 2O, into metastudtite, (UO 2)(O 2)(H 2O) 2, two important corrosion phases observed on the surface of uranium dioxide exposed to water, is revealed using density functional perturbation theory. Phonon calculations within the quasi-harmonic approximation predict that the standard entropy change for the (UO 2)(O 2)(H 2O) 2·2H 2O → (UO 2)(O 2)(H 2O) 2 + 2H 2O reaction is ΔS 0 = +80 J·mol –1·K –1 for the production of water in the liquid state and +389 J·mol–1·K–1 for water vapor. Similarmore » to bulk H 2O(l), the bulk modulus of (UO 2)(O 2)(H 2O) 2·2H 2O increases with temperature, contrasting with (UO 2)(O 2)(H 2O) 2 which features the typical Anderson–Gruneisen temperature dependence of oxide solids. Upon removal of interstitial H 2O in studtite, the most important changes in the shear modulus, the parameter limiting the mechanical stability, arise in the planes normal to chain propagation directions. Lastly, the present findings have important implications for the dehydration of other hygroscopic materials.« less

Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation

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

Weck, Philippe F.; Kim, Eunja

The interplay between thermodynamics and mechanical properties in the transformation of studtite, (UO 2)(O 2)(H 2O) 2·2H 2O, into metastudtite, (UO 2)(O 2)(H 2O) 2, two important corrosion phases observed on the surface of uranium dioxide exposed to water, is revealed using density functional perturbation theory. Phonon calculations within the quasi-harmonic approximation predict that the standard entropy change for the (UO 2)(O 2)(H 2O) 2·2H 2O → (UO 2)(O 2)(H 2O) 2 + 2H 2O reaction is ΔS 0 = +80 J·mol –1·K –1 for the production of water in the liquid state and +389 J·mol–1·K–1 for water vapor. Similarmore » to bulk H 2O(l), the bulk modulus of (UO 2)(O 2)(H 2O) 2·2H 2O increases with temperature, contrasting with (UO 2)(O 2)(H 2O) 2 which features the typical Anderson–Gruneisen temperature dependence of oxide solids. Upon removal of interstitial H 2O in studtite, the most important changes in the shear modulus, the parameter limiting the mechanical stability, arise in the planes normal to chain propagation directions. Lastly, the present findings have important implications for the dehydration of other hygroscopic materials.« less

Ruthenium(II) piano stool coordination compounds with aminomethylphosphanes: Synthesis, characterisation and preliminary biological study in vitro.

PubMed

Płotek, Michał; Starosta, Radosław; Komarnicka, Urszula K; Skórska-Stania, Agnieszka; Kołoczek, Przemysław; Kyzioł, Agnieszka

2017-05-01

Reaction of {[Ru(η 6 -p-cymene)Cl] 2 (μ-Cl) 2 } (1) with aminomethylphosphane derived from morpholine (P{CH 2 N(CH 2 CH 2 ) 2 O} 3 (A), PPh 2 {CH 2 N(CH 2 CH 2 ) 2 O} (B)) or piperazine (P{CH 2 N(CH 2 CH 2 ) 2 NCH 2 CH 3 } 3 (C), PPh 2 {CH 2 N(CH 2 CH 2 ) 2 NCH 2 CH 3 } (D)) results in four new piano stool ruthenium(II) coordination compounds: [Ru(η 6 -p-cymene)Cl 2 (A)] (2A), [Ru(η 6 -p-cymene)Cl 2 (B)] (2B), [Ru(η 6 -p-cymene)Cl 2 (C)] (2C) and [Ru(η 6 -p-cymene)Cl 2 (D)] (2D). Every complex was fully characterized using spectroscopic methods ( 1 H, 13 C{ 1 H}, 31 P{ 1 H} NMR and ESI-MS), elemental analysis, X-ray single crystal diffraction and DFT calculations. Preliminary studies of in vitro cytotoxicity on the A549 (human lung adenocarcinoma) and MCF7 (human breast adenocarcinoma) cell lines revealed 2A-2D activity in the same order of magnitude as in the case of cisplatin. Additionally, the study confirmed the ability of 2A-2D to interact with DNA helix and transferrin. Copyright © 2017 Elsevier Inc. All rights reserved.

P2X2 knockout mice and P2X2/P2X3 double knockout mice reveal a role for the P2X2 receptor subunit in mediating multiple sensory effects of ATP

PubMed Central

Cockayne, Debra A; Dunn, Philip M; Zhong, Yu; Rong, Weifang; Hamilton, Sara G; Knight, Gillian E; Ruan, Huai-Zhen; Ma, Bei; Yip, Ping; Nunn, Philip; McMahon, Stephen B; Burnstock, Geoffrey; Ford, Anthony PDW

2005-01-01

Extracellular ATP plays a role in nociceptive signalling and sensory regulation of visceral function through ionotropic receptors variably composed of P2X2 and P2X3 subunits. P2X2 and P2X3 subunits can form homomultimeric P2X2, homomultimeric P2X3, or heteromultimeric P2X2/3 receptors. However, the relative contribution of these receptor subtypes to afferent functions of ATP in vivo is poorly understood. Here we describe null mutant mice lacking the P2X2 receptor subunit (P2X2−/−) and double mutant mice lacking both P2X2 and P2X3 subunits (P2X2/P2X3Dbl−/−), and compare these with previously characterized P2X3−/− mice. In patch-clamp studies, nodose, coeliac and superior cervical ganglia (SCG) neurones from wild-type mice responded to ATP with sustained inward currents, while dorsal root ganglia (DRG) neurones gave predominantly transient currents. Sensory neurones from P2X2−/− mice responded to ATP with only transient inward currents, while sympathetic neurones had barely detectable responses. Neurones from P2X2/P2X3Dbl−/− mice had minimal to no response to ATP. These data indicate that P2X receptors on sensory and sympathetic ganglion neurones involve almost exclusively P2X2 and P2X3 subunits. P2X2−/− and P2X2/P2X3Dbl−/− mice had reduced pain-related behaviours in response to intraplantar injection of formalin. Significantly, P2X3−/−, P2X2−/−, and P2X2/P2X3Dbl−/− mice had reduced urinary bladder reflexes and decreased pelvic afferent nerve activity in response to bladder distension. No deficits in a wide variety of CNS behavioural tests were observed in P2X2−/− mice. Taken together, these data extend our findings for P2X3−/− mice, and reveal an important contribution of heteromeric P2X2/3 receptors to nociceptive responses and mechanosensory transduction within the urinary bladder. PMID:15961431

Analysis of Multimode Low-Probability-of-Intercept (LPI) Communications With Atmospheric Effects

DTIC Science & Technology

1996-12-01

of the Requirements for the Degree of Master of Science in Electrical Engineering Ala Ghordlo, B.ENG Captain, Royal Jordanian Air Force December...2-10 2.1.3.5 Atmospheric Quality Factor ............... 2-10 2.2 Propagation Models And Atmospheric Models ............ 2-12 2.2.1 The...Hata Model .............................. 2-12 2.2.2 The MPM Model ....... ...................... 2-13 2.2.3 Discussion of M odels .................... 2

[Distribution of genotypes of alcohol dehydrogenase 2 and aldehyde dehydrogenase 2 in Japanese twin children].

PubMed

Qu, W; Yamagata, Z; Wu, D; Zhang, B; Zhang, Y

1999-03-01

In order to prevent alcohol related deseases, this study investigated the distribution of the genes controlling alcohol metabolism in Japan's twin. Restriction fragment length polymorphism-polymerase chain reaction (RFLP-PCR) technique was used to measure the control gene of alcohol metabolized enzymes and the genotypes of alcohol dehydrogenase 2 (ADH2) and aldehyde dehydrogenase 2 (ALDH2), which were distributed in Japan's twins. At the same time, according to the difference in genotypes, the sensitive individuals were screened from the study subjects. The distribution of ADH2 and ALDH2 genes were consistent with the Hardy-weinberg equation. The three genotypes of ADH2 gene were ADH2(1)/ADH2(1) (1.1%), ADH2(1)/ADH2(2) (44.6%) and ADH2(2)/ADH2(2) (54.3%). And those of ALDH2 gene were ALDH2(1)/ALDH2(1) (41.3%), ALDH2(1)/ALDH2(2) (39.1%) and ALDH2(2)/ALDH2(2) (19.6%). The frequency of ADH2 and ALDH2 genes was 0.255, 0.745 and 0.609, 0.391 respectively. Not only the distribution of genotypes of ADH2 and ALDH2 is known, but also the sensitive individuals are found, which can help prevent alcohol related disease.

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2012 CFR

2012-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2014 CFR

2014-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2011 CFR

2011-07-01

... sulfonate); and ethanol, 2-[1-[[2-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy... sulfonate); and ethanol, 2-[1-[[2-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy...,2′-[oxybis(2,1-ethanediyloxy)]bis-, bis(4-methylbenzene-sulfonate) (PMN P-93-1195, CAS no. 19249-03...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2010 CFR

2010-07-01

... sulfonate); and ethanol, 2-[1-[[2-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy... sulfonate); and ethanol, 2-[1-[[2-[2-[[(4-methylphenyl)sulfonyl] oxy]ethoxy] ethoxy]methyl]-2-(2-propenyloxy...,2′-[oxybis(2,1-ethanediyloxy)]bis-, bis(4-methylbenzene-sulfonate) (PMN P-93-1195, CAS no. 19249-03...

A family of silver(I) complexes built with 2-sulfoterephthalic acid monosodium salt and different aminopyridine ligands: Syntheses, structures and properties

NASA Astrophysics Data System (ADS)

Zhang, Jie; Tan, Gai-Xiu; Liu, Bao-Lin; Dai, Yu-Bei; Xu, Na; Wen, Wei-Fen; Cao, Chong; Xiao, Hong-Ping

2017-05-01

Five Ag(I) coordination complexes, namely, [Ag6(2-stp)2(3-methyl-2-apy)3·H2O]n (1), [Ag3(2-stp)(4-methyl-2-apy)3]n (2), [Na2Ag18(2-stp)4(2-Hstp)4(5-methyl-2-apy)16 (H2O)4·11H2O]n (3), Ag3(2-stp)(6-methy-2-apy)4·H2O (4), and [Ag6(2-stp)2(6-methyl-2-apy)8(H2O)2·H2O]n (5) (2-NaH2stp = 2-sulfoterephthalic acid monosodium salt, 3-methyl-2-apy = 3-methyl-2-aminopyridine, 4-methyl-2-apy = 4-methyl-2-aminopyridine, 5-methyl-2-apy = 5-methyl-2-aminopyridine, 6-methyl-2-apy = 6-methyl-2-aminopyridine), have been synthesized and structurally characterized. Complexes 1 and 2 show two-dimensional network. In complex 3, the adjacent Ag10 units are bridged by 5-methyl-2-apy ligands to form a 2D infinite undulated sheet. Adjacent 2D sheets are linked by coordinative bonds between carboxylic oxygen atoms and Na(I) ions to form a 3D coordination polymer. Complex 4 is a 0-D discrete trinuclear molecule, and the self-complementary the Osbnd H⋯O and Nsbnd H⋯O hydrogen bonds incorporating hydrogen bond motifs extend these molecules into a 2D supramolecular framework. Compound 5 exhibits 1D-chain structure. However, complex 5 shows 3D supramolecular structure results from the linkage of neighboring layers through a rich hydrogen-bonding between uncoordinated sulfonates, amino groups and coordinated carboxylates. The thermogravimetric analyses and photoluminescence of the complexes were also investigated.

Synthesis, characterization, structural and biological aspects of copper(II) dithiocarbamate complexes - Part II, [Cu{S2CN(Me)(R1)}2], [Cu{S2CN(Me)(R2)}2] and [Cu{S2CN(R3)(R4)}2] {R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH}

NASA Astrophysics Data System (ADS)

Ferreira, Isabella P.; de Lima, Geraldo M.; Paniago, Eucler B.; Takahashi, Jacqueline A.; Krambrock, Klaus; Pinheiro, Carlos B.; Wardell, James L.; Visentin, Lorenzo C.

2013-09-01

Three new copper(II) dithiocarbamates (DTC), [Cu{S2CN(Me)(R1)}2] (1), [Cu{S2CN(Me)(R2)}2] (2) and [Cu{S2CN(R3)(R4)}2] (3) with R1 = CH2CH(OMe)2, R2 = 2-methyl-1,3-dioxolane, R3 = CH2(CH2)2NCHPhOCH2Ph and R4 = CH2CH2OH, have been synthesized and characterized by different spectroscopic techniques. Complexes (1) and (2) display typical EPR spectra for separated Cu(II) centers, and the spectrum of (3) is characteristic of two magnetically coupled Cu(II) ions with S = 1. The X-ray crystallographic determination has shown that complexes (1) and (2) crystallise in the triclinic and monoclinic systems. In addition both complexes are monomers in which the geometry at each Cu(II) is square planar. The in vitro antimicrobial activity of the sodium salts of ligands, and of the Cu(II)-DTC complexes have been screened against Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus, Penicillium citrinum and Curvularia senegalensis, as well as Gram positive and Gram negative bacteria. Finally, the toxic effects of complexes (1)-(3) were performed using Chlorella vulgaris.

Synthesis, structural characterization, and electrochemical properties of dinuclear Ni/Mn model complexes for the active site of [NiFe]-hydrogenases.

PubMed

Song, Li-Cheng; Li, Jia-Peng; Xie, Zhao-Jun; Song, Hai-Bin

2013-10-07

Four new dinuclear Ni/Mn model complexes RN(PPh2)2Ni(μ-SEt)2(μ-Cl)Mn(CO)3 (7, R = p-MeC6H4CH2; 8, R = EtO2CCH2) and RN(PPh2)2Ni(μ-SEt)2(μ-Br)Mn(CO)3 (9, R = p-MeC6H4CH2; 10, R = EtO2CCH2) have been prepared via the four separated step-reactions involving six new precursors RN(PPh2)2 (1, R = p-MeC6H4CH2; 2, R = EtO2CCH2), RN(PPh2)2NiCl2 (3, R = p-MeC6H4CH2; 4, R = EtO2CCH2), and RN(PPh2)2Ni(SEt)2 (5, R = p-MeC6H4CH2; 6, R = EtO2CCH2). The Et3N-assisted aminolysis of Ph2PCl with p-MeC6H4CH2NH2 or EtO2CCH2NH2·HCl in CH2Cl2 gave the azadiphosphine ligands 1 and 2 in 38% and 53% yields, whereas the coordination reaction of 1 or 2 with NiCl2·6H2O in CH2Cl2/MeOH afforded the mononuclear Ni dichloride complexes 3 and 4 in 59% and 78% yields, respectively. While thiolysis of 3 or 4 with EtSH under the assistance of Et3N in CH2Cl2 produced the mononuclear Ni dithiolate complexes 5 and 6 in 64% and 68% yields, further treatment of 5 and 6 with Mn(CO)5Cl or Mn(CO)5Br resulted in formation of the dinuclear Ni/Mn model complexes 7-10 in 31-73% yields. All the new compounds 1-10 have been structurally characterized, while model complexes 7 and 9 have been found to be catalysts for HOAc proton reduction to hydrogen under CV conditions.

Alkyl complexes of strontium and barium: synthesis and structural characterization of [(Me3Si)2(MeOMe2Si)C]2Sr(THF) and [(Me3Si)2(MeOMe2Si)C]2Ba(MeOCH2CH2OMe).

PubMed

Izod, Keith; Liddle, Stephen T; Clegg, William

2003-06-25

Metathesis between either SrI2 or BaI2 and 2 equiv of {(Me3Si)2(MeOMe2Si)C}K in THF yields the novel heavier alkali metal dialkyls {(Me3Si)2(MeOMe2Si)C}2M(L) [M(L) = Sr(THF) (2), Ba(DME) (3) (DME = 1,2-dimethoxyethane)] after recrystallization.

Coordination polymers of 5-substituted isophthalic acid

DOE PAGES

McCormick, Laura J.; Morris, Samuel A.; Slawin, Alexandra M. Z.; ...

2015-12-10

In this work, the synthesis and characterisation of five coordination polymers - Ni 2(mip) 2 (H 2O) 8 ·2H 2O (1), Zn 6(mip) 5(OH) 2(H 2O) 4 ·7.4H 2O (2), Zn 6(mip) 5(OH) 2(H 2O) 2 ·4H 2O (3), Mn(HMeOip) 2 (4), and Mn 3(tbip) 2(Htbip) 2(EtOH) 2 (5) - are reported. Preliminary nitric oxide release data on compounds 2 and 3 are also given.

The Mechanics of Long Bone Fractures.

DTIC Science & Technology

1981-01-31

r = .99) between wet density and ultimate bending strength for 37 specimens of human femoral bone. Evans (1973) studied embalmed human tibial...Work 2 2.2 Methods 6 2.2.1 Torsional Loading 6 2.2.2 The Effects of Combined Loading 10 2.2.3 Cancellous Bone Effects 11 2.3 Results 11 2.3.1...PROPERTIES 21 3.1 Previous Work 22 3.2 Methods 26 3.2.1 Cross Sectional Property Software 26 3.2.2 CT Scanning Procedure 28 3.2.3 Linear Dependency of

Phase, current, absorbance, and photoluminescence of double and triple metal ion-doped synthetic and salmon DNA thin films

NASA Astrophysics Data System (ADS)

Chopade, Prathamesh; Reddy Dugasani, Sreekantha; Reddy Kesama, Mallikarjuna; Yoo, Sanghyun; Gnapareddy, Bramaramba; Lee, Yun Woo; Jeon, Sohee; Jeong, Jun-Ho; Park, Sung Ha

2017-10-01

We fabricated synthetic double-crossover (DX) DNA lattices and natural salmon DNA (SDNA) thin films, doped with 3 combinations of double divalent metal ions (M2+)-doped groups (Co2+-Ni2+, Cu2+-Co2+, and Cu2+-Ni2+) and single combination of a triple M2+-doped group (Cu2+-Ni2+-Co2+) at various concentrations of M2+ ([M2+]). We evaluated the optimum concentration of M2+ ([M2+]O) (the phase of M2+-doped DX DNA lattices changed from crystalline (up to ([M2+]O) to amorphous (above [M2+]O)) and measured the current, absorbance, and photoluminescent characteristics of multiple M2+-doped SDNA thin films. Phase transitions (visualized in phase diagrams theoretically as well as experimentally) from crystalline to amorphous for double (Co2+-Ni2+, Cu2+-Co2+, and Cu2+-Ni2+) and triple (Cu2+-Ni2+-Co2+) dopings occurred between 0.8 mM and 1.0 mM of Ni2+ at a fixed 0.5 mM of Co2+, between 0.6 mM and 0.8 mM of Co2+ at a fixed 3.0 mM of Cu2+, between 0.6 mM and 0.8 mM of Ni2+ at a fixed 3.0 mM of Cu2+, and between 0.6 mM and 0.8 mM of Co2+ at fixed 2.0 mM of Cu2+ and 0.8 mM of Ni2+, respectively. The overall behavior of the current and photoluminescence showed increments as increasing [M2+] up to [M2+]O, then decrements with further increasing [M2+]. On the other hand, absorbance at 260 nm showed the opposite behavior. Multiple M2+-doped DNA thin films can be used in specific devices and sensors with enhanced optoelectric characteristics and tunable multi-functionalities.

Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C-Si bond activation and catalytic activity in ethylene polymerization.

PubMed

Lyubov, Dmitry M; Cherkasov, Anton V; Fukin, Georgy K; Ketkov, Sergey Yu; Shavyrin, Andrey S; Trifonov, Alexander A

2014-10-14

The reaction of Ap(9Me)Lu(CH2SiMe3)2(thf) (Ap(9Me) = (2,4,6-trimethylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) with two molar equivalents of PhSiH3 affords a trinuclear alkyl-hydrido cluster [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2]. The analogous reactions with Ap(9Me)Ln(CH2SiMe3)2(thf) (Ln = Y, Yb) are more complex and result in the formation of mixtures of two types of trinuclear alkyl-hydrido complexes [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiH2Ph)(thf)2] differing in the alkyl group. The DFT calculations of [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] (Ap* = (2,6-diisopropylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) confirm localization of the HOMO on the Ap*-Y(1A)-CH2SiMe3 fragment, thus explaining its enhanced reactivity. Analysis of the electron density distribution reveals the Y-H and H-H bonding interactions in the (Y)3(μ(2)-H)3(μ(3)-H)2 moiety. The NMR studies of diamagnetic complexes [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] demonstrated that the trinuclear cores are retained in the solution and revealed exchange between μ(3)- and μ(2)-bridging hydrido ligands. Complexes [(Ap*Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2], the cationic yttrium hydrido cluster [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(thf)3](+)[B(C6F5)4](-) as well as [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] proved to be active in catalysis of ethylene polymerization under mild conditions.

Teaching the fundamentals of electron transfer reactions in mitochondria and the production and detection of reactive oxygen species

PubMed Central

Mailloux, Ryan J.

2015-01-01

Mitochondria fulfill a number of biological functions which inherently depend on ATP and O2−•/H2O2 production. Both ATP and O2−•/H2O2 are generated by electron transfer reactions. ATP is the product of oxidative phosphorylation whereas O2−• is generated by singlet electron reduction of di-oxygen (O2). O2−• is then rapidly dismutated by superoxide dismutase (SOD) producing H2O2. O2−•/H2O2 were once viewed as unfortunately by-products of aerobic respiration. This characterization is fitting considering over production of O2−•/H2O2 by mitochondria is associated with range of pathological conditions and aging. However, O2−•/H2O2 are only dangerous in large quantities. If produced in a controlled fashion and maintained at a low concentration, cells can benefit greatly from the redox properties of O2−•/H2O2. Indeed, low rates of O2−•/H2O2 production are required for intrinsic mitochondrial signaling (e.g. modulation of mitochondrial processes) and communication with the rest of the cell. O2−•/H2O2 levels are kept in check by anti-oxidant defense systems that sequester O2−•/H2O2 with extreme efficiency. Given the importance of O2−•/H2O2 in cellular function, it is imperative to consider how mitochondria produce O2−•/H2O2 and how O2−•/H2O2 genesis is regulated in conjunction with fluctuations in nutritional and redox states. Here, I discuss the fundamentals of electron transfer reactions in mitochondria and emerging knowledge on the 11 potential sources of mitochondrial O2−•/H2O2 in tandem with their significance in contributing to overall O2−•/H2O2 emission in health and disease. The potential for classifying these different sites in isopotential groups, which is essentially defined by the redox properties of electron donator involved in O2−•/H2O2 production, as originally suggested by Brand and colleagues is also surveyed in detail. In addition, redox signaling mechanisms that control O2−•/H2O2 genesis from these sites are discussed. Finally, the current methodologies utilized for measuring O2−•/H2O2 in isolated mitochondria, cell culture and in vivo are reviewed. PMID:25744690

Syntheses and structural characterization of non-centrosymmetric Na{sub 2}M{sub 2}M'S{sub 6} (M, M′=Ga, In, Si, Ge, Sn, Zn, Cd) sulfides

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

Yohannan, Jinu P.; Vidyasagar, Kanamaluru, E-mail: kvsagar@iitm.ac.in

Seven new non-centrosymmetric Na{sub 2}M{sub 2}M’S{sub 6} sulfides, namely, Na{sub 2}Sn{sub 2}ZnS{sub 6}(1){sub ,} Na{sub 2}Ga{sub 2}GeS{sub 6}(2), Na{sub 2}Ga{sub 2}SnS{sub 6}(3-α), Na{sub 2}Ga{sub 2}SnS{sub 6}(3-β){sub ,} Na{sub 2}Ge{sub 2}ZnS{sub 6}(4){sub ,} Na{sub 2}Ge{sub 2}CdS{sub 6}(5){sub ,} Na{sub 2}In{sub 2}SiS{sub 6}(6) and Na{sub 2}In{sub 2}GeS{sub 6}(7), were synthesized by high temperature solid state reactions and structurally characterized by single crystal X-ray diffraction. They crystallize in non-centrosymmetric Fdd2 and Cc space groups and their three-dimensional [M{sub 2}M′S{sub 6}]{sup 2-}framework structures consist of MS{sub 4} and M′S{sub 4} tetrahedra corner-connected to one another in either orderly or disordered fashion. Sodium ions residemore » in the tunnels of the anionic framework. Compounds 1, 2 and 3-α have the structure of known Li{sub 2}Ga{sub 2}GeS{sub 6}, whereas compounds 6 and 7 are isostructural with known Li{sub 2}In{sub 2}GeS{sub 6} compound. Isostructural compounds 4 and 5 represent a new structural variant. Compounds 3-α and its new monoclinic structural variant 3-β have disordered structural framework. All of them are wide band gap semiconductors. Na{sub 2}Ga{sub 2}GeS{sub 6}(2), Na{sub 2}Ga{sub 2}SnS{sub 6}(3), Na{sub 2}Ge{sub 2}ZnS{sub 6}(4) and Na{sub 2}In{sub 2}GeS{sub 6}(7) compounds are found to be second-harmonic generation (SHG) active. Compounds 1, 2 and 3-α melt congruently. - Graphical abstract: Na{sub 2}Ga{sub 2}GeS{sub 6}, Na{sub 2}Ga{sub 2}SnS{sub 6}, Na{sub 2}Ge{sub 2}ZnS{sub 6}, Na{sub 2}In{sub 2}GeS{sub 6}, Na{sub 2}Sn{sub 2}ZnS{sub 6}, Na{sub 2}Ge{sub 2}CdS{sub 6} and Na{sub 2}In{sub 2}SiS{sub 6} have non-centrosymmetric structures and the first four compounds are SHG active. Display Omitted - Highlights: • Seven new Na{sub 2}M{sub 2}M′S{sub 6} compounds with non-centrosymmetric structures were synthesized. • They are wide band gap semiconductors. • Na{sub 2}Ga{sub 2}GeS{sub 6}, Na{sub 2}Ga{sub 2}SnS{sub 6}, Na{sub 2}Ge{sub 2}ZnS{sub 6} and Na{sub 2}In{sub 2}GeS{sub 6} are SHG active.« less

Analysis of Several PLA2 mRNA in Human Meningiomas

PubMed Central

Denizot, Yves; De Armas, Rafael; Durand, Karine; Robert, Sandrine; Moreau, Jean-Jacques; Caire, François; Weinbreck, Nicolas; Labrousse, François

2009-01-01

In view of the important oncogenic action of phospholipase A2(PLA2) we investigated PLA2 transcripts in human meningiomas. Real-time PCR was used to investigate PLA2 transcripts in 26 human meningioma tumors. Results indicated that three Ca2+-dependent high molecular weight PLA2 (PLA2-IVA, PLA2-IVB, PLA2-IVC), one Ca2+-independent high molecular weight PLA2 (PLA2-VI) and five low molecular weight secreted forms of PLA2 (PLA2-IB, PLA2-IIA, PLA2-III, PLA2-V, and PLA2-XII) are expressed with PLA2-IVA, PLA2-IVB, PLA2-VI, and PLA2-XIIA as the major expressed forms. PLA2-IIE, PLA2-IIF, PLA2-IVD, and PLA2-XIIB are not detected. Plasma (PLA2-VIIA) and intracellular (PLA2-VIIB) platelet-activating factor acetylhydrolase transcripts are expressed in human meningiomas. However no difference was found for PLA2 transcript amounts in relation to the tumor grade, the subtype of meningiomas, the presence of inflammatory infiltrated cells, of an associated edema, mitosis, brain invasion, vascularisation or necrosis. In conclusion numerous genes encoding multiples forms of PLA2 are expressed in meningiomas where they might act on the phospholipid remodeling and on the local eicosanoid and/or cytokine networks. PMID:20339511

Strategies for the Construction of Supramolecular Dimers versus Homoleptic 1D Coordination Polymers Starting from the Diphosphorus [Cp2Mo2(CO)4(η2‐P2)] Complex and Silver(I) Salts

PubMed Central

Elsayed Moussa, Mehdi; Fleischmann, Martin; Peresypkina, Eugenia V.; Dütsch, Luis; Seidl, Michael; Balázs, Gabor

2017-01-01

The reactions of the tetrahedral diphosphorus [Cp2Mo2(CO)4(η2‐P2)] (1; Cp = C5H5) complex with Ag[Al{OC(CF3)3}4] (AgTEF) (A) and Ag[FAl{OC(C6F5)(C6F10)}3] (AgFAl) (B) were studied. The first reaction led to the formation of the [Ag2(η2‐1)2(η1:η1‐1)2][TEF]2 (2) dimer and the [Ag2(η1:η1‐1)3]n[TEF]2n (3) coordination polymer, whereas the second reaction afforded the [Ag2(η1:η1‐1)2(η1‐CH2Cl2)2(η2‐C7H8)2][FAl]2 (4) or the [Ag2(η2‐1)2(η1:η1‐1)2][FAl]2 (5) dimer and the [Ag2(η1:η1‐1)4]n[FAl]2n (6) coordination polymer. In each case, the products obtained depended on the ratio of the reactants and/or the synthetic procedure. PMID:28943780

Conversion of nitrogen oxides in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures subjected to a dc corona discharge

NASA Astrophysics Data System (ADS)

Dors, Mirosław; Mizeraczyk, Jerzy

1996-10-01

This paper concerns the influence of a direct current (dc) corona discharge on production and reduction of NO, NO2 and N2O in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures. The corona discharge was generated in a needle-to-plate reactor. The positively polarized electrode consisted of 7 needles. The grounded electrode was a stainless steel plate. The gas flow rate through the reactor was varied from 28 to 110 cm3/s. The time-averaged discharge current ranged from 0 to 6 mA. It was found that in the N2:O2:CO2 mixture the corona discharge produced NO, NO2 and N2O. In the N2:O2:CO2:NO2 mixture the reduction of NO2 was between 6-56%, depending on the concentration of O2, gas flow rate and corona discharge current. The NO2 reduction was accompanied by production of NO and N2O. The results show that efficient reduction of nitrogen oxides by a corona discharge cannot be expected in the mixtures containing N2 and O2 if reducing additives are not employed.

Homoleptic diphosphacyclobutadiene complexes [M(η(4)-P2C2R2)2]x- (M = Fe, Co; x = 0, 1).

PubMed

Wolf, Robert; Ehlers, Andreas W; Khusniyarov, Marat M; Hartl, František; de Bruin, Bas; Long, Gary J; Grandjean, Fernande; Schappacher, Falko M; Pöttgen, Rainer; Slootweg, J Chris; Lutz, Martin; Spek, Anthony L; Lammertsma, Koop

2010-12-27

The preparation and comprehensive characterization of a series of homoleptic sandwich complexes containing diphosphacyclobutadiene ligands are reported. Compounds [K([18]crown-6)(thf)(2)][Fe(η(4)-P(2)C(2)tBu(2))(2)] (K1), [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)tBu(2))(2)] (K2), and [K([18]crown-6)(thf)(2)][Co(η(4)-P(2)C(2)Ad(2))(2)] (K3, Ad = adamantyl) were obtained from reactions of [K([18]crown-6)(thf)(2)][M(η(4)-C(14)H(10))(2)] (M = Fe, Co) with tBuC[triple bond]P (1, 2), or with AdC[triple bond]P (3). Neutral sandwiches [M(η(4)-P(2)C(2)tBu(2))(2)] (4: M = Fe 5: M = Co) were obtained by oxidizing 1 and 2 with [Cp(2)Fe]PF(6). Cyclic voltammetry and spectro-electrochemistry indicate that the two [M(η(4)-P(2)C(2)tBu(2))(2)](-)/[M(η(4)-P(2)C(2)tBu(2))(2)] moieties can be reversibly interconverted by one electron oxidation and reduction, respectively. Complexes 1-5 were characterized by multinuclear NMR, EPR (1 and 5), UV/Vis, and Mössbauer spectroscopies (1 and 4), mass spectrometry (4 and 5), and microanalysis (1-3). The molecular structures of 1-5 were determined by using X-ray crystallography. Essentially D(2d)-symmetric structures were found for all five complexes, which show the two 1,3-diphosphacyclobutadiene rings in a staggered orientation. Density functional theory calculations revealed the importance of covalent metal-ligand π bonding in 1-5. Possible oxidation state assignments for the metal ions are discussed.

Unsaturated Mn complex decorated hybrid thioarsenates: Syntheses, crystal structures and physical properties

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

Yue, Cheng-Yang; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002; Lei, Xiao-Wu, E-mail: xwlei_jnu@163.com

2016-03-15

The incorporation of unsaturated [Mn(1,2-dap)]{sup 2+}, [Mn(1,2-dap){sub 2}]{sup 2+}, [Mn(2,2-bipy)]{sup 2+} (1,2-dap=1,2-diaminopropane) complex cations with thioarsenate anions of [As{sup III}S{sub 3}]{sup 3−} and [As{sup V}S{sub 4}]{sup 3−} led to three new hybrid manganese thioarsenates, namely, [Mn(1,2-dap)]{sub 2}MnAs{sub 2}S{sub 6} (1), [Mn(1,2-dap){sub 2}]{[Mn(1,2-dap)]_2As_2S_8} (2) and (NH{sub 4})[Mn(2,2-bipy){sub 2}]AsS{sub 4} (3). In compound 1, the unsaturated [Mn(1,2-dap)]{sup 2+} complexes, [MnS{sub 4}]{sup 6−} tetrahedra and [As{sup III}S{sub 3}]{sup 3−} trigonal-pyramids are condensed to form the 1D [Mn(1,2-dap)]{sub 2}MnAs{sub 2}S{sub 6} chain, whereas compound 2 features 2D layer composed of [Mn(1,2-dap)]{sup 2+} and [Mn(1,2-dap){sub 2}]{sup 2+} complexes as well as [As{sup V}S{sub 4}]{sup 3−}more » tetrahedral units. For compound 3, two [As{sup V}S{sub 4}]{sup 3−} anions bridge two [Mn(2,2-bipy)]{sup 2+} complex cations into a butterfly like {[Mn(2,2-bipy)]_2As_2S_8}{sup 2−} anionic unit. Magnetic measurements indicate the ferrimagnetic behavior for compound 1 and antiferromagnetic (AF) behaviors for compounds 2–3. The UV–vis diffuse-reflectance measurements and electronic structural calculations based on density functional theory (DFT) revealed the title compounds belong to semiconductors with band gaps of 2.63, 2.21, and 1.97 eV, respectively. The narrow band-gap of compound 3 led to the efficient and stable photocatalytic degradation activity over organic pollutant than N-doped P25 under visible light irradiation. - Highlights: Three new hybrid manganese thioarsenates have been prepared and structurally characterized. These hybrid phases feature interesting magnetic and visible light responding photocatalytic properties.« less

Mix and match: templating chiral Schiff base ligands to suit the needs of the metal ion.

PubMed

Constable, Edwin C; Zhang, Guoqi; Housecroft, Catherine E; Zampese, Jennifer A

2010-06-14

One-pot reactions of 2,2'-bipyridine-6-carbaldehyde, (1S,2S)-(-)-1,2-diphenyl-1,2-diaminoethane and FeCl(2).4H(2)O or Zn(OAc)(2).2H(2)O (2 : 1 : 1) at room temperature in MeOH lead to [Fe{(S,S)-5}(2)][PF(6)]Cl or [Zn{(S,S)-5}(2)][PF(6)](2) in which (S,S)-5 contains an imidazolidine ring, produced by intramolecular cyclization. This has been confirmed with the single-crystal structure of 2{P-[Fe{(S,S)-5}(2)][PF(6)]Cl}.H(2)O. The diastereoselectivity observed in the solid state has been confirmed by NMR spectroscopy for solutions of [Fe{(S,S)-5}(2)][PF(6)]Cl and [Zn{(S,S)-5}(2)][PF(6)](2). At room temperature, a minor product competes with the formation of [Fe{(S,S)-5}(2)][PF(6)]Cl, and the preference for these complexes is switched by carrying out the reaction in MeOH at reflux. In this case the major product is M-[Fe(2){(S,S)-4}(2)][PF(6)](4) in which (S,S)-4 is the hexadentate Schiff base ligand formed by condensation of two equivalents of 2,2'-bipyridine-6-carbaldehyde with (1S,2S)-(-)-1,2-diphenyl-1,2-diaminoethane; the single-crystal structure of 4{M-[Fe(2){(S,S)-4}(2)][PF(6)](4)}.8Me(2)CO.5MeCN.3H(2)O confirms the assembly of a double helicate. When pyridine-6-carbaldehyde replaces 2,2'-bipyridine-6-carbaldehyde in the iron(II)-templated reaction with (1S,2S)-(-)-1,2-diphenyl-1,2-diaminoethane, the product is [Fe{(S,S)-7}(2)][PF(6)](2) (3 : 2 mixture of diastereoisomers in solution) in which (S,S)-7 is an asymmetrical Schiff base, formed by reaction of only one of the amine groups in (1S,2S)-(-)-1,2-diphenyl-1,2-diaminoethane. The solid state structure of P-[Fe{(S,S)-7}(2)][PF(6)](2).MeCN is presented.

Role of the ancillary ligand N,N-dimethylaminoethanol in the sensitization of Eu(III) and Tb(III) luminescence in dimeric beta-diketonates.

PubMed

Eliseeva, Svetlana V; Kotova, Oxana V; Gumy, Frédéric; Semenov, Sergey N; Kessler, Vadim G; Lepnev, Leonid S; Bünzli, Jean-Claude G; Kuzmina, Natalia P

2008-04-24

Two types of dimeric complexes [Ln2(hfa)6(mu2-O(CH2)2NHMe2)2] and [Ln(thd)2(mu2,eta2-O(CH2)2NMe2)]2 (Ln = YIII, EuIII, GdIII, TbIII, TmIII, LuIII; hfa- = hexafluoroacetylacetonato, thd- = dipivaloylmethanato) are obtained by reacting [Ln(hfa)3(H2O)2] and [Ln(thd)3], respectively, with N,N-dimethylaminoethanol in toluene and are fully characterized. X-ray single crystal analysis performed for the TbIII compounds confirms their dimeric structure. The coordination mode of N,N-dimethylaminoethanol depends on the nature of the beta-diketonate. In [Tb2(hfa)6(mu2-O(CH2)2NHMe2)2], eight-coordinate TbIII ions adopt distorted square antiprismatic coordination environments and are O-bridged by two zwitterionic N,N-dimethylaminoethanol ligands with a Tb1...Tb2 separation of 3.684(1) A. In [Tb(thd)2(mu2,eta2-O(CH2)2NMe2)]2, the N,N-dimethylaminoethanol acts as chelating-bridging O,N-donor anion and the TbIII ions are seven-coordinate; the Tb1...Tb1A separation amounts to 3.735(2) A within centrosymmetric dimers. The dimeric complexes are thermally stable up to 180 degrees C, as shown by thermogravimetric analysis, and their volatility is sufficient for quantitative sublimation under reduced pressure. The EuIII and TbIII dimers display metal-centered luminescence, particularly [Eu2(hfa)6(O(CH2)2NHMe2)2] (quantum yield Q(L)Ln = 58%) and [Tb(thd)2(O(CH2)2NMe2)]2 (32%). Consideration of energy migration paths within the dimers, based on the study of both pure and EuIII- or TbIII-doped (0.01-0.1 mol %) LuIII analogues, leads to the conclusion that both the beta-diketone and N,N-dimethylaminoethanol ligands contribute significantly to the sensitization process of the EuIII luminescence. The ancillary ligand increases considerably the luminescence of [Eu2(hfa)6(O(CH2)2NHMe2)2], compared to [Ln(hfa)3(H2O)2], through the formation of intra-ligand states while it is detrimental to TbIII luminescence in both beta-diketonates. Thin films of the most luminescent compound [Eu2(hfa)6(O(CH2)2NHMe2)2] obtained by vacuum sublimation display photophysical properties analogous to those of the solid-state sample, thus opening perspectives for applications in electroluminescent devices.

Cation Dependence of the Dimerization Enthalpy for A2 [tetracyanoethylene]2 (A=NMe4 , Mepy, NEt4 ) Possessing a Long, Multicenter Bond.

PubMed

Graham, Adora G; Fedin, Matvey V; Miller, Joel S

2017-09-12

[TCNE] .- (TCNE=tetracyanoethylene) has been isolated as D 2h π-[TCNE] 2 2- possessing a long, 2.9 Å multicenter 2-electron-4-center (2e - /4c) C-C bond, and as C 2 π-[TCNE] 2 2- possessing a longer, 3.04 Å multicenter 2e - /6c (4 C+2 N atoms) bond. Temperature-dependent UV/Vis spectroscopic measurements in 2-methyltetrahydrofuran (MeTHF) has led to the determination of the dimerization, 2[TCNE] .- ⇌π-[TCNE] 2 2- , equilibrium constants, K eq (T), [[TCNE] 2 2- ]/[[TCNE] .- ] 2 , enthalpy, ΔH, and entropy, ΔS, of dimerization for [Mepy] 2 [TCNE] 2 (Mepy=N-methylpyridinium, H 3 CNC 5 H 5 + ) possessing D 2h π-[TCNE] 2 2- and [NMe 4 ] 2 [TCNE] 2 possessing C 2 π-[TCNE] 2 2- conformations in the solid state; however, both form D 2h π-[TCNE] 2 2- in MeTHF solution. Based on ΔH=-3.6±0.1 kcal mol -1 (-15.2 kJ mol -1 ), and ΔS=-11±1 eu (-47 J mol -1  K -1 ) and ΔH=-2.4±0.2 kcal mol -1 (-10.2 kJ mol -1 ), and ΔS=-8±1 eu (-32 J mol -1  K -1 ) in MeTHF for [NMe 4 ] 2 [TCNE] 2 and [Mepy] 2 [TCNE] 2 , respectively, the calculated K eq (298 K) are 1.6 and 1.3 m -1 , respectively. The observed K eq (145 K) are 3 and 2 orders of magnitude greater for [NMe 4 ] 2 [TCNE] 2 and [Mepy] 2 [TCNE] 2 , respectively. The K eq (130 K) is 4470, 257, ≈0.8, and ≪0.1 m -1 for [NMe 4 ] 2 [TCNE] 2 , [Mepy] 2 [TCNE] 2 , [NEt 4 ] 2 [TCNE] 2 , and [N(nBu) 4 ] 2 [TCNE] 2 , respectively, decreasing with increasing cation size. At standard conditions and below ambient temperature the equilibrium favors the dimer for the NMe 4 + and Mepy + cations. From the decreasing enthalpy, NMe 4 + >Mepy + , along with the decrease in dimer formation K eq (T) as NMe 4 + >Mepy + >NEt 4 + >N(nBu) 4 + , the dimer bond energy decreases with increasing cation size in MeTHF. This is attributed to a decrease in the [A] + ⋅⋅⋅[TCNE] - attractive interactions with increasing cation size. Solid state UV/Vis spectroscopic determinations of [NMe 4 ] 2 [TCNE] 2 are reported and compared to D 2h π-[TCNE] 2 2- conformers. The feasibility and limitations of temperature-dependent electron paramagnetic resonance (EPR) measurements for the determination of K eq (T) are also discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Installation Restoration Program. Stage 3. Remedial Investigation/ Feasibility Study. Elmendorf Air Force Base, Alaska. Volume 5. Appendix G

DTIC Science & Technology

1990-05-01

Pentachloronitrobenzene ND mg/kg 2.5 S P henaceti n NO mg/kg 2- Picoline ND mg/kgI Pronamideh NO mg/kg 2.5I benzene ND mg/kg 2.5 2, 6-Di chi orophenol ND mg/kg 2.5 I...mg/kg 2.5 Pentachloronitrobenzene NO mg/kg 2.5 Phenaceti n ND mg/kg 2.5 2- Picoline ND mg/kg 2.5 Pronamide ND mg/kg 2.5 1 ,2,4,5-Tetrachloro benzene ND...Phenacetin ND mg/kg 2.5 2- Picoline ND mg/kg 2.5 Pronami de ND mg/kg 2.5 1,2,4,5-Tetrachlorobenzene ND mg/kg 2.5 2, 6-Di chi orophenol ND mg/kg 2.5 2-Methyl

Synthesis of Carboxylate Cp*Zr(IV) Species: Toward the Formation of Novel Metallocavitands.

PubMed

Daigle, Maxime; Bi, Wenhua; Légaré, Marc-André; Morin, Jean-François; Fontaine, Frédéric-Georges

2015-06-01

With the intent of generating metallocavitands isostructural to species [(CpZr)3(μ(3)-O)(μ(2)-OH)3(κO,O,μ(2)-O2C(R))3](+), the reaction of Cp*2ZrCl2 and Cp*ZrCl3 with phenylcarboxylic acids was carried out. Depending on the reaction conditions, five new complexes were obtained, which consisted of Cp*2ZrCl(κ(2)-OOCPh) (1), (Cp*ZrCl(κ(2)-OOCPh))2(μ-κ(2)-OOCPh)2 (2), [(Cp*Zr(κ(2)-OOCPh))2(μ-κ(2)-OOCPh)2(μ(2)-OH)2]·Et2O (3·Et2O), [[Cp*ZrCl2](μ-Cl)(μ-OH)(μ-O2CC6H5)[Cp*Zr

Organotin Selenide Clusters and Hybrid Capsules.

PubMed

Dehnen, Stefanie; Hanau, Katharina; Rinn, Niklas; Argentari, Mario

2018-05-22

Several compounds with unique structural motifs that have already been known from organotin sulfide chemistry, but remained unprecedented in organotin selenide chemistry so far, have been synthesized. The reaction of [(R1Sn)4Se6] (R1 = CMe2CH2C(O)Me) with N2H4·H2O/(SiMe3)2Se and with PhN2H3/(SiMe3)2Se led to the formation of [{(R2Sn)2SnSe4}2(µ-Se)2] (1) and [{(R3Sn)2SnSe4}2(µ-Se)2] (2) (R2 = CMe2CH2C(Me)NNH2, R3 = CMe2CH2C(Me)NNPhH), respectively. Addition of o-phthalaldehyde to [(R2Sn)4Se6] yielded a cluster with intramolecular bridging of the organic groups, [(R4Sn2)2Se6] (3, R4 = (CMe2CH2C(Me)NNCH)2C6H4). The introduction of organic ligands with longer chains finally allowed the isolation of inorganic-organic capsules of the type [(µ-R)3(Sn3Se4)2]X2, with R = (CMe2CH2C(Me)NNHC(O))2(CH2)4, X = [SnC3], Cl (4a, 4b) or R = CMe2CH2C(Me)NNH)2, X = [SnCl3] (5). The capsules enclose solvent molecules and/or anions as guests. All compounds were characterized via single-crystal X-ray diffraction, NMR spectroscopy and mass spectrometry. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Using Squares to Sum Squares

ERIC Educational Resources Information Center

DeTemple, Duane

2010-01-01

Purely combinatorial proofs are given for the sum of squares formula, 1[superscript 2] + 2[superscript 2] + ... + n[superscript 2] = n(n + 1) (2n + 1) / 6, and the sum of sums of squares formula, 1[superscript 2] + (1[superscript 2] + 2[superscript 2]) + ... + (1[superscript 2] + 2[superscript 2] + ... + n[superscript 2]) = n(n + 1)[superscript 2]…

Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions.

PubMed

Thuéry, Pierre; Harrowfield, Jack

2016-03-07

Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC-(CH2)n-2-COOH (H2Cn; n = 7-10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn(2+), Fe(3+), Co(2+), Ni(2+), and Cu(2+)) and 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen). In contrast to previously reported triple-stranded helicates obtained with C9(2-) and C12(2-), all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy)3][(UO2)2(C7)3]·3H2O (1), [Cu(phen)2]2[(UO2)3(C7)4(H2O)2]·2H2O (2), and [Cu(bipy)2]2[(UO2)2(C9)3] (6), in which the 3d cation was reduced in situ, are 1D ladderlike polymers displaying tetra- or hexanuclear rings, of sufficient width to encompass two counterions in 2 and 6. The three complexes [Co(phen)3][(UO2)3(C8)3(O)]·H2O (3), [Ni(phen)3][(UO2)3(C8)3(O)]·H2O (4) and [Co(phen)3][(UO2)3(C9)3(O)]·H2O (5) contain bis(μ3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply furrowed 2D assemblies. Depending on the nature of the counterion, C10(2-) gives [Ni(bipy)3][(UO2)2(C10)3]·2H2O (7), a 2D network displaying elongated decanuclear rings containing the counterions, or [Mn(phen)3][(UO2)2(C10)3]·6H2O (8), [Co(phen)3][(UO2)2(C10)3]·7H2O (9), and [Ni(phen)3][(UO2)2(C10)3]·7H2O (10), which consist of 2D assemblies with honeycomb topology; the hexanuclear rings in 8-10 are chairlike and occupied by one counterion and two uranyl groups from neighboring layers. Two complexes of the ligand with the longest chain, C12(2-), are reported. [UO2(C12)(bipy)] (11) is a neutral 1D species in which bipy chelates the uranyl ion and plays an important role in the packing through π-stacking interactions. Two polymeric units, 1D and 2D, coexist in the complex [Ni(bipy)3][(UO2)2(C12)3][UO2(C12)(H2O)2]·H2O (12); the 2D network has the honeycomb topology, but the hexanuclear rings are markedly convoluted, with local features akin to those in helicates, and the counterions are embedded in intralayer cavities. Emission spectra measured in the solid state show in most cases various degrees of quenching, with intense and well-resolved uranyl emission being observed only for complexes 2 and 11.

Halide addition/abstraction in phosphido derivatives: isolation of the thallium and silver intermediates.

PubMed

Forniés, Juan; Fortuño, Consuelo; Ibáñez, Susana; Martín, Antonio

2008-07-07

Reaction of unsaturated (44e (-) skeleton) [PdPt 2(mu-PPh 2) 2(mu-P 2Ph 4)(R F) 4] 4 with Br (-) produces the saturated (48e (-) skeleton) complex [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 5 without any M-M' bond. Attempts to eliminate Br (-) of 5 with Ag (+) in CH 2Cl 2 as a solvent gives a mixture of [(R F) 2Pt (III)(mu-PPh 2) 2Pt (III)(R F) 2] and some other unidentified products as a consequence of oxidation and partial fragmentation. However, when the reaction of 5 with Ag (+) is carried out in CH 3CN, no oxidation is observed but the elimination of Br (-) and the formation of [(R F) 2(CH 3CN)Pt(mu-PPh 2)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 6 (46e (-) skeleton), a complex with a Pt-Pd bond, takes place. It is noteworthy that the reaction of 5 with TlPF 6 in CH 2Cl 2 does not precipitate TlBr but forms the adduct [(R F) 2PtTl(mu-PPh 2)(mu-Br)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 7 with a Pt-Tl bond. Likewise, 5 reacts with [AgOClO 3(PPh 3)] in CH 2Cl 2 forming the adduct [AgPdPt 2(mu-Br)(mu-PPh 2) 2(mu-Ph 2P-PPh 2)(R F) 4(PPh 3)] 8, which contains a Pt-Ag bond. Both adducts are unstable in a CH 3CN solution, precipitating TlBr or AgBr and yielding the unsaturated 6. The treatment of [NBu 4] 2[(R F) 2Pt(mu-PPh 2) 2Pd(mu-PPh 2) 2Pt(R F) 2] in CH 3CN with I 2 (1:1 molar ratio) at 233 K yields a mixture of 4 and 6, which after recrystallization from CH 2Cl 2 is totally converted in 4. If the reaction with I 2 is carried out at room temperature, a mixture of the isomers [NBu 4][(R F) 2Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2)(mu-P 2Ph 4)Pt(R F) 2] 9 and [NBu 4][(R F)(PPh 2R F)Pt(mu-PPh 2)(mu-I)Pd(mu-PPh 2) 2Pt(R F) 2] 10 are obtained. The structures of the complexes have been established on the bases of NMR data, and the X-ray structures of 5- 8 have been studied. The relationship between the different complexes has been studied.

Hydrodeoxygenation of p -Cresol over Pt/Al 2 O 3 Catalyst Promoted by ZrO 2 , CeO 2 , and CeO 2 –ZrO 2

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

Wang, Weiyan; Wu, Kui; Liu, Pengli

2016-07-20

ZrO 2-Al 2O 3 and CeO 2-Al 2O 3 were prepared by a co-precipitation method and selected as supports for Pt catalysts. The effects of CeO 2 and ZrO 2 on the surface area and Brønsted acidity of Pt/Al 2O 3 were studied. In the hydrodeoxygenation (HDO) of p-cresol, the addition of ZrO 2 promoted the direct deoxygenation activity on Pt/ZrOO 2-Al 2O 3 via Caromatic-O bond scission without benzene ring saturation. Pt/CeOO 2-Al 2O 3 exhibited higher deoxygenation extent than Pt/Al 2O 3 due to the fact that Brønsted acid sites on the catalyst surface favored the adsorption ofmore » p-cresol. With the advantages of CeO 2 and ZrO 2 taken into consideration, CeO 2-ZrOO 2-Al 2O 3 was prepared, leading to the highest HDO activity of Pt/CeO 2-ZrOO 2-Al 2O 3. The deoxygenation extent for Pt/CeO 2-ZrOO 2-Al 2O 3 was 48.4% and 14.5% higher than that for Pt/ZrO2O 2-Al 2O 3 and Pt/CeOO 2-Al 2O 3, respectively.« less

Manganese Silylene Hydride Complexes: Synthesis and Reactivity with Ethylene to Afford Silene Hydride Complexes.

PubMed

Price, Jeffrey S; Emslie, David J H; Britten, James F

2017-05-22

Reaction of the ethylene hydride complex trans-[(dmpe) 2 MnH(C 2 H 4 )] (1) with Et 2 SiH 2 at 20 °C afforded the silylene hydride [(dmpe) 2 MnH(=SiEt 2 )] (2 a) as the trans-isomer. By contrast, reaction of 1 with Ph 2 SiH 2 at 60 °C afforded [(dmpe) 2 MnH(=SiPh 2 )] (2 b) as a mixture of the cis (major) and trans (minor) isomers, featuring a Mn-H-Si interaction in the former. The reaction to form 2 b also yielded [(dmpe) 2 MnH 2 (SiHPh 2 )] (3 b); [(dmpe) 2 MnH 2 (SiHR 2 )] (R=Et (3 a) and Ph (3 b)) were accessed cleanly by reaction of 2 a and 2 b with H 2 , and the analogous reactions with D 2 afforded [(dmpe) 2 MnD 2 (SiHR 2 )] exclusively. Both 2 a and 2 b engaged in unique reactivity with ethylene, generating the silene hydride complexes cis-[(dmpe) 2 MnH(R 2 Si=CHMe)] (R=Et (4 a), Ph (4 b)). Compounds trans-2 a, cis-2 b, 3 b, and 4 b were crystallographically characterized, and bonding in 2 a, 2 b, 4 a, and 4 b was probed computationally. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The reaction of H2O2 with NO2 and NO

NASA Technical Reports Server (NTRS)

Gray, D.; Lissi, E.; Heicklen, J.

1972-01-01

The reactions of NO and NO2 with H2O2 have been examined at 25 C. Reaction mixtures were monitored by continuously bleeding through a pinhole into a monopole mass spectrometer. NO2 was also monitored by its optical absorption in the visible part of the spectrum. Reaction mixtures containing initially 1.5 - 2.5 torr of NO2 and 0.8 - 1.4 torr of H2O2 or 1 - 12 torr of NO and 0.5 - 1.5 torr of H2O2 were studied. The H2O2 - NO reaction was complex. There was an induction period followed by a marked acceleration in reactant removal. The final products of the reaction, NO2, probably H2O, and possibly HONO2 were produced mainly after all the H2O2 was removed. The HONO intermediate was shown to disproportionate to NO2 + NO + H2O in a relatively slow first order reaction. The acceleration in H2O2 removal after the NO - H2O2 reaction is started is caused by NO2 catalysis.

12 CFR Appendix L to Part 226 - Assumed Loan Periods for Computations of Total Annual Loan Cost Rates

Code of Federal Regulations, 2011 CFR

2011-01-01

... (in years) 62 2 [11] 21 29 63 2 [10] 20 28 64 2 [10] 19 27 65 2 [9] 18 25 66 2 [9] 18 25 67 2 [9] 17 24 68 2 [8] 16 22 69 2 [8] 16 22 70 2 [8] 15 21 71 2 [7] 14 20 72 2 [7] 13 18 73 2 [7] 13 18 74 2 [6...] 8 11 82 2 [4] 8 11 83 2 [4] 7 10 84 2 [4] 7 10 85 2 [3] 6 8 86 2 [3] 6 8 87 2 [3] 6 8 88 2 [3] 5 7...

Development of a Low Cost Molded Plastic Missile/RPV Control Surface Actuator

DTIC Science & Technology

1975-10-01

Glass Fiber 3 2.1.2.2 Nylon/30% Glaso Fiber 7 2.2 Phase I Testing Of Polyimide/Glass 8 j/ Burst Testsl 11tig 2.2.2atgu TechShatset S.2. Phse Cliner oldng...Dimensional and Hard- 23 a >~ ness Change Results19 2.2.4.2.3 Weight Changes 23 2.2.5 Phase II Environmental Testing 27 II I -ii TALIO ONET TABLE OF...CONTENTS (CONT’D) SECTION PAGE 2.3 Phase I Analysis and Design 27 2.3.1 Sizing and Optimizing AR 27 2.3.2 Valve Sizing 36 2.3.3 Pistons Side Load and Rocker

Updated 2013 College of American Pathologists/American Society of Clinical Oncology (CAP/ASCO) guideline recommendations for human epidermal growth factor receptor 2 (HER2) fluorescent in situ hybridization (FISH) testing increase HER2 positive and HER2 equivocal breast cancer cases; retrospective study of HER2 FISH results of 836 invasive breast cancers.

PubMed

Singh, Kamaljeet; Tantravahi, Umadevi; Lomme, Michele M; Pasquariello, Terese; Steinhoff, Margaret; Sung, C James

2016-06-01

For dual probe HER2 FISH assay, the 2013 CAP/ASCO guideline recommendations lowered the HER2/CEP17 ratio cut off for HER2 amplification to ≥2.0 and introduced an average HER2 copy number criterion for HER2 amplification (≥6.0/cell) and HER2 equivocal categories (≥4 and <6/cell). The HER2/CEP17 equivocal category is eliminated. The aim of this study is to assess the impact of 2013 HER2 FISH testing guideline recommendations update on the assignment of HER2 status with dual probe HER2 FISH assay. Dual probe HER2 FISH assay results on breast cancers from 09/2009 to 07/2015 that underwent reflex HER2 FISH testing after equivocal HER2 (2+) immunohistochemistry (IHC) were reviewed. HER2 copy number, CEP17 signals, and HER2/CEP ratios were noted. HER2 status was assigned as HER2 negative (HER2-), HER2 equivocal (HER2e), and HER2 amplified (HER2+) by applying both 2007 and 2013 CAP/ASCO HER2 FISH guideline recommendations and results were compared. New guidelines reclassified HER2 FISH status in a significant proportion of cases (8.3 %, 69/836; p = .021). There were 22 (2.6 %) more HER2+, 17 (2.1 %) more HER2e, and 39 (4.1 %) fewer HER2- tumors. Change of HER2 status correlated significantly with ≥3 CEP17 signals (38 vs. 2 %; p < .001). The 2013 CAP/ASCO guideline recommendations for HER2 FISH testing by dual probe assay increased the HER2 amplified and HER2 equivocal tumors. Increase in HER2 equivocal tumors would potentially increase the frequency of repeat HER2 testing. Tumors with ≥3 CEP17 signals, so-called chromosome 17 polysomy, are more likely to be impacted and classified as HER2 equivocal.

Enhancement of luminescence properties in Er3+ doped TeO2-Na2O-PbX (X=O and F) ternary glasses.

PubMed

Kumar, Kaushal; Rai, S B; Rai, D K

2007-04-01

An enhancement of luminescence properties in Er3+ doped ternary glasses is observed on the addition of PbO/PbF2. The infrared to visible upconversion emission bands are observed at 410, 525, 550 and 658 nm, due to the 2H9/2-->4I15/2, 2H11/2-->4I15/2, 4S3/2-->4I15/2, 4F9/2-->4I15/2 transitions respectively, on excitation with 797 nm laser line. A detailed study reveals that the 2H9/2-->4I15/2 transition arises due to three step upconversion process while other transitions arise due to two step absorption. On excitation with 532 nm radiation, ultraviolet and violet upconversion bands centered at 380, 404, 410 and 475 nm wavelengths are observed along with one photon luminescence bands at 525, 550, 658 and 843 nm wavelengths. These bands are found due to the 4G11/2-->4I15/2, 2P3/2-->4I13/2, 2H9/2-->4I15/2, 2P3/2-->4I11/2, 2H11/2-->4I15/2, 4S3/2-->4I15/2, 4F9/2-->4I15/2 and 4S3/2-->4I13/2 transitions, respectively. Though incorporation of PbO and PbF2 both enhances fluorescence intensities however, PbF2 content has an important influence on upconversion luminescence emission. The incorporation of PbF2 enhances the red emission (658 nm) intensity by 1.5 times and the violet emission (410 nm) intensity by 2.0 times. A concentration dependence study of fluorescence reveals the rapid increase in the red (4F9/2-->4I15/2) emission intensity relative to the green (4S3/2-->4I15/2) emission with increase in the Er3+ ion concentration. This behaviour has been explained in terms of an energy transfer by relaxation between excited ions.

Antiferromagnetism in semiconducting SrMn2Sb2 and BaMn2Sb2 single crystals

NASA Astrophysics Data System (ADS)

Sangeetha, N. S.; Smetana, V.; Mudring, A.-V.; Johnston, D. C.

2018-01-01

Crystals of SrMn2Sb2 and BaMn2Sb2 were grown using Sn flux and characterized by powder and single-crystal x-ray diffraction, respectively, and by single-crystal electrical resistivity ρ , heat capacity Cp, and magnetic susceptibility χ measurements versus temperature T , and magnetization versus field M (H ) isotherm measurements. SrMn2Sb2 adopts the trigonal CaAl2Si2 -type structure, whereas BaMn2Sb2 crystallizes in the tetragonal ThCr2Si2 -type structure. The ρ (T ) data indicate semiconducting behaviors for both compounds with activation energies of ≳0.35 eV for SrMn2Sb2 and 0.16 eV for BaMn2Sb2 . The χ (T ) and Cp(T ) data reveal antiferromagnetic (AFM) ordering at TN = 110 K for SrMn2Sb2 and 450 K for BaMn2Sb2 . The anisotropic χ (T ≤TN) data also show that the ordered moments in SrMn2Sb2 are aligned in the hexagonal a b plane, whereas the ordered moments in BaMn2Sb2 are aligned collinearly along the tetragonal c axis. The a b -plane M (H ) data for SrMn2Sb2 exhibit a continuous metamagnetic transition at low fields 0

40 CFR 180.257 - Chloroneb; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

..., sugar, tops 0.2 Cowpea, forage 2.0 Cowpea, hay 2.0 Cattle, fat 0.2 Cattle, meat 0.2 Cattle, meat byproducts 0.2 Cotton, gin byproducts 1.0 Cotton, undelinted seed 0.2 Goat, fat 0.2 Goat, meat 0.2 Goat, meat byproducts 0.2 Hog, fat 0.2 Hog, meat 0.2 Hog, meat byproducts 0.2 Horse, fat 0.2 Horse, meat 0.2 Horse, meat...

40 CFR 180.364 - Glyphosate; tolerances for residues.

Code of Federal Regulations, 2013 CFR

2013-07-01

..., globe 0.2 Asparagus 0.5 Atemoya 0.2 Avocado 0.2 Bamboo, shoots 0.2 Banana 0.2 Barley, bran 30 Beet... Galangal, roots 0.2 Ginger, white, flower 0.2 Gourd, buffalo, seed 0.1 Governor's plum 0.2 Gow kee, leaves... Longan 0.2 Lychee 0.2 Mamey apple 0.2 Mango 0.2 Mangosteen 0.2 Marmaladebox 0.2 Mioga, flower 0.2 Noni 0...

40 CFR 180.257 - Chloroneb; tolerances for residues.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., sugar, tops 0.2 Cowpea, forage 2.0 Cowpea, hay 2.0 Cattle, fat 0.2 Cattle, meat 0.2 Cattle, meat byproducts 0.2 Cotton, gin byproducts 1.0 Cotton, undelinted seed 0.2 Goat, fat 0.2 Goat, meat 0.2 Goat, meat byproducts 0.2 Hog, fat 0.2 Hog, meat 0.2 Hog, meat byproducts 0.2 Horse, fat 0.2 Horse, meat 0.2 Horse, meat...

Air Traffic Control/Active Beacon Collision Avoidance System Knoxville Simulation.

DTIC Science & Technology

1980-05-01

I’s & AIRCRAFT 2’s POSITION VECTOR. ENTER (X1l,Y,Zl,,ZI,2) & (X2,Y2,Z2,X2,Y2,i2) As x = XI-X2 Y= Yl-Y2 VRX =Xi-X2 VRY = YI-Y2 MD2 -(4X*\\’RY - AY*vHJ...2 VRX 2 + vRy 2 M SQRT(MD2) YES MD> MDCM FILTER + OR - COMAND IF FITER VAVE TITRj-SITnLD PERFORMANCE LEATl. VALIE 3 o . U mi 5 3.0 1in t ;u~i:F-2

Design and syntheses of hybrid metal–organic materials based on K{sub 3}[M(C{sub 2}O{sub 4}){sub 3}]·3H{sub 2}O [M(III)=Fe, Al, Cr] metallotectons

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

Sun, Yayong; Zong, Yingxia; Ma, Haoran

2016-05-15

By using K{sub 3}[M(C{sub 2}O{sub 4}){sub 3}]·3H{sub 2}O [M(III)=Fe, Al, Cr] (C{sub 2}O{sub 4}{sup 2−}=oxalate) metallotectons as the starting material, we have synthesized eight novel complexes with formulas [{Fe(C_2O_4)_2(H_2O)_2}{sub 2}]·(H–L{sub 1}){sub 2}·H{sub 2}O 1, [Fe(C{sub 2}O{sub 4})Cl{sub 2}]·(H{sub 2}–L{sub 2}){sub 0.5}·(L{sub 2}){sub 0.5}·H{sub 2}O 2, [{Fe(C_2O_4)_1_._5Cl_2}{sub 2}]·(H–L{sub 3}){sub 4}3, [Fe{sub 2}(C{sub 2}O{sub 4})Cl{sub 8}]·(H{sub 2}–L{sub 4}){sub 2}·2H{sub 2}O 4, K[Al(C{sub 2}O{sub 4}){sub 3}]·(H{sub 2}–L{sub 5})·2H{sub 2}O 5, K[Al(C{sub 2}O{sub 4}){sub 3}]·(H–L{sub 6}){sub 2}·2H{sub 2}O 6, K[Cr(C{sub 2}O{sub 4}){sub 3}]·2H{sub 2}O 7, Na[Fe(C{sub 2}O{sub 4}){sub 3}]·(H–L{sub 6}){sub 2}·2H{sub 2}O 8 (with L{sub 1}=4-dimethylaminopyridine, L{sub 2}=2,3,5,6-tetramethylpyrazine, L{sub 3}=2-aminobenzimidazole, L{sub 4}=1,4-bis-(1H-imidazol-1-yl)benzene, L{sub 5}=1,4-bis((2-methylimidazol-1-yl)methyl)benzene,more » L{sub 6}=2-methylbenzimidazole). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra and thermogravimetric analyses. Compound 3 is a 2D H-bonded supramolecular architecture. Others are 3D supramolecular structures. Compound 1 shows a [Fe(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O){sub 2}]{sup −} unit and 3D antionic H-bonded framework. Compound 2 features a [Fe(C{sub 2}O{sub 4})Cl{sub 2}]{sup -} anion and 1D iron-oxalate-iron chain. Compound 3 features a [Fe{sub 2}(C{sub 2}O{sub 4}){sub 3}Cl{sub 4}]{sup 4−} unit. Compound 4 features distinct [Fe{sub 2}(C{sub 2}O{sub 4})Cl{sub 8}]{sup 4−} units, which are mutual linked by water molecules to generated a 2D H-bonded network. Compound 5 features infinite ladder-like chains constructed by [Al(C{sub 2}O{sub 4}){sub 3}]{sup 3−} units and K{sup +} cations. The 1D chains are further extended into 3D antionic H-bonded framework through O–H···O H-bonds. Compounds 6–8 show 2D [KAl(C{sub 2}O{sub 4}){sub 3}]{sup 2−} layer, [KCr(C{sub 2}O{sub 4}){sub 3}]{sup 2−} layer and [NaFe(C{sub 2}O{sub 4}){sub 3}]{sup 2−} layer, respectively. - Graphical abstract: We report here eight novel complexes by using [M(C{sub 2}O{sub 4}){sub 3}]{sup 3−} [M(III)=Fe, Al, Cr] metallotectons as the starting materials. These complexes show supramolecular architectures bonded by charge-assisted hydrogen bonds.« less

Hydrogen peroxide formation during iron deposition in horse spleen ferritin using O2 as an oxidant.

PubMed

Lindsay, S; Brosnahan, D; Watt, G D

2001-03-20

The reaction of Fe2+ with O2 in the presence of horse spleen ferritin (HoSF) results in deposition of FeOH3 into the hollow interior of HoSF. This reaction was examined at low Fe2+/HoSF ratios (5-100) under saturating air at pH 6.5-8.0 to determine if H2O2 is a product of the iron deposition reaction. Three methods specific for H2O2 detection were used to assess H2O2 formation: (1) a fluorometric method with emission at 590 nm, (2) an optical absorbance method based on the reaction H2O2 + 3I- + 2H+ = I3- + 2H2O monitored at 340 nm for I3- formation, and (3) a differential pulsed electrochemical method that measures O2 and H2O2 concentrations simultaneously. Detection limits of 0.25, 2.5, and 5.0 microM H2O2 were determined for the three methods, respectively. Under constant air-saturation conditions (20% O2) and for a 5-100 Fe2+/HoSF ratio, Fe2+ was oxidized and the resulting Fe3+ was deposited within HoSF but no H2O2 was detected as predicted by the reaction 2Fe2+ + O2 + 6H2O = 2Fe(OH)3 + H2O2 + 4H+. Two other sets of conditions were also examined: one with excess but nonsaturating O2 and another with limiting O2. No H2O2 was detected in either case. The absence of H2O2 formation under these same conditions was confirmed by microcoulometric measurements. Taken together, the results show that under low iron loading conditions (5-100 Fe2+/HoSF ratio), H2O2 is not produced during iron deposition into HoSF using O2 as an oxidant. This conclusion is inconsistent with previous, carefully conducted stoichiometric and kinetic measurements [Xu, B., and Chasteen, N. D. (1991) J. Biol. Chem. 266, 19965], predicting that H2O2 is a quantitative product of the iron deposition reaction with O2 as an oxidant, even though it was not directly detected. Possible explanations for these conflicting results are considered.

New Rh 2 (II,II) Architecture for the Catalytic Reduction of H +

DOE PAGES

White, Travis A.; Witt, Suzanne E.; Li, Zhanyong; ...

2015-09-25

Formamidinate-bridged Rh 2 II,II complexes containing diimine ligands of the formula cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ (Rh 2-NN 2), where DTolF = p-ditolylformamidinate and NN = dppn (benzo[i]dipyrido[3,2-a:2',3'-h]quinoxaline), dppz (dipyrido[3,2-a:2',3'-c]phenazine), and phen (1,10-phenanthroline), electrocatalytically reduce H + to H 2 in DMF solutions containing CH 3COOH at a glassy carbon electrode. Cathodic scans in the absence of acid display a Rh III,II/II,II reduction at -0.90 V vs Fc +/Fc followed by NN 0/– reduction at -1.13, -1.36, and -1.65 V for Rh 2-dppn 2, Rh 2-dppz 2, and Rh 2-phen 2, respectively. Upon the addition of acid, Rh 2-dppnmore » 2 and Rh 2-dppz 2 undergo reduction–protonation–reduction at each pyrazine-containing NN ligand prior to the Rh 2 II,II/II,I reduction. The Rh 2 II,I species is thus protonated at one of the metal centers, resulting in the formation of the corresponding Rh 2 II,III-hydride. In the case of Rh 2-phen 2, the reduction of the phen ligand is followed by intramolecular electron transfer to the Rh 2 II,II core in the presence of protons to form a Rh 2 II,III-hydride species. Further reduction and protonation at the Rh 2 core for all three complexes rapidly catalyzes H 2 formation with varied calculated turnover frequencies (TOF) and overpotential values (η): 2.6 × 10 4 s –1 and 0.56 V for Rh 2-dppn, 2.8 × 10 4 s –1 and 0.50 V for Rh 2-dppz 2, and 5.9 × 10 4 s –1 and 0.64 V for Rh 2-phen 2. Bulk electrolysis confirmed H 2 formation, and further CH 3COOH addition regenerates H 2 production, attesting to the robust nature of the architecture. The cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ architecture benefits by combining electron-rich formamidinate bridges, a redox-active Rh 2 II,II core, and electron-accepting NN diimine ligands to allow for the electrocatalysis of H + substrate to H 2 fuel.« less

Spectroscopy of berylliumlike xenon ions using dielectronic recombination

NASA Astrophysics Data System (ADS)

Bernhardt, D.; Brandau, C.; Harman, Z.; Kozhuharov, C.; Böhm, S.; Bosch, F.; Fritzsche, S.; Jacobi, J.; Kieslich, S.; Knopp, H.; Nolden, F.; Shi, W.; Stachura, Z.; Steck, M.; Stöhlker, Th; Schippers, S.; Müller, A.

2015-07-01

Be-like 136X{{e}50+} ions have been investigated employing the resonant electron-ion collision process of dielectronic recombination (DR) as a spectroscopic tool. The experiments were performed at the experimental storage ring in Darmstadt, Germany, using its electron cooler as a target for free electrons. DR Rydberg resonance series 2{{s}2}+{{e}-}\\to 2s2{{p}{{j\\prime }}}n{{l}j} for the associated intra-L-shell transitions 2{{s}2}{{ }1}{{S}0}-2s2{{p}1/2}{{ }3}{{P}1},2{{s}2}{{ }1}{{S}0}-2s2{{p}3/2}{{ }3}{{P}2} and 2{{s}2}{{ }1}{{S}0}-2s2{{p}3/2}{{ }1}{{P}1} were observed with high resolution. In addition to these excitations from the ground state we determined resonances associated with excitations 2s2{{p}1/2}{{ }3}{{P}0}\\to 2{{p}1/2}2{{p}3/2}{{ }3}{{P}1} of ions initially in the metastable 2s2{{p}1/2}{{ }3}{{P}0} state. The corresponding excitation energies were determined to be E{{(}1}{{S}0}\\to {{ }3}{{P}1})=127.269(46) eV, E{{(}1}{{S}0}\\to {{ }3}{{P}2})=469.474(81) eV and E{{(}1}{{S}0}\\to {{ }1}{{P}1})=532.801(16) eV, and E{{(}3}{{P}0}\\to 2{{p}1/2}2{{p}3/2}{{ }3}{{P}1})=533.733(22) eV. These excitation energies are compared with previous measurements and with recent state-of-the-art atomic structure calculations.

Delivering Transmembrane Peptide Complexes to the Gas Phase Using Nanodiscs and Electrospray Ionization

NASA Astrophysics Data System (ADS)

Li, Jun; Richards, Michele R.; Kitova, Elena N.; Klassen, John S.

2017-10-01

The gas-phase conformations of dimers of the channel-forming membrane peptide gramicidin A (GA), produced from isobutanol or aqueous solutions of GA-containing nanodiscs (NDs), are investigated using electrospray ionization-ion mobility separation-mass spectrometry (ESI-IMS-MS) and molecular dynamics (MD) simulations. The IMS arrival times measured for (2GA + 2Na)2+ ions from isobutanol reveal three different conformations, with collision cross-sections (Ω) of 683 Å2 (conformation 1, C1), 708 Å2 (C2), and 737 Å2 (C3). The addition of NH4CH3CO2 produced (2GA + 2Na)2+ and (2GA + H + Na)2+ ions, with Ω similar to those of C1, C2, and C3, as well as (2GA + 2H)2+, (2GA + 2NH4)2+, and (2GA + H + NH4)2+ ions, which adopt a single conformation with a Ω similar to that of C2. These results suggest that the nature of the charging agents, imparted by the ESI process, can influence dimer conformation in the gas phase. Notably, the POPC NDs produced exclusively (2GA + 2NH4)2+ dimer ions; the DMPC NDs produced both (2GA + 2H)2+ and (2GA + 2NH4)2+ dimer ions. While the Ω of (2GA + 2H)2+ is similar to that of C2, the (2GA + 2NH4)2+ ions from NDs adopt a more compact structure, with a Ω of 656 Å2. It is proposed that this compact structure corresponds to the ion conducting single stranded head-to-head helical GA dimer. These findings highlight the potential of NDs, combined with ESI, for transferring transmembrane peptide complexes directly from lipid bilayers to the gas phase. [Figure not available: see fulltext.

A set of new transition metal-based coordination complexes dependent upon Hpztza ligand (Hpztza=2-(5-(pyrazin-2-yl)-2H-tetrazol-2-yl) acetic acid)

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

Yang Jie; Shen Lei; Yang Gaowen, E-mail: ygwsx@126.com

2012-02-15

Reaction of MCl{sub 2}{center_dot}4H{sub 2}O (M=Zn, Cd, Mn, Co, Ni) with 2-(5-(pyrazin-2-yl)-2H-tetrazol-2-yl) acetic acid (Hpztza) yielded a set of new M(II)/pztza complexes, [Cd(pztza){sub 2}(H{sub 2}O){sub 6}]{center_dot}3H{sub 2}O{center_dot}(Hpztza) (1), [M(pztza){sub 2}(H{sub 2}O){sub 2}; M=Cd(2), Zn(7), Mn(9)], [Cd(pztza){sub 2}]{center_dot}2(CH{sub 3}OH) (3), [Co(pztza){sub 2}(H{sub 2}O){sub 2}]{center_dot}6H{sub 2}O (4), [Co(pztza)(H{sub 2}O)Cl] (6) and [M(pztza){sub 2}(H{sub 2}O){sub 2}]{center_dot}2H{sub 2}O [M=Co(5), Zn(8), Ni(10)]. These compounds were structurally characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 featured a mononuclear structure, complexes 4, 5, 7, 8, 10 showed 1D chains and complexes 2, 3, 6, 9 displayed 2D layer structures. Furthermore, the luminescence propertiesmore » of 1-10 were investigated at room temperature in the solid state. - Graphical abstract: Ten new coordination polymers with 2-(5-(pyrazin-2-yl)-2H-tetrazol-2-yl) acetic acid (Hpztza) ligand have been synthesized and their structures have been characterized. All of the complexes show photoluminescence at room temperature. Highlights: Black-Right-Pointing-Pointer Ten novel transition metal-based coordination complexes with 2-(5-(pyrazin-2-yl)-2H-tetrazol-2-yl) acetic acid (Hpztza) are reported. Black-Right-Pointing-Pointer Complexes 1-10 are described as mononuclear structure, 1D and 2D frameworks with diverse architecture. Black-Right-Pointing-Pointer Six coordination complexes show emission at room temperature in the solid state.« less

Studies of a series of [Ni(P(R)2N(Ph)2)2(CH3CN)]2+ complexes as electrocatalysts for H2 production: substituent variation at the phosphorus atom of the P2N2 ligand.

PubMed

Kilgore, Uriah J; Stewart, Michael P; Helm, Monte L; Dougherty, William G; Kassel, W Scott; DuBois, Mary Rakowski; DuBois, Daniel L; Bullock, R Morris

2011-11-07

A series of [Ni(P(R)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) complexes containing the cyclic diphosphine ligands [P(R)(2)N(Ph)(2) = 1,5-diaza-3,7-diphosphacyclooctane; R = benzyl (Bn), n-butyl (n-Bu), 2-phenylethyl (PE), 2,4,4-trimethylpentyl (TP), and cyclohexyl (Cy)] have been synthesized and characterized. X-ray diffraction studies reveal that the cations of [Ni(P(Bn)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) and [Ni(P(n-Bu)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) have distorted trigonal bipyramidal geometries. The Ni(0) complex [Ni(P(Bn)(2)N(Ph)(2))(2)] was also synthesized and characterized by X-ray diffraction studies and shown to have a distorted tetrahedral structure. These complexes, with the exception of [Ni(P(Cy)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2), all exhibit reversible electron transfer processes for both the Ni(II/I) and Ni(I/0) couples and are electrocatalysts for the production of H(2) in acidic acetonitrile solutions. The heterolytic cleavage of H(2) by [Ni(P(R)(2)N(Ph)(2))(2)(CH(3)CN)](BF(4))(2) complexes in the presence of p-anisidine or p-bromoaniline was used to determine the hydride donor abilities of the corresponding [HNi(P(R)(2)N(Ph)(2))(2)](BF(4)) complexes. However, for the catalysts with the most bulky R groups, the turnover frequencies do not parallel the driving force for elimination of H(2), suggesting that steric interactions between the alkyl substituents on phosphorus and the nitrogen atom of the pendant amines play an important role in determining the overall catalytic rate. © 2011 American Chemical Society

Antiferromagnetism in semiconducting SrMn 2 Sb 2 and BaMn 2 Sb 2 single crystals

DOE PAGES

Sangeetha, N. S.; Smetana, V.; Mudring, A. -V.; ...

2018-01-03

Here, crystals of SrMn 2Sb 2 and BaMn 2Sb 2 were grown using Sn flux and characterized by powder and single-crystal x-ray diffraction, respectively, and by single-crystal electrical resistivity ρ, heat capacity C p, and magnetic susceptibility χ measurements versus temperature T, and magnetization versus field M(H) isotherm measurements. SrMn 2Sb 2 adopts the trigonal CaAl 2Si 2-type structure, whereas BaMn 2Sb 2 crystallizes in the tetragonal ThCr 2Si 2-type structure. The ρ(T) data indicate semiconducting behaviors for both compounds with activation energies of ≳0.35 eV for SrMn 2Sb 2 and 0.16 eV for BaMn 2Sb 2. The χ(T) andmore » C p(T) data reveal antiferromagnetic (AFM) ordering at T N = 110 K for SrMn 2Sb 2 and 450 K for BaMn 2Sb 2. The anisotropic χ(T≤T N) data also show that the ordered moments in SrMn 2Sb 2 are aligned in the hexagonal ab plane, whereas the ordered moments in BaMn 2Sb 2 are aligned collinearly along the tetragonal c axis. The ab-plane M(H) data for SrMn 2Sb 2 exhibit a continuous metamagnetic transition at low fields 02Sb 2 exhibits no metamagnetic transitions up to 5.5 T. The χ(T) and C p(T) data for both SrMn 2Sb 2 and BaMn 2Sb 2 indicate strong dynamic short-range AFM correlations above their respective T N up to at least 900 K within a local-moment picture, corresponding to quasi-two-dimensional magnetic behavior. The present results and a survey of the literature for Mn pnictides with the CaAl 2Si 2 and ThCr 2Si 2 crystal structures show that the T N values for the CaAl 2Si 2-type compounds are much smaller than those for the ThCr 2Si 2-type materials.« less

Synthesis and characterization of the divalent samarium Zintl-phases SmMg 2Bi 2 and SmMg 2Sb 2

DOE PAGES

Ramirez, D.; Gallagher, A.; Baumbach, R.; ...

2015-08-29

Here, single crystals of LnMg 2Bi 2 (Ln = Yb, Eu, Sm) and SmMg 2Sb 2 were synthesized using Mg-Bi metal and Mg-Sb metal fluxes, respectively. The crystal structures are of the CaAl 2Si 2 type with space group P3 m1 (#164, Z = 1): SmMg 2Bi 2 ( a = 4.7745(1)Å, c = 7.8490(2)Å), EuMg 2Bi 2 ( a = 4.7702(1)Å, c = 7.8457(2) Å), YbMg 2Bi 2 ( a = 4.7317(2)Å, c = 7.6524(3) Å), and SmMg 2Sb 2 ( a = 4.6861(1) Å, c = 7.7192(2) Å). Heat capacity, electrical transport, and magnetization of all bismuth containingmore » phases were measured. The materials behave as “poor metals” with resistivity between 2 and 10 mΩ·cm. Temperature independent Van Vleck paramagnetism is observed in SmMg 2Bi 2 indicative of divalent samarium (Sm 2+) ions.« less

Mn2+ concentration manipulated red emission in BaMg2Si2O7:Eu2+,Mn2+

NASA Astrophysics Data System (ADS)

Ye, Song; Zhang, Jiahua; Zhang, Xia; Lu, Shaozhe; Ren, Xinguang; Wang, Xiaojun

2007-02-01

The luminescent properties of concentration dependence are reported in BaMg2Si2O7:Eu2+,Mn2+ red phosphor. It is observed that the broad red emission of Mn2+ consists of two bands, located at 620 and 675 nm, respectively, which are attributed to two different Mn2+ centers [Mn2+(I) and Mn2+(II)] substituting for two nonidentical Mg2+ sites [Mg2+(I) and Mg2+(II)] in the host. It is also found that the relative emission intensity of the Mn2+(II) to the Mn2+(I) increases with increasing Mn2+ concentration, leading to a red-shift of the overall emission. A detail analysis on the energy transfer from Eu2+ to the two Mn2+ centers is presented, which indicates that the number ratio of Mn2+(II) to Mn2+(I) increases with increasing Mn2+ concentration. This result is interpreted by the preferential formation of Mn2+(I) substituting for Mg2+(I) site. Based on energy transfer, the emission intensity ratios of Mn2+(I) to Eu2+ and Mn2+(II) to Eu2+, which is Mn2+ concentration dependent, are calculated using related fluorescence lifetimes. The calculated results are in good agreement with that obtained experimentally in the emission spectra.

Activation of SO2 with [(η(5) -C5 Me5 )2 Ln(THF)2 ] (Ln=Eu, Yb) leading to dithionite and sulfinate complexes.

PubMed

Klementyeva, Svetlana V; Gamer, Michael T; Schmidt, Anna-Corina; Meyer, Karsten; Konchenko, Sergey N; Roesky, Peter W

2014-10-13

The reaction of decamethylytterbocene [(η(5) -C5 Me5 )2 Yb(THF)2 ] with SO2 at low temperature gave two new compounds, namely, the Yb(III) dithionite/sulfinate complex [{(η(5) -C5 Me5 )2 Yb(μ3 ,1κ(2) O(1,3) ,2κ(3) O(2,2',4) -S2 O4 )}2 {(η(5) -C5 Me5 )Yb(μ,1κO,2κO'-C5 Me5 SO2 )}2 ] (1) and the Yb(III) dithionite complex [{(η(5) -C5 Me5 )2 Yb}2 (μ,1κ(2) O(1,3) ,2κ(2) O(2,4) -S2 O4 )] (2). After extraction of 1, the mixture was heated to give the dinuclear tetrasulfinate complex [{(η(5) -C5 Me5 )Yb}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 a). In contrast, from the reaction of [(η(5) -C5 Me5 )2 Eu(THF)2 ] with SO2 only the tetrasulfinate complex [{(η(5) -C5 Me5 )Eu}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 b) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO2 molecules to form the dithionite anion S2 O4 (2-) ; and 2) nucleophilic attack of one metallocene C5 Me5 ligand on the sulfur atom of SO2 . The compounds presented are the first dithionite and sulfinate complexes of the f-elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NO and H2O2 contribute to SO2 toxicity via Ca2+ signaling in Vicia faba guard cells.

PubMed

Yi, Min; Bai, Heli; Xue, Meizhao; Yi, Huilan

2017-04-01

NO and H 2 O 2 have been implicated as important signals in biotic and abiotic stress responses of plants to the environment. Previously, we have shown that SO 2 exposure increased the levels of NO and H 2 O 2 in plant cells. We hypothesize that, as signaling molecules, NO and H 2 O 2 mediate SO 2 -caused toxicity. In this paper, we show that SO 2 hydrates caused guard cell death in a concentration-dependent manner in the concentration range of 0.25 to 6 mmol L -1 , which was associated with elevation of intracellular NO, H 2 O 2 , and Ca 2+ levels in Vicia faba guard cells. NO donor SNP enhanced SO 2 toxicity, while NO scavenger c-PTIO and NO synthesis inhibitors L-NAME and tungstate significantly prevented SO 2 toxicity. ROS scavenger ascorbic acid (AsA) and catalase (CAT), Ca 2+ chelating agent EGTA, and Ca 2+ channel inhibitor LaCl 3 also markedly blocked SO 2 toxicity. In addition, both c-PTIO and AsA could completely block SO 2 -induced elevation of intracellular Ca 2+ level. Moreover, c-PTIO efficiently blocked SO 2 -induced H 2 O 2 elevation, and AsA significantly blocked SO 2 -induced NO elevation. These results indicate that extra NO and H 2 O 2 are produced and accumulated in SO 2 -treated guard cells, which further activate Ca 2+ signaling to mediate SO 2 toxicity. Our findings suggest that both NO and H 2 O 2 contribute to SO 2 toxicity via Ca 2+ signaling.

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

White, Travis A.; Witt, Suzanne E.; Li, Zhanyong

Formamidinate-bridged Rh 2 II,II complexes containing diimine ligands of the formula cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ (Rh 2-NN 2), where DTolF = p-ditolylformamidinate and NN = dppn (benzo[i]dipyrido[3,2-a:2',3'-h]quinoxaline), dppz (dipyrido[3,2-a:2',3'-c]phenazine), and phen (1,10-phenanthroline), electrocatalytically reduce H + to H 2 in DMF solutions containing CH 3COOH at a glassy carbon electrode. Cathodic scans in the absence of acid display a Rh III,II/II,II reduction at -0.90 V vs Fc +/Fc followed by NN 0/– reduction at -1.13, -1.36, and -1.65 V for Rh 2-dppn 2, Rh 2-dppz 2, and Rh 2-phen 2, respectively. Upon the addition of acid, Rh 2-dppnmore » 2 and Rh 2-dppz 2 undergo reduction–protonation–reduction at each pyrazine-containing NN ligand prior to the Rh 2 II,II/II,I reduction. The Rh 2 II,I species is thus protonated at one of the metal centers, resulting in the formation of the corresponding Rh 2 II,III-hydride. In the case of Rh 2-phen 2, the reduction of the phen ligand is followed by intramolecular electron transfer to the Rh 2 II,II core in the presence of protons to form a Rh 2 II,III-hydride species. Further reduction and protonation at the Rh 2 core for all three complexes rapidly catalyzes H 2 formation with varied calculated turnover frequencies (TOF) and overpotential values (η): 2.6 × 10 4 s –1 and 0.56 V for Rh 2-dppn, 2.8 × 10 4 s –1 and 0.50 V for Rh 2-dppz 2, and 5.9 × 10 4 s –1 and 0.64 V for Rh 2-phen 2. Bulk electrolysis confirmed H 2 formation, and further CH 3COOH addition regenerates H 2 production, attesting to the robust nature of the architecture. The cis-[Rh 2 II,II(μ-DTolF) 2(NN) 2] 2+ architecture benefits by combining electron-rich formamidinate bridges, a redox-active Rh 2 II,II core, and electron-accepting NN diimine ligands to allow for the electrocatalysis of H + substrate to H 2 fuel.« less

Synthesis and reactivity of bis(tetramethylcyclopentadienyl) yttrium metallocenes including the reduction of Me(3)SiN(3) to [(Me(3)Si)(2)N](-) with [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-N(2)).

PubMed

Lorenz, Sara E; Schmiege, Benjamin M; Lee, David S; Ziller, Joseph W; Evans, William J

2010-07-19

The metallocene precursors needed to provide the tetramethylcyclopentadienyl yttrium complexes (C(5)Me(4)H)(3)Y, [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-N(2)), and [(C(5)Me(4)H)(2)Y(mu-H)](2) for reactivity studies have been synthesized and fully characterized, and their reaction chemistry has led to an unexpected conversion of an azide to an amide. (C(5)Me(4)H)(2)Y(mu-Cl)(2)K(THF)(x), 1, synthesized from YCl(3) and KC(5)Me(4)H reacts with allylmagnesium chloride to make (C(5)Me(4)H)(2)Y(eta(3)-C(3)H(5)), 2, which is converted to [(C(5)Me(4)H)(2)Y][(mu-Ph)(2)BPh(2)], 3, with [Et(3)NH][BPh(4)]. Complex 3 reacts with KC(5)Me(4)H to form (C(5)Me(4)H)(3)Y, 4. The reduced dinitrogen complex, [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-N(2)), 5, can be synthesized from either [(C(5)Me(4)H)(2)Y](2)[(mu-Ph)(2)BPh(2)], 3, or (C(5)Me(4)H)(3)Y, 4, with potassium graphite under a dinitrogen atmosphere. The (15)N labeled analogue, [(C(5)Me(4)H)(2)Y(THF)](2)(mu-eta(2):eta(2)-(15)N(2)), 5-(15)N, has also been prepared, and the (15)N NMR data have been compared to previously characterized reduced dinitrogen complexes. Complex 2 reacts with H(2) to form the corresponding hydride, [(C(5)Me(4)H)(2)Y(mu-H)](2), 6. Complex 5 displays similar reactivity to that of the analogous [(C(5)Me(4)H)(2)Ln(THF)](2)(mu-eta(2):eta(2)-N(2)) complexes (Ln = La, Lu), with substrates such as phenazine, anthracene, and CO(2). In addition, 5 reduces Me(3)SiN(3) to form (C(5)Me(4)H)(2)Y[N(SiMe(3))(2)], 7.

Synthesis and structure of tetranuclear orthometallated Pd(II) complexes derived from bis-iminophosphoranes.

PubMed

Bielsa, Raquel; Navarro, Rafael; Soler, Tatiana; Urriolabeitia, Esteban P

2008-04-07

The reaction of Pd(OAc)2 with bis-iminophosphoranes Ph3P=NCH2CH2CH2N=PPh3 (1a), [C6H4(C(O)N=PPh3)2-1,3] (1b) and [C6H4(C(O)N=PPh3)2-1,2] (1c), gives the orthopalladated tetranuclear complexes [{Pd(mu-Cl){C6H4(PPh2=NCH2-kappa-C,N)-2}}2CH2]2 (2a) [{Pd(mu-OAc){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',3']2 (2b) and [{Pd(mu-OAc){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',2']2 (2c). The reaction takes place in CH2Cl2 for 1a, but must be performed in glacial acetic acid for 1b and 1c. The process implies in all cases the activation of a C-H bond on a Ph ring of the phosphonium group, with concomitant formation of endo complexes. This is the expected behaviour for 1a, but for 1b and 1c reverses the exo orientation observed in other ketostabilized iminophosphoranes. The influence of the solvent in the orientation of the reaction is discussed. The dinuclear acetylacetonate complexes [{Pd(acac-O,O'){C6H4(PPh2=NCH2-kappa-C,N)-2}}2CH2] (3a), [{Pd(acac-O,O'){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',3'] (3b) and [{Pd(acac-O,O'){C6H4(PPh2=NC(O)-kappa-C,N)-2}}2C6H4-1',2'] (3c) have been obtained from the halide-bridging tetranuclear derivatives. The X-ray crystal structure of [3c.4CHCl3] is also reported.

Multifunctional phosphate-based inorganic-organic hybrid nanoparticles.

PubMed

Heck, Joachim G; Napp, Joanna; Simonato, Sara; Möllmer, Jens; Lange, Marcus; Reichardt, Holger M; Staudt, Reiner; Alves, Frauke; Feldmann, Claus

2015-06-17

Phosphate-based inorganic-organic hybrid nanoparticles (IOH-NPs) with the general composition [M](2+)[Rfunction(O)PO3](2-) (M = ZrO, Mg2O; R = functional organic group) show multipurpose and multifunctional properties. If [Rfunction(O)PO3](2-) is a fluorescent dye anion ([RdyeOPO3](2-)), the IOH-NPs show blue, green, red, and near-infrared fluorescence. This is shown for [ZrO](2+)[PUP](2-), [ZrO](2+)[MFP](2-), [ZrO](2+)[RRP](2-), and [ZrO](2+)[DUT](2-) (PUP = phenylumbelliferon phosphate, MFP = methylfluorescein phosphate, RRP = resorufin phosphate, DUT = Dyomics-647 uridine triphosphate). With pharmaceutical agents as functional anions ([RdrugOPO3](2-)), drug transport and release of anti-inflammatory ([ZrO](2+)[BMP](2-)) and antitumor agents ([ZrO](2+)[FdUMP](2-)) with an up to 80% load of active drug is possible (BMP = betamethason phosphate, FdUMP = 5'-fluoro-2'-deoxyuridine 5'-monophosphate). A combination of fluorescent dye and drug anions is possible as well and shown for [ZrO](2+)[BMP](2-)0.996[DUT](2-)0.004. Merging of functional anions, in general, results in [ZrO](2+)([RdrugOPO3]1-x[RdyeOPO3]x)(2-) nanoparticles and is highly relevant for theranostics. Amine-based functional anions in [MgO](2+)[RaminePO3](2-) IOH-NPs, finally, show CO2 sorption (up to 180 mg g(-1)) and can be used for CO2/N2 separation (selectivity up to α = 23). This includes aminomethyl phosphonate [AMP](2-), 1-aminoethyl phosphonate [1AEP](2-), 2-aminoethyl phosphonate [2AEP](2-), aminopropyl phosphonate [APP](2-), and aminobutyl phosphonate [ABP](2-). All [M](2+)[Rfunction(O)PO3](2-) IOH-NPs are prepared via noncomplex synthesis in water, which facilitates practical handling and which is optimal for biomedical application. In sum, all IOH-NPs have very similar chemical compositions but can address a variety of different functions, including fluorescence, drug delivery, and CO2 sorption.

Molecular and polymeric uranyl and thorium hybrid materials featuring methyl substituted pyrazole dicarboxylates and heterocyclic 1,3-diketones

NASA Astrophysics Data System (ADS)

Carter, Korey P.; Kerr, Andrew T.; Taydakov, Ilya V.; Cahill, Christopher L.

2018-02-01

A series of seven novel f-element bearing hybrid materials have been prepared from either methyl substituted 3,4 and 4,5-pyrazoledicarboxylic acids, or heterocyclic 1,3- diketonate ligands using hydrothermal conditions. Compounds 1, [UO2(C6H4N2O4)2(H2O)], and 3, [Th(C6H4N2O4)4(H2O)5]·H2O feature 1-Methyl-1H-pyrazole-3,4-dicarboxylate ligands (SVI-COOH 3,4), whereas 2, [UO2(C6H4N2O4)2(H2O)], and 4, [Th(C6H5N2O4)(OH)(H2O)6]2·2(C6H5N2O4)·3H2O feature 1-Methyl-1H-pyrazole-4,5-dicarboxylate moieties (SVI-COOH 4,5). Compounds 5, [UO2(C13H15N4O2)2(H2O)]·2H2O and 6, [UO2(C11H11N4O2)2(H2O)]·4.5H2O feature 1,3-bis(4-N1-methyl-pyrazolyl)propane-1,3-dione and 1,3-bis(4-N1,3-dimethyl-pyrazolyl)propane-1,3-dione respectively, whereas the heterometallic 7, [UO2(C11H11N4O2)2(CuCl2)(H2O)]·2H2O is formed by using 6 as a metalloligand starting material. Single crystal X-ray diffraction indicates that all coordination to either [UO2]2+ or Th(IV) metal centers is through O-donation as anticipated. Room temperature, solid-state luminescence studies indicate characteristic uranyl emissive behavior for 1 and 2, whereas those for 5 and 6 are weak and poorly resolved.

Synthesis of [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y Ceramic and its Application in Efficient Plasma Decomposition of CO2

NASA Astrophysics Data System (ADS)

Li, Ruixing; Tang, Qing; Yin, Shu; Sato, Tsugio

According to both the first principle and materials chemistry, a method for fabricating [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y ceramic was investigated. It was considered that the sintering was promoted by self-accelerated diffusion due to the formation of point defects caused by doping with Li2Si2O5. Consequently, a concept of non-stoichiometrically activated sintering, which was enhanced by point defects without the help of a grain boundary phase, was systematically studied in the Ca1-xSrxTiO3-Li2Si2O5 system. The mechanical and dielectric properties of [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y were greatly enhanced by adding Li2Si2O5. To improve CO2 decomposition activity, [(Ca1-xSrx)2-2y](Ti2-2yLi2y)Si2yO6-y, which possesses both high permittivity and high dielectric strength was used as a dielectric barrier to decompose CO2 by dielectric barrier discharges (DBDs) plasma without using any catalyst and auxiliary substance. It successfully generated DBDs plasma and the CO2 conversion was much higher than that using an alumina or a silica glass barrier which was widely used as the dielectric barrier in previous studies.

Synthesis, crystal structure and study of magnetocaloric effect and single molecular magnetic behaviour in discrete lanthanide complexes.

PubMed

Adhikary, Amit; Sheikh, Javeed Ahmad; Biswas, Soumava; Konar, Sanjit

2014-06-28

The synthesis, crystal structure and magnetic properties of four polynuclear lanthanide coordination complexes having molecular formulae, [Gd3(2)(1)L(H2O)8(Cl)](Cl)4·10H2O (1), [Dy3L(2)(1)(H2O)9](Cl)5·6H2O (2) [Gd6L(2)(2)(HCO2)4(μ3-OH)4(DMF)6(H2O)2](Cl)2·4H2O (3) and [Dy6L(2)(2)(HCO2)4(μ3-OH)4(DMF)6(H2O)2](Cl)2·4H2O (4) (where H2L(1) = bis[(2-pyridyl)methylene]pyridine-2,6-dicarbohydrazide and H4L(2) = bis[2-hydroxy-benzylidene]pyridine-2,6-dicarbohydrazide) are reported. Structural investigation by X-ray crystallography reveals similar structural features for complexes 1 and 2 and they exhibit butterfly like shapes of the molecules. Non-covalent interactions between the molecules create double helical arrangements for both molecules. Complexes 3 and 4 are isostructural and the core structures feature four distorted hemi-cubanes connected by vertex sharing. Magnetic studies unveil significant magnetic entropy changes for complexes 1, 3 and slow relaxation of magnetization for both dysprosium analogues 2 and 4.

Synthesis and structure of the first discrete dinuclear cationic aluminum complexes.

PubMed

Wang, Xingbao; Dorcet, Vincent; Luo, Yi; Carpentier, Jean-Francois; Kirillov, Evgueni

2016-08-02

The reactions of the charge neutral dinuclear aluminum tetraalkyl complexes of di-Schiff base ligands, i.e. [AlMe2{ON}-R-{ON}AlMe2] (1a, R = 1,3-propylene; 1b, R = 1,3-cyclohexylene) with B(C6F5)3 and [H(Et2O)2](+)[H2N{B(C6F5)3}2](-) were investigated. When B(C6F5)3 was used as the cationizing agent (1 or 2 equiv. vs. Al), only monocationic dinuclear complexes [2a,b]+[MeB(C6F5)3]- were obtained. In contrast, with [H(Et2O)2](+)[H2N{B(C6F5)3}2](-), both mixed-dicationic [3a,b·(OEt2)2]2+[MeB(C6F5)3]-[H2N{B(C6F5)3}2]- and homo-dicationic [3a,b·(OEt2)2]2+[H2N{B(C6F5)3}2]-2 ion-pairs were prepared. All cationic complexes were characterized by (1)H, (13)C, (19)F and (11)B NMR spectroscopy, and an X-ray diffraction study was performed for [3b·(OEt2)2]2+[H2N{B(C6F5)3}2]-2.

Experimental Determination of Lead Interactions with Citrate and EDTA in NaCl and MgCl2 Solutions to High Ionic Strength and Its Applications.

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

Xiong, Yongliang; Kirkes, Leslie Dawn; Westfall, Terry

For this study, the interactions of lead with citrate and ethylenediaminetetraacetate (EDTA) are investigated based on solubility measurements as a function of ionic strength at room temperature (22.5 ± 0.5°C) in NaCl and M gCl 2 solutions. The formation constants (log β 1 0 ) for Pb[C 3H 5O(COO) 3]– (abbreviated as PbCitrate –) and Pb[(CH 2COO) 2N(CH2) 2N(CH 2COO) 2)] 2– (abbreviated as PbEDTA 2–) Pb 2+ + [C 3H 5O(COO) 3] 3– = Pb[C 3H 5O(COO) 3] – (1) Pb 2+ + (CH 2COO) 2N(CH 2) 2N(CH 2COO) 2) 4- = Pb[(CH 2COO) 2N(CH 2) 2N(CH 2COO) 2)]more » 2– (2) are evaluated as 7.28 ± 0.18 (2σ) and 20.00 ± 0.20 (2σ), respectively, with a set of Pitzer parameters describing the specific interactions in NaCl and M gCl 2 media. Based on these parameters, the interactions of lead with citrate and EDTA in various low temperature environments can be accurately modelled.« less

Effect of heavy-metal on synthesis of siderophores by Pseudomonas aeruginosa ZGKD3

NASA Astrophysics Data System (ADS)

Shi, Peili; Xing, Zhukang; Zhang, Yuxiu; Chai, Tuanyao

2017-01-01

Most siderophore-producing bacteria could improve the plant growth. Here, the effect of heavy-metal on the growth, total siderophore and pyoverdine production of the Cd tolerance Pseudomonas aeruginosa ZGKD3 were investigated. The results showed that ZGKD3 exhibited tolerance to heavy metals, and the metal tolerance decreased in the order Mn2+>Pb2+>Ni2+>Cu2+>Zn2+>Cd2+. The total siderophore and pyoverdine production of ZGKD3 induced by metals of Cd2+, Cu2+, Zn2+, Ni2+, Pb2+ and Mn2+ were different, the total siderophore and pyoverdine production reduced in the order Cd2+>Pb2+>Mn2+>Ni2+>Zn2+ >Cu2+ and Zn2+>Cd2+>Mn2+>Pb2+>Ni2+>Cu2+, respectively. These results suggested that ZGKD3 could grow in heavy-metal contaminated soil and had the potential of improving phytoremediation efficiency in Cd and Zn contaminated soils.

CFS Seasonal Climate Forecasts

Science.gov Websites

Europe Prec E1 E2 E3 E1 E2 E3 E1 E2 E3 E1 E2 E3 Europe T2m E1 E2 E3 E1 E2 E3 E1 E2 E3 E1 E2 E3 Misc (E3 E2 E3 E1 E2 E3 US SM E1 E2 E3 E1 E2 E3 E1 E2 E3 E1 E2 E3 Europe Prec E1 E2 E3 E1 E2 E3 E1 E2 E3 E1 E2 E3 Europe T2m E1 E2 E3 E1 E2 E3 E1 E2 E3 E1 E2 E3 Misc (E3) Global u200-u850 Atlantic u200-u850

Accession Medical Standards Analysis and Research Activity (AMSARA), 2015 Annual Report

DTIC Science & Technology

2016-03-01

419 4.4 Internal derangement of knee 1,705 2.2 975 2.1 384 2.5 284 3.0 Contact dermatitis and other eczema 1,558 2.0 1048 2.2 300 2.0 238 2.5...and unspecified disorders of bone and cartilage 302 2.6 254 2.8 4 2.8 3 2.5 Contact dermatitis and other eczema 280 2.4 230 2.6 6 4.2 6 4.9... Contact dermatitis and other eczema 500 2.9 181 1.7 104 2.8 26 1.3 Hearing loss 607 3.6 94 0.9 100 2.7 6 0.3 Recurrent dislocation of joint 263

Formation of {Co(dppe)}2{μ2-η(2):η(2)-η(2):η(2)-[(C60)2]} Dimers Bonded by Single C-C Bonds and Bridging η(2)-Coordinated Cobalt Atoms.

PubMed

Konarev, Dmitri V; Troyanov, Sergey I; Ustimenko, Kseniya A; Nakano, Yoshiaki; Shestakov, Alexander F; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2015-05-18

Coordination of two bridging cobalt atoms to fullerenes by the η(2) type in {Co(dppe)}2{μ2-η(2):η(2)-η(2):η(2)-[(C60)2]}·3C6H4Cl2 [1; dppe = 1,2-bis(diphenylphosphino)ethane] triggers fullerene dimerization with the formation of two intercage C-C bonds of 1.571(4) Å length. Coordination-induced fullerene dimerization opens a path to the design of fullerene structures bonded by both covalent C-C bonds and η(2)-coordination-bridged metal atoms.

2011 Summer Student Research

DTIC Science & Technology

2012-08-29

material using solid reaction method for SOFC application. The start materials are Sr2CO3, Ga2O3 ,V2O5 and Sc2O3. The powders were mixed proportionally...according to the chemical reaction equation (1) and (2) as below: 4SrCO3+ V2O5+ Ga2O3 = 2 Sr2GaVO6+4CO2 (1) 4SrCO3+ V2O5+ Sc2O3 = 2 Sr2ScVO6+4CO2...the XRD patterns of the compound in air and H2 reduction atmosphere using Sr2CO3, Ga2O3 and V2O5 as starting materials, respectively. The main

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

Morozkin, A.V., E-mail: morozkin@tech.chem.msu.ru; Isnard, O.; Université Grenoble Alpes, Inst. Néel, F-38042 Grenoble

The crystal structure of new Mo{sub 2}NiB{sub 2}-type (Gd, Tb, Dy){sub 2}Ni{sub 2.35}Si{sub 0.65} (Immm, No. 71, oI10) and La{sub 2}Ni{sub 3}-type (Dy, Ho){sub 2}Ni{sub 2.5}Si{sub 0.5} (Cmce No. 64, oC20) compounds has been established using powder X-ray diffraction studies. Magnetization measurements show that the Mo{sub 2}NiB{sub 2}-type Gd{sub 2}Ni{sub 2.35}Si{sub 0.65} undergoes a ferromagnetic transition at ~66 K, whereas isostructural Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} shows an antiferromagnetic transition at ~52 K and a field-induced metamagnetic transition at low temperatures. Neutron diffraction study shows that, in zero applied field, Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} exhibits c-axis antiferromagnetic order with propagation vectormore » K=[1/2, 0, 1/2] below its magnetic ordering temperature and Tb magnetic moment reaches a value of 8.32(5) μ{sub B} at 2 K. The La{sub 2}Ni{sub 3}-type Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} exhibits ferromagnetic like transition at ~42 K with coexisting antiferromagnetic interactions and field induced metamagnetic transition below ~17 K. The magnetocaloric effect of Gd{sub 2}Ni{sub 2.35}Si{sub 0.65}, Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} and Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} is calculated in terms of isothermal magnetic entropy change and it reaches a maximum value of −14.3 J/kg K, −5.3 J/kg K and −10.3 J/kg K for a field change of 50 kOe near 66 K, 52 K and 42 K, respectively. Low temperature magnetic ordering with enhanced anisotropic effects in Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} and Dy{sub 2}Ni{sub 2.35}Si{sub 0.65} is accompanied by a positive magnetocaloric effect with isothermal magnetic entropy changes of +12.8 J/kg K and ~+9.9 J/kg K, respectively at 7 K for a field change of 50 kOe. - Graphical abstract: The (Gd, Tb, Dy){sub 2}Ni{sub 2.35}Si{sub 0.65} supplement the series of Mo{sub 2}NiB{sub 2}-type rare earth compounds, whereas the (Dy, Ho){sub 2}Ni{sub 2.5}Si{sub 0.5} supplement the series of La{sub 2}Ni{sub 3}-type rare earth compounds. The variation of alloy’s composition by ~3 at% i.e. from Dy{sub 2}Ni{sub 2.35}Si{sub 0.65} to Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} leads to significant transformation of crystal structure of compound with different variant of distortion of Po-type rare earth sublattice, as in Gd–Co–Ga and Er–Ni–In systems: the Mo{sub 2}NiB{sub 2}-type Gd{sub 2}Co{sub 2}Ga and La{sub 2}Ni{sub 3}-type Gd{sub 2}Co{sub 2.9}Ga{sub 0.1}, and Mo{sub 2}FeB{sub 2}-type Er{sub 2}Ni{sub 1.78}In and Mn{sub 2}AlB{sub 2}-type Er{sub 2}Ni{sub 2}In. Magnetization measurements indicate collinear ferromagnetic ordering of Mo{sub 2}NiB{sub 2}-type Gd{sub 2}Ni{sub 2.35}Si{sub 0.65} and a complex antiferromagnetic ordering with low-temperature metamagnetic nature for Mo{sub 2}NiB{sub 2}-type Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} compounds. However, neutron diffraction study in zero applied field of Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} reveals c-axis pure antiferromagnetic ordering of terbium sublattice with K=[1/2, 0, 1/2] propagation vector. Magnetization measurements indicate ferromagnetic order with coexisting antiferromagnetic interactions and low-temperature metamagnetic state for La{sub 2}Ni{sub 3}-type Dy{sub 2}Ni{sub 2.5}Si{sub 0.5}. We suggest possible polymorphism in other Mo{sub 2}FeB{sub 2}-type, Mo{sub 2}NiB{sub 2}-type, La{sub 2}Ni{sub 3}-type and Mn{sub 2}AlB{sub 2}-type rare earth compounds with corresponding change in their magnetic properties. - Highlights: • (Gd, Tb, Dy){sub 2}Ni{sub 2.35}Si{sub 0.65} compounds crystallize in the Mo{sub 2}NiB{sub 2}-type structure. • (Dy, Ho){sub 2}Ni{sub 2.5}Si{sub 0.5} compounds crystallize in the La{sub 2}Ni{sub 3}-type structure. • Gd{sub 2}Ni{sub 2.35}Si{sub 0.65} shows pure ferromagnetic type ordering. • Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} and Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} show mixed ferro-antiferromagnetic ordering. • Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} and Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} exhibit low-temperature metamagnetic behaviour.« less

The conformations of 13-vertex ML2C2B10 metallacarboranes: experimental and computational studies.

PubMed

Dalby, Kelly J; Ellis, David; Erhardt, Stefan; McIntosh, Ruaraidh D; Macgregor, Stuart A; Rae, Karen; Rosair, Georgina M; Settels, Volker; Welch, Alan J; Hodson, Bruce E; McGrath, Thomas D; Stone, F Gordon A

2007-03-21

The docosahedral metallacarboranes 4,4-(PMe(2)Ph)2-4,1,6-closo-PtC(2)B(10)H(12), 4,4-(PMe(2)Ph)2-4,1,10-closo-PtC(2)B(10)H(12), and [N(PPh(3))2][4,4-cod-4,1,10-closo-RhC(2)B(10)H(12)] were prepared by reduction/metalation of either 1,2-closo-C(2)B(10)H(12) or 1,12-closo-C(2)B(10)H(12). All three species were fully characterized, with a particular point of interest of the latter being the conformation of the {ML2} fragment relative to the carborane ligand face. Comparison with conformations previously established for six other ML(2)C(2)B(10) species of varying heteroatom patterns (4,1,2-MC(2)B(10), 4,1,6-MC(2)B(10), 4,1,10-MC(2)B(10), and 4,1,12-MC(2)B(10)) reveals clear preferences. In all cases a qualitative understanding of these was afforded by simple MO arguments applied to the model heteroarene complexes [(PH3)2PtC(2)B(4)H(6)]2- and [(PH3)2PtCB(5)H(6)]3-. Moreover, DFT calculations on [(PH3)2PtC(2)B(4)H(6)]2- in its various isomeric forms approximately reproduced the observed conformations in the 4,1,2-, 4,1,6-, and 4,1,10-MC(2)B(10) species, although analogous calculations on [(PH3)2PtCB(5)H(6)]3- did not reproduce the conformation observed in the 4,1,12-MC(2)B(10) metallacarborane. DFT calculations on (PH3)2PtC(2)B(10)H(12) yielded good agreement with experimental conformations in all four isomeric cases. Apparent discrepancies between observed and computed Pt-C distances were probed by further refinement of the 4,1,2- model to 1,2-(CH2)3-4,4-(PMe3)2-4,1,2-closo-PtC(2)B(10)H(10). This still has a more distorted structure than measured experimentally for 1,2-(CH2)3-4,4-(PMe(2)Ph)2-4,1,2-closo-PtC(2)B(10)H(10), but the structural differences lie on a very shallow potential energy surface. For the model compound a henicosahedral transition state was located 8.3 kcal mol(-1) above the ground-state structure, consistent with the fluxionality of 1,2-(CH2)3-4,4-(PMe(2)Ph)2-4,1,2-closo-PtC(2)B(10)H(10) in solution.

Insights into the intramolecular donor stabilisation of organostannylene palladium and platinum complexes: syntheses, structures and DFT calculations.

PubMed

Wagner, Michael; Deáky, Vajk; Dietz, Christina; Martincová, Jana; Mahieu, Bernard; Jambor, Roman; Herres-Pawlis, Sonja; Jurkschat, Klaus

2013-05-17

The syntheses of the transition metal complexes cis-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)2MX2] (1, M = Pd, X = Cl; 2, M = Pd, X = Br; 3, M = Pd, X = I; 4, M = Pt, X = Cl), cis-[{2,6-(Me2NCH2)2C6H3SnCl}2MX2] (5, M = Pd, X = I; 6, M = Pt, X = Cl), trans-[{2,6-(Me2NCH2)2C6H3SnI}2PtI2] (7) and trans-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)PdI2]2 (8) are reported. Also reported is the serendipitous formation of the unprecedented complexes trans-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)2Pt(SnCl3)2] (10) and [(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)3Pt(SnCl3)2] (11). The compounds were characterised by elemental analyses, (1)H, (13)C, (31)P, (119)Sn and (195)Pt NMR spectroscopy, single-crystal X-ray diffraction analysis, UV/Vis spectroscopy and, in the cases of compounds 1, 3 and 4, also by Mössbauer spectroscopy. All the compounds show the tin atoms in a distorted trigonal-bipyramidal environment. The Mössbauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic lability of the complexes was studied by redistribution reactions between compounds 1 and 3 as well as between 1 and cis-[{2,6-(Me2 NCH2)2C6H3SnCl}2PdCl2]. DFT calculations provided insights into both the bonding situation of the compounds and the energy difference between the cis and trans isomers. The latter is influenced by the donor strength of the pincer-type ligands. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A series of divalent metal coordination polymers based on isomeric tetracarboxylic acids: synthesis, structures and magnetic properties.

PubMed

Han, Min-Le; Duan, Ya-Ping; Li, Dong-Sheng; Xu, Guo-Wang; Wu, Ya-Pan; Zhao, Jun

2014-12-14

Five new coordination polymers, namely, [Mn(2,2′-bipy)(H2O)2(H2L1)]n (1), {[Co(btb)(H2O)2(H2L1)]·0.5H2O}n (2), [Co(bib)(H2O)2(H2L1)]n (3), [Ni2(bpm)(H2O)3(L2)]n (4), and {[Co2(H2O)3(OH)(HL2)]·H2O}n (5), (H4L1 = 1,1′:2′,1′′-terphenyl-4,4′,4′′,5′-tetracarboxylic acid, H4L2 = 1,1′:2′,1′′-terphenyl-3,3′′,4′,5′-tetracarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bib = 1,4-bis(imidazol-1-yl)butane, bpm = bis(4-pyridyl)amine), have been obtained under hydrothermal conditions. Complex 1 exhibits a 3D supramolecular framework based on 1D chains. Both complexes 2 and 3 are 3D supramolecular frameworks constructed from 1D zig-zag chains. Complex 4 features a 3D tetra-nodal (3,4,4,5)-connected architecture containing 1D μ-COO bridged chains with (5(2)·6(2)·7.9)(5(2)·6(4)·7(3)·8)2(5(2)·6)2(6(3)·7(2)·9) topology. Complex 5 shows a 3D penta-nodal (3,4,4,6,6)-connected net containing 1D μ-OH/μ-COO bridged chains and mononuclear Co(II) nodes with a (4(2)·6(3)·8)(4(3))2(4(4)·6(2))2(4(4)·6(6)·8(5))2(4(4)·6(7)·8(4)) topology. Variable-temperature magnetic susceptibility measurements reveal that complexes 2 and 3 show antiferromagnetic interactions between the adjacent Co(II) ions, whereas 4 is a ferromagnetic system.

Monomeric and oligomeric amine-borane sigma-complexes of rhodium. intermediates in the catalytic dehydrogenation of amine-boranes.

PubMed

Douglas, Thomas M; Chaplin, Adrian B; Weller, Andrew S; Yang, Xinzheng; Hall, Michael B

2009-10-28

A combined experimental/quantum chemical investigation of the transition metal-mediated dehydrocoupling reaction of H(3)B.NMe(2)H to ultimately give the cyclic dimer [H(2)BNMe(2)](2) is reported. Intermediates and model complexes have been isolated, including examples of amine-borane sigma-complexes of Rh(I) and Rh(III). These come from addition of a suitable amine-borane to the crystallographically characterized precursor [Rh(eta(6)-1,2-F(2)C(6)H(4))(P(i)Bu(3))(2)][BAr(F)(4)] [Ar(F) = 3,5-(CF(3))(2)C(6)H(3)]. The complexes [Rh(eta(2)-H(3)B.NMe(3))(P(i)Bu(3))(2)][BAr(F)(4)] and [Rh(H)(2)(eta(2)-H(3)B.NHMe(2))(P(i)Bu(3))(2)][BAr(F)(4)] have also been crystallographically characterized. Other intermediates that stem from either H(2) loss or gain have been characterized in solution by NMR spectroscopy and ESI-MS. These complexes are competent in the catalytic dehydrocoupling (5 mol %) of H(3)B.NMe(2)H. During catalysis the linear dimer amine-borane H(3)B.NMe(2)BH(2).NHMe(2) is observed which follows a characteristic intermediate time/concentration profile. The corresponding amine-borane sigma-complex, [Rh(P(i)Bu(3))(2)(eta(2)-H(3)B.NMe(2)BH(2).NHMe(2))][BAr(F)(4)], has been isolated and crystallographically characterized. A Rh(I) complex of the final product, [Rh(P(i)Bu(3))(2){eta(2)-(H(2)BNMe(2))(2)}][BAr(F)(4)], is also reported, although this complex lies outside the proposed catalytic cycle. DFT calculations show that the first proposed dehydrogenation step, to give H(2)B horizontal lineNMe(2), proceeds via two possible routes of essentially the same energy barrier: BH or NH activation followed by NH or BH activation, respectively. Subsequent to this, two possible low energy routes that invoke either H(2)/H(2)B horizontal lineNMe(2) loss or H(2)B horizontal lineNMe(2)/H(2) loss are suggested. For the second dehydrogenation step, which ultimately affords [H(2)BNMe(2)](2), a number of experimental observations suggest that a simple intramolecular route is not operating: (i) the isolated complex [Rh(P(i)Bu(3))(2)(eta(2)-H(3)B.NMe(2)BH(2).NHMe(2))][BAr(F)(4)] is stable in the absence of amine-boranes; (ii) addition of H(3)B.NMe(2)BH(2).NHMe(2) to [Rh(P(i)Bu(3))(2)(eta(2)-H(3)B.NMe(2)BH(2).NHMe(2))][BAr(F)(4)] initiates dehydrocoupling; and (iii) H(2)B horizontal lineNMe(2) is also observed during this process.

Potentiometric titration for determining the composition and stability of metal(II) alginates and pectinates in aqueous solutions

NASA Astrophysics Data System (ADS)

Kaisheva, N. Sh.; Kaishev, A. Sh.

2015-07-01

The compositions and stabilities of Cu2+, Mn2+, Pb2+, Ca2+, Zn2+, Cd2+, Co2+, and Ni2+ alginates and pectinates are determined in aqueous solutions via titrimetry and potentiometry with calculations performed using Bjerrum's method, the curve intersection technique, and the equilibrium shift method. It is found that the interaction between Cu2+ and polyuronides is a stepwise process and, depending on the ligand concentration and the method of determination, Cu2+ alginate can be characterized by its ML, ML2, and ML3 compositions (where M is the metal ion and L is the structural unit of polyuronide) and stability constants logβ = 2.65, 5.00-5.70, and 7.18-7.80, respectively. The compositions of Cu2+ pectinates are ML and ML2 with logβ = 3.00 and 7.64-7.94, respectively. It is concluded that Pb2+, Ca2+, Mn2+, Zn2+, Cd2+, Co2+, and Ni2+ ions form only alginates and pectinates of ML2 composition with logβ values of 3.45 (Pb2+ alginate), 2.20 (Ca2+ alginate), 1.06 (Mn2+ alginate), 3.51 (Pb2+ pectinate), 2.35 (Ca2+ pectinate), and 1.24 (Mn2+ pectinate). The pectinates are shown to be more stable than the alginates, the most stable compounds being those formed by polyuronides and Cu2+. The least stable are those with Mn2+.

Sensitive and selective detection of trivalent chromium using Hyper Rayleigh Scattering with 5,5'-dithio-bis-(2-nitrobenzoic acid)-modified gold nanoparticles.

PubMed

Hughes, Shantelle I; Dasary, Samuel S R; Singh, Anant K; Glenn, Zachery; Jamison, Hakim; Ray, Paresh C; Yu, Hongtao

2013-03-01

Hyper Rayleigh Scattering (HRS) and absorption spectral assays using surface-modified gold nanoparticles (AuNP) have been developed for sensitive and selective detection of trivalent chromium (Cr 3+ ) from other metal ions including hexavalent chromium (as Cr 2 O 7 2- ). Gold nanoparticles of 13 nm, covalently attached with 5,5'-dithio- bis -(2-nitrobenzoic acid) (AuNP-DTNBA), is used as a probe for both the absorption and HRS assays. AuNP-DTNBA is able to detect Cr 3+ at 20 ppb level at pH 6.0 using absorption spectral change of the AuNP-DTNBA. Visible color change can be observed when mixed with 250 ppb of Cr 3+ , while there is no color change when mixed with 2 ppm level of some of the most common metal ions such as Cr 2 O 7 2- , Hg 2+ , Ba 2+ , Fe 3+ , Pb 2+ , Na + , Zn 2+ , Cd 2+ , Co 2+ , Mn 2+ , Ca 2+ , and Ni 2+ . However, a color change is observed when mixed with Ni 2+ , Zn 2+ , and Cd 2+ at a concentration higher than 2 ppm. The detection limit for the HRS assay is on a remarkable 25 ppt level, and there is no detectable HRS signal at 2 ppm level for Cr 2 O 7 2- , Hg 2+ , Ba 2+ , Fe 3+ , Pb 2+ , Na + , Zn 2+ , Cd 2+ , Co 2+ , Mn 2+ , Ca 2+ , and Ni 2+ .

Synthesis of Zr2WP2O12/ZrO2 Composites with Adjustable Thermal Expansion.

PubMed

Zhang, Zhiping; Sun, Weikang; Liu, Hongfei; Xie, Guanhua; Chen, Xiaobing; Zeng, Xianghua

2017-01-01

Zr 2 WP 2 O 12 /ZrO 2 composites were fabricated by solid state reaction with the goal of tailoring the thermal expansion coefficient. XRD, SEM and TMA were used to investigate the composition, microstructure, and thermal expansion behavior of Zr 2 WP 2 O 12 /ZrO 2 composites with different mass ratio. Relative densities of all the resulting Zr 2 WP 2 O 12 /ZrO 2 samples were also tested by Archimedes' methods. The obtained Zr 2 WP 2 O 12 /ZrO 2 composites were comprised of orthorhombic Zr 2 WP 2 O 12 and monoclinic ZrO 2 . As the increase of the Zr 2 WP 2 O 12 , the relative densities of Zr 2 WP 2 O 12 /ZrO 2 ceramic composites increased gradually. The coefficient of thermal expansion of the Zr 2 WP 2 O 12 /ZrO 2 composites can be tailored from 4.1 × 10 -6 K -1 to -3.3 × 10 -6 K -1 by changing the content of Zr 2 WP 2 O 12 . The 2:1 Zr 2 WP 2 O 12 /ZrO 2 specimen shows close to zero thermal expansion from 25 to 700°C with an average linear thermal expansion coefficient of -0.09 × 10 -6 K -1 . These adjustable and near zero expansion ceramic composites will have great potential application in many fields.

Varying the Lewis base coordination of the Y2N2 core in the reduced dinitrogen complexes {[(Me3Si)2N]2(L)Y}2(μ-η2:η2-N2) (L = benzonitrile, pyridines, triphenylphosphine oxide, and trimethylamine N-oxide).

PubMed

Corbey, Jordan F; Farnaby, Joy H; Bates, Jefferson E; Ziller, Joseph W; Furche, Filipp; Evans, William J

2012-07-16

The effect of the neutral donor ligand, L, on the Ln(2)N(2) core in the (N═N)(2-) complexes, [A(2)(L)Ln](2)(μ-η(2):η(2)-N(2)) (Ln = Sc, Y, lanthanide; A = monoanion; L = neutral ligand), is unknown since all of the crystallographically characterized examples were obtained with L = tetrahydrofuran (THF). To explore variation in L, displacement reactions between {[(Me(3)Si)(2)N](2)(THF)Y}(2)(μ-η(2):η(2)-N(2)), 1, and benzonitrile, pyridine (py), 4-dimethylaminopyridine (DMAP), triphenylphosphine oxide, and trimethylamine N-oxide were investigated. THF is displaced by all of these ligands to form {[(Me(3)Si)(2)N](2)(L)Y}(2)(μ-η(2):η(2)-N(2)) complexes (L = PhCN, 2; py, 3; DMAP, 4; Ph(3)PO, 5; Me(3)NO, 6) that were fully characterized by analytical, spectroscopic, density functional theory, and X-ray crystallographic methods. The crystal structures of the Y(2)N(2) cores in 2-5 are similar to that in 1 with N-N bond distances between 1.255(3) Å and 1.274(3) Å, but X-ray analysis of the N-N distance in 6 shows it to be shorter: 1.198(3) Å.

Structure of complexes of uranyl succinate with carbamide and dimethylurea

NASA Astrophysics Data System (ADS)

Serezhkina, L. B.; Grigor'ev, M. S.; Seliverstova, N. V.; Serezhkin, V. N.

2017-09-01

Three new succinate-containing complexes of uranyl with carbamide ( Urea) and N,N'-dimethylurea ( s-Dmur) are synthesized and studied by IR spectroscopy and X-ray diffraction. Structures of the same type, [UO2( Urea)4(H2O)][(UO2)2(C4H4O4)3] · 3H2O and [UO2( Urea)4(H2O)][(UO2)2(C4H4O4)3] · 2 Urea contain two sorts of uranium-containing complex groups, namely, mononuclear [UO2( Urea)4(H2O)]2+ cations and two-dimensional [(UO2)2(C4H4O4)3]2- anions described by crystal-chemical formulas AM 5 1 and A 2 Q 3 02, respectively ( A = UO2 2+, M 1 = Urea or H2O, Q 02 = C4H4O4 2-), and differ only in the nature of noncoordinated molecules—water and carbamide. The main structural groups of the [(UO2)2(C4H4O4)2( s-Dmur)3] crystals are [(UO2)2(C4H4O4)2( s-Dmur)3] chains belonging to the A 2 Q 2 02 M 3 1 ( A = UO2 2+, Q 02 = C4H4O4 2-, M 1 = s-Dmur) crystal-chemical group. Specific features of intermolecular interactions in the crystal structures are revealed using the Voronoi-Dirichlet method of molecular polyhedra.

VAPOR PRESSURES, LIQUID MOLAR VOLUMES, VAPOR NON- IDEALITY, AND CRITICAL PROPERTIES OF CF3OCF2CF2CF3, c-CF2CF2CF2CF2O, CF3OCF2OCF3, AND CF3OCF2CF2H

EPA Science Inventory

New measurements of the thermophysical properties of CF3OCF2CF2CF3 and c -CF2CF2CF2CF2O are reported from T ≈ 235 K to the critical region. Liquid-phase volumetric results for CF3OCF2OCF3 and CF3OCF2CF2H (235 < T/K < 303) are reported to supplement the information already availab...

Optimum Aeroelastic Characteristics for Composite Supermaneuverable Aircraft.

DTIC Science & Technology

1986-07-31

1󈨌D22 1 k 16 ’ cD 22YI Y6 WL k 17 ’ cD 22 Y, Y7 k 18 ’ -2cD 26YI1 Y6 gi 0 k19 : -2cD26Y I y 7 k1,10 12 2c Bo 10 1 󈧐D22 1 10 22 cD22 (y2 )2 k23 -2cD...2 6y1Y2 k24 -2cD 2 6 Y2Y 2 3 ,, 11 10 k -S-D + 2cD a 25 12 D22 5 2 12 5 2 k26 cD22 Y2 Y6 k27 cD22 y2 Y7 28 -2cD 2 6 Y2 Y6 k29 -2cD 26Y2 Y7 k’ "" 0y

Inhibition of ATPase activity in rat synaptic plasma membranes by simultaneous exposure to metals.

PubMed

Carfagna, M A; Ponsler, G D; Muhoberac, B B

1996-03-08

Inhibition of Na+/K+-ATPase and Mg2+-ATPase activities by in vitro exposure to Cd2+, Pb2+ and Mn2+ was investigated in rat brain synaptic plasma membranes (SPMs). Cd2+ and Pb2+ produced a larger maximal inhibition of Na+/K+-ATPase than of Mg2+-ATPase activity. Metal concentrations causing 50% inhibition of Na+/K+-ATPase activity (IC50 values) were Cd2+ (0.6 microM) < Pb2+ (2.1 microM) < Mn2+ (approximately 3 mM), and the former two metals were substantially more potent in inhibiting SPM versus synaptosomal Na+/K+-ATPase. Dixon plots of SPM data indicated that equilibrium binding of metals occurs at sites causing enzyme inhibition. In addition, IC50 values for SPM K+-dependent p-nitrophenylphosphatase inhibition followed the same order and were Cd2+ (0.4 microM) < Pb2+ (1.2 microM) < Mn2+ (300 microM). Simultaneous exposure to the combinations Cd2+/Mn2+ or Pb2+/Mn2+ inhibited SPM Na+/K+-ATPase activity synergistically (i.e., greater than the sum of the metal-induced inhibitions assayed separately), while Cd2+/Pb2+ caused additive inhibition. Simultaneous exposure to Cd2+/Pb2+ antagonistically inhibited Mg2+-ATPase activity while Cd2+/Mn2+ or Pb2+/Mn2+ additively inhibited Mg2+-ATPase activity at low Mn2+ concentrations, but inhibited antagonistically at higher concentrations. The similar IC50 values for Cd2+ and Pb2+ versus Mn2+ inhibition of Na+/K+-ATPase and the pattern of inhibition/activation upon exposure to two metals simultaneously support similar modes of interaction of Cd2+ and Pb2+ with this enzyme, in agreement with their chemical reactivities.

Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes supported by the imidodiphosphinate ligand [N(i-Pr2PO)2]-.

PubMed

Wang, Guo-Cang; Sung, Herman H Y; Dai, Feng-Rong; Chiu, Wai-Hang; Wong, Wai-Yeung; Williams, Ian D; Leung, Wa-Hung

2013-03-04

Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes containing the imidodiphosphinate ligand [N(i-Pr2PO)2](-) have been synthesized, and their reactivity was investigated. Treatment of Ce[N(i-Pr2PO)2]3Cl (1) with AgMO4 (M = Re, Mn) afforded Ce[N(i-Pr2PO)2]3(ReO4) (2) or Ce2[N(i-Pr2PO)2]6(MnO4)2 (3). In the solid state, 3 is composed of a [Ce2{N(i-Pr2PO)2}6(MnO4)](+) moiety featuring a weak Ce-OMn interaction [Ce-OMn distance = 2.528(8) Å] and a noncoordinating MnO4(-) counteranion. While 3 is stable in the solid state and acetonitrile solution, it decomposes readily in other organic solvents, such as CH2Cl2. 3 can oxidize ethylbenzene to acetophenone at room temperature. Treatment of 1 with AgBF4, followed by reaction with [n-Bu4N]2[MoO4], afforded [Ce{N(i-Pr2PO)2}3]2(μ-MoO4) (4). Reaction of trans-Ce[N(i-Pr2PO)2]2(NO3)2 (5), which was prepared from (NH4)2Ce(NO3)6 and K[N(i-Pr2PO)2], with 2 equiv of [n-Bu4N][Cp*MoO3] yielded trans-Ce[N(i-Pr2PO)2]2(Cp*MoO3)2 (6). 4 can catalyze the oxidation of methyl phenyl sulfide with tert-butyl hydroperoxide with high selectivity. The crystal structures of complexes 3-6 have been determined.

PSEUDO-BINARY SYSTEMS INVOLVING RARE EARTH LAVES PHASES

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

Wernick, J.H.; Haszko, S.E.; Dorsi, D.

1962-06-01

The phase relations in a number of pseudo-binary systems involving rare earth Laves phases were determined. Complete series of cubic solid-solutions occur in the DyMn/sub 2/HoMn/sub 2/, HoMn/sub 2/-HoFe/sub 2/, DyMn/sub 2/-DyFe/ sub 2/, HoMn/sub 2/-HoAl/ sub 2/, TbMn/sub 2/TbAl/sub 2/, and DyMn/sub 2/-DyAl/ sub 2/ pseudobinary systems. Deviations from linearity in the lattice constants with composition occur in all these systems. Complete series of cubic solidsolutions also exist in the GdAl/sub 2/-ErAl/sub 2/, GdAl/sub 2/-PrAl/sub 2/ , GdAl/sub 2/-NdAl/sub 2/, GdAl/sub 2/-DyAl/sub 2/, TbAl/sub 2/-NdAl/sub 2/, and T bAl/sub 2/-DyAl/sub 2/ systems. For these systems, no deviation from linearitymore » occurs in the lattice constants. For the DyFe/sub 2/-DyAl/sub 2/ and DyCo/sub 2/- DyAl/sub 2/ systems, two new ternary phases, DyFeAl and DyCoAl, form and have the MgZn/sub 2/ structure. Their structures were determined from x-ray powder data only. The electronic state giving rise to the formation of these ternary phases is discussed qualitatively. For the DyMn/sub 2/TmMn/sub 2/ system, the range of composition in which the cubic MgCu/sub 2/ and hexagonal MgZn/sub 2/ structures exist are reported. No complete series of solid solutions or intermediate phases are formed in the DyNi/sub 2/-DyAl/sub 2/ system. (auth)« less

Erratum to: Blood HbO2 and HbCO2 dissociation curves at varied O2, CO2, pH, 2,3-DPG and temperature levels.

PubMed

Dash, Ranjan K; Bassingthwaighte, James B

2010-04-01

New mathematical model equations for O(2) and CO(2) saturations of hemoglobin (S(HbO)(2) and S(HbCO)(2) are developed here from the equilibrium binding of O(2) and CO(2) with hemoglobin inside RBCs. They are in the form of an invertible Hill-type equation with the apparent Hill coefficients KHbO(2) and KHbCO(2) in the expressions for SHbO(2) and SHbCO(2) dependent on the levels of O(2) and CO(2) partial pressures (P(O)(2) and P(CO)(2)), pH, 2,3-DPG concentration, and temperature in blood. The invertibility of these new equations allows PO(2) and PCO(2) to be computed efficiently from S(HbO)(2) and S(HbCO)(2) and vice versa. The oxyhemoglobin (HbO(2)) and carbamino-hemoglobin (HbCO(2)) dissociation curves computed from these equations are in good agreement with the published experimental and theoretical curves in the literature. The model solutions describe that, at standard physiological conditions, the hemoglobin is about 97.2% saturated by O(2) and the amino group of hemoglobin is about 13.1% saturated by CO(2). The O(2) and CO(2) content in whole blood are also calculated here from the gas solubilities, hematocrits, and the new formulas for S(HbO)(2) and S(HbCO)(2). Because of the mathematical simplicity and invertibility, these new formulas can be conveniently used in the modeling of simultaneous transport and exchange of O(2) and CO(2) in the alveoli-blood and blood-tissue exchange systems.

Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

PubMed

Yang, Jingying; Xie, Zuowei

2015-04-14

Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

Detection methods for atoms and radicals in the gas phase

NASA Astrophysics Data System (ADS)

Hack, W.

This report lists atoms and free radicals in the gas phase which are of interest for environmental and flame chemistry and have been detected directly. The detection methods which have been used are discussed with respect to their range of application, specificity and sensitivity. In table 1, detection methods for the five atoms of group IV (C, Si, Ge, Sn, Pb) and about 60 radicals containing at least one atom of group IV are summarized (CH, Cd, Cf, CC1, CBr, Cn, Cs, CSe, CH2, CD2, Chf, Cdf, CHC1, CHBr, CF2, CC12, CBr2, CFC1, CFBr, CH3, CD3, CF3, CH2F, CH2C1, CH2Br, CHF2, CHC12, CHBr2, Hco, Fco, CH30, CD30, CH2OH, CH3S, Nco, CH4N, CH302, CF302; C2, C2N, C2H, C20, C2HO, C2H3, C2F3, C2H5, C2HsO, C2H4OH, CH3CO, CD3CO, C2H3O, C2H502, CH3COO2, C2H4N, C2H6N, C3; Si, SiF, SiF2, SiO, SiC, Si2; Ge, GeC, GeO, GeF, GeF2, GeCl2, Sn, SnF, SnO, SnF2, Pb, PbF, PbF2, PbO, PbS). In table 2 detection methods for about 25 other atoms and 60 radicals are listed: (H, D, O, O2, Oh, Od, HO2, DO2, F, Ci, Br, I, Fo, Cio, BrO, Io, FO2, C1O2, Li, Na, K, Rb, Cs, N, N3, Nh, Nd, Nf, Nci, NBr, NH2, ND2, Nhd, Nhf, NF2, NC12, N2H3, No, NO2, NO3, Hno, Dno, P, Ph, Pd, Pf, Pci, PH2, PD2, PF2, Po, As, AsO, AsS, Sb, Bi, S, S2, Sh, Sd, Sf, SF2, So, Hso, Dso, Sn, Se, Te, Se2, SeH, SeD, SeF, SeO, SeS, SeN, TeH, TeO, Bh, BH2, Bo, Bn, B02, Cd, Hg, UF5). The tables also cite some recent kinetic applications of the various methods.

Structural, thermal, and magnetic study of solvation processes in spin-crossover [Fe(bpp)(2)][Cr(L)(ox)(2)](2).nH(2)O complexes.

PubMed

Clemente-León, Miguel; Coronado, Eugenio; Giménez-López, M Carmen; Romero, Francisco M

2007-12-24

The influence of lattice water in the magnetic properties of spin-crossover [Fe(bpp)2]X2.nH2O salts [bpp = 2,6-bis(pyrazol-3-yl)pyridine] is well-documented. In most cases, it stabilizes the low-spin state compared to the anhydrous compound. In other cases, it is rather the contrary. Unraveling this mystery implies the study of the microscopic changes that accompany the loss of water. This might be difficult from an experimental point of view. Our strategy is to focus on some salts that undergo a nonreversible dehydration-hydration process without loss of crystallinity. By comparison of the structural and magnetic properties of original and rehydrated samples, several rules concerning the role of water at the microscopic level can be deduced. This paper reports on the crystal structure, thermal studies, and magnetic properties of [Fe(bpp)2][Cr(bpy)(ox)2]2.2H2O (1), [Fe(bpp)2][Cr(phen)(ox)2]2.0.5H2O.0.5MeOH (2), and [Fe(bpp)2][Cr(phen)(ox)2]2.5.5H2O.2.5MeOH (3). Salt 1 contains both high-spin (HS) and low-spin (LS) Fe2+ cations in a 1:1 ratio. Dehydration yields the anhydrous spin-crossover compound with T1/2 downward arrow = 353 K and T1/2 upward arrow = 369 K. Rehydration affords the dihydrate [Fe(bpp)2][Cr(bpy)(ox)2]2.2H2O (1r) with 100% HS Fe2+ sites. Salt 2 also contains both HS and LS Fe2+ cations in a 1:1 ratio. Dehydration yields the anhydrous spin-crossover compound with T1/2 downward arrow = 343 K and T1/2 upward arrow = 348 K. Rehydration affords [Fe(bpp)2][Cr(phen)(ox)2]2.0.5H2O (2r) with 72% Fe2+ sites in the LS configuration. The structural, magnetic, and thermal properties of these rehydrated compounds 1r and 2r are also discussed. Finally, 1 has been dehydrated and resolvated with MeOH to give [Fe(bpp)2][Cr(bpy)(ox)2]2.MeOH (1s) with 33% HS Fe2+ sites. The influence of the guest solvent in the Fe2+ spin state can anticipate the future applications of these compounds in solvent sensing.

Synthesis and characterization of new fluoride-containing manganese vanadates A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F

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

Sanjeewa, Liurukara D.; McGuire, Michael A.; Smith Pellizzeri, Tiffany M.

2016-09-15

Large single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO{sub 4}F{sub 2} building blocks. The A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed of zigzag chains ofmore » edge-sharing MnO{sub 4}F{sub 2} units running along the a-axis, and interconnected through V{sub 2}O{sub 7} pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn{sup 2+} indicated that Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} is antiferromagnetic with a Neél temperature, T{sub N}=~3 K and a Weiss constant, θ, of −11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}. Mn{sub 2}(VO{sub 4})F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn{sup 2+}. These interpenetrating chains are additionally connected through isolated VO{sub 4} tetrahedra to form the condensed structure. - Graphical abstract: New vanadate fluorides A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}(VO{sub 4})F have been synthesized hydrothermally. Upon cooling, the one-dimensional Mn(II) substructure results in antiferromagnetic ordering. Display Omitted - Highlights: • Single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}, (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown hydrothermally. • The use of fluoride mineralizers in the synthesis led to the formation of new compounds without OH{sup −} groups. • The structure of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} features zigzag chains of MnO{sub 4}F{sub 2} units. • Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} exhibits antiferromagnetic ordering with a Neel temperature of ~3 K. • Mn{sub 2}VO{sub 4}F possesses a condensed framework structure with disordered fluorine atoms.« less

40 CFR 180.379 - Fenvalerate; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 4/2/10 Almond, hulls 15.0 4/2/10 Apple 2.0 4/2/10 Artichoke, globe 0.2 4/2/10 Bean, dry, seed 0.25 4/2/10 Bean, snap, succulent 2.0 4/2/10 Broccoli 2.0 4/2/10 Blueberry 3.0 4/2/10 Cabbage 10.0 4/2/10...

KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid.

PubMed

Schlueter, John A; Geiser, Urs; Funk, Kylee A

2008-02-01

The title compound, poly[potassium [diaquapenta-micro(2)-dicyanamido-dicadmium(II)] dihydrate], {K[Cd(2)(C(2)N(3))(5)(H(2)O)(2)].2H(2)O}(n), contains two-dimensional anionic sheets of {[Cd(2){N(CN)(2)}(H(2)O)(2)](-)}(n) with a modified (6,3)-net (layer group cm2m, No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.

Robust hydrogen-bonded self-assemblies from biimidazole complexes. Synthesis and structural characterization of [M(biimidazole)2(OH2)2]2+ (M = Co2+, Ni2+) complexes and carboxylate modules.

PubMed

Atencio, Reinaldo; Chacón, Mirbel; González, Teresa; Briceño, Alexander; Agrifoglio, Giuseppe; Sierraalta, Anibal

2004-02-21

A robust heteromeric hydrogen-bonded synthon [R2(2) (9)-Id] is exploited to drive the modular self-assembly of four coordination complexes [M(H2biim)2(OH2)2]2+ (M = Co2+, Ni2+) and carboxylate counterions. This strategy allowed us to build molecular architectures of 0-, 1-, and 2-dimensions. A hydrogen-bonded 2D-network with cavities has been designed, which maintains its striking integrity after reversible water desorption-resorption processes.

The vanadium nitrogenase of Azotobacter chroococcum. Reduction of acetylene and ethylene to ethane.

PubMed Central

Dilworth, M J; Eady, R R; Eldridge, M E

1988-01-01

1. The vanadium (V-) nitrogenase of Azobacter chroococcum transfers up to 7.4% of the electrons used in acetylene (C2H2) reduction for the formation of ethane (C2H6). The apparent Km for C2H2 (6 kPa) is the same for either ethylene (C2H4) or ethane (C2H6) formation and much higher than the reported Km values for C2H2 reduction to C2H4 by molybdenum (Mo-) nitrogenases. Reduction of C2H2 in 2H2O yields predominantly [cis-2H2]ethylene. 2. The ratio of electron flux yielding C2H6 to that yielding C2H4 (the C2H6/C2H4 ratio) is increased by raising the ratio of Fe protein to VFe protein and by increasing the assay temperature up to at least 40 degrees C. pH values above 7.5 decrease the C2H6/C2H4 ratio. 3. C2H4 and C2H6 formation from C2H2 by V-nitrogenase are not inhibited by H2. CO inhibits both processes much less strongly than it inhibits C2H4 formation from C2H2 with Mo-nitrogenase. 4. Although V-nitrogenase also catalyses the slow CO-sensitive reduction of C2H4 to C2H6, free C2H4 is not an intermediate in C2H6 formation from C2H2. 5. Propyne (CH3C identical to CH) is not reduced by the V-nitrogenase. 6. Some implications of these results for the mechanism of C2H6 formation by the V-nitrogenase are discussed. PMID:3162672

Synthesis and structural characterisation of alkali metal complexes of heteroatom-stabilised 1,4- and 1,6-dicarbanions.

PubMed

Izod, Keith; Bowman, Lyndsey J; Wills, Corinne; Clegg, William; Harrington, Ross W

2009-05-07

A straightforward Peterson olefination reaction between either [{(Me(2)PhSi)(3)C}Li(THF)] or in situ-generated [(Me(3)Si)(2){Ph(2)P(BH(3))}CLi(THF)(n)] and paraformaldehyde gives the alkenes (Me(2)PhSi)(2)C[double bond, length as m-dash]CH(2) () and (Me(3)Si){Ph(2)P(BH(3))}C[double bond, length as m-dash]CH(2) (), respectively, in good yield. Ultrasonic treatment of with lithium in THF yields the lithium complex [{(Me(2)PhSi)(2)C(CH(2))}Li(THF)(n)](2) (), which reacts in situ with one equivalent of KOBu(t) in diethyl ether to give the potassium salt [{(Me(2)PhSi)(2)C(CH(2))}K(THF)](2) (). Similarly, ultrasonic treatment of with lithium in THF yields the lithium complex [[{Ph(2)P(BH(3))}(Me(3)Si)C(CH(2))]Li(THF)(3)](2).2THF (). The bis(phosphine-borane) [(Me(3)Si){Me(2)(H(3)B)P}CH(Me(2)Si)(CH(2))](2) () may be prepared by the reaction of [Me(2)P(BH(3))CH(SiMe(3))]Li with half an equivalent of ClSiMe(2)CH(2)CH(2)SiMe(2)Cl in refluxing THF. Metalation of with two equivalents of MeLi in refluxing THF yields the lithium complex [[{Me(2)P(BH(3))}(Me(3)Si)C{(SiMe(2))(CH(2))}]Li(THF)(3)](2) (), whereas metalation with two equivalents of MeK in cold diethyl ether yields the potassium complex [[{Me(2)P(BH(3))}(Me(3)Si)C{(SiMe(2))(CH(2))}](2)K(2)(THF)(4)](infinity) () after recrystallisation. X-Ray crystallography shows that, whereas the lithium complex crystallises as a discrete molecular species, the potassium complexes and crystallise as sheet and chain polymers, respectively.

On-surface Fenton and Fenton-like reactions appraised by paper spray ionization mass spectrometry.

PubMed

Resende, S F; Oliveira, B S; Augusti, R

2018-06-21

On-surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe 2+ / H 2 O 2 ) and Fenton-like (M n+ / H 2 O 2 ; M n+ = Fe 3+ , Co 2+ , Cu 2+ , Mn 2+ ) systems was investigated by using paper spray ionization mass spectrometry (PS-MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS-MS analyzes). The results indicated the following order in the rates of such reactions: Fe 2+ /H 2 O 2 > H 2 O 2 > Cu 2+ /H 2 O 2 > M n+ / H 2 O 2 (M n+ = Fe 3+ , Co 2+ , Mn 2+ ) ~ M n+ (M n+ = Fe 2+ , Fe 3+ , Co 2+ , Cu 2+ , Mn 2 . The superior capability of Fe 2+ /H 2 O 2 in causing the degradation of sildenafil indicates that Fe 2+ efficiently decomposes H 2 O 2 to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H 2 O 2 can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, i. e. Fe 3+ , Co 2+ , Cu 2+ and Mn 2+ . A unique oxidation by-product was detected in the reaction between Fe 2+ /H 2 O 2 with sildenafil and a possible structure for it was proposed based on the MS/MS data. The on-surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS-MS shown to be a convenient platform to promptly monitor on-surface oxidation reactions. This article is protected by copyright. All rights reserved.

The binding of carbon dioxide by horse haemoglobin

PubMed Central

Kilmartin, J. V.; Rossi-Bernardi, L.

1971-01-01

1. Three modified horse haemoglobins have been prepared: (i) αc2βc2, in which both the α-amino groups of the α- and β-chains have reacted with cyanate, (ii) αc2β2, in which the α-amino groups of the α-chains have reacted with cyanate, and (iii) α2βc2, in which the two α-amino groups of the β-chain have reacted with cyanate. 2. The values of n (the Hill constant) for αc2βc2, α2βc2 and αc2β2 were (respectively) 2.5, 2.0 and 2.6, indicating the presence of co-operative interactions between the haem groups for all derivatives. 3. In the alkaline pH range (about pH8.0) all the derivatives show the same charge as normal haemoglobin whereas in the acid pH range (about pH6.0) αc2βc2 differs by four protonic charges and αc2β2, α2βc2 by two protonic charges from normal haemoglobin, indicating that the expected number of ionizing groups have been removed. 4. αc2β2 and αc2βc2 show a 25% decrease in the alkaline Bohr effect, in contrast with α2βc2, which has the same Bohr effect as normal haemoglobin. 5. The deoxy form of αc2βc2 does not bind more CO2 than the oxy form of αc2βc2, whereas αc2β2 and α2βc2 show intermediate binding. 6. The results reported confirm the hypothesis that, under physiological conditions, haemoglobin binds CO2 through the four terminal α-amino groups and that the two terminal α-amino groups of α-chains are involved in the Bohr effect. ImagesPLATE 1 PMID:5166592

Abnormal end-tidal PO(2) and PCO(2) at the anaerobic threshold correlate well with impaired exercise gas exchange in patients with left ventricular dysfunction.

PubMed

Kano, Hiroto; Koike, Akira; Hoshimoto-Iwamoto, Masayo; Nagayama, Osamu; Sakurada, Koji; Suzuki, Takeya; Tsuneoka, Hidekazu; Sawada, Hitoshi; Aizawa, Tadanori; Wasserman, Karlman

2012-01-01

The aim of the present study was to compare the end-tidal O(2) pressure (PETO(2)) to end-tidal CO(2) pressure (PETCO(2)) in cardiac patients during rest and during 2 states of exercise: at anaerobic threshold (AT) and at peak. The purpose was to see which metabolic state, PETO(2) or PETCO(2), best correlated with exercise limitation. Thirty-eight patients with left ventricular (LV) ejection fraction <40% underwent cardiopulmonary exercise testing (CPX). PETO(2) and PETCO(2) were measured during CPX, along with peak O(2) uptake (VO(2)), AT, slope of the increase in ventilation (VE) relative to the increase in CO(2) output (VCO(2)) (VE vs. VCO(2) slope), and the ratio of the increase in VO(2) to the increase in work rate (ΔVO(2)/ΔWR). Both PETO(2) and PETCO(2) measured at AT were best correlated with peakVO(2), AT, ΔVO(2)/ΔWR and VE vs. VCO(2) slope. PETO(2) at AT correlated with reduced peak VO(2) (r=-0.60), reduced AT (r=-0.52), reduced ΔVO(2)/ΔWR (r=-0.55) and increased VE vs. VCO(2) slope (r=0.74). PETCO(2) at AT correlated with reduced peak VO(2) (r=0.67), reduced AT (r=0.61), reduced ΔVO(2)/ΔWR (r=0.58) and increased VE vs. VCO(2) slope (r=-0.80). PETCO(2) and PETO(2) at AT correlated with peak VO(2), AT and ΔVO(2)/ΔWR, but best correlated with increased VE vs. VCO(2) slope. PETO(2) and PETCO(2) at AT can be used as a prime index of impaired cardiopulmonary function during exercise in patients with LV failure.

Reduction of RuVI≡N to RuIII-NH3 by Cysteine in Aqueous Solution.

PubMed

Wang, Qian; Man, Wai-Lun; Lam, William W Y; Yiu, Shek-Man; Tse, Man-Kit; Lau, Tai-Chu

2018-05-21

The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru VI (N)(OH 2 )] + (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru III (NH 3 )(OH 2 )] + by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru VI (N)(OH 2 )] + + 3HSCH 2 CH(NH 3 )CO 2 → [(L)Ru III (NH 3 )(OH 2 )] + + 1.5(SCH 2 CH(NH 3 )CO 2 ) 2 . Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k 2 [1][Cys]. Studies on the effects of acidity indicate that both HSCH 2 CH(NH 3 + )CO 2 - and - SCH 2 CH(NH 3 + )CO 2 - are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a), [(L)Ru III (NH 2 SCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (3), and [(L)Ru IV (NH 2 )(OH 2 )] + (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 )(OH 2 )] + (2b) and [(L)Ru IV (NH 2 )(OH 2 )] + (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a) and the final ruthenium(III) ammine species, [(L)Ru III (NH 3 )(MeOH)] + (5) (where H 2 O was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.

Accession Medical Standards Analysis and Research Activity (AMSARA) 2015, Annual Report, and four Supplemental Applicants and Accessions Tables for: Army, Air Force, Marine, and Navy

DTIC Science & Technology

2016-03-11

1,705 2.2 975 2.1 384 2.5 284 3.0 Contact dermatitis and other eczema 1,558 2.0 1048 2.2 300 2.0 238 2.5 Corneal opacity and other disorders of...and cartilage 302 2.6 254 2.8 4 2.8 3 2.5 Contact dermatitis and other eczema 280 2.4 230 2.6 6 4.2 6 4.9 Curvature of spine 264 2.3 98 1.1 4 2.8 3...3.9 98 4.8 Affective psychoses 663 3.9 364 3.4 123 3.3 49 2.4 Curvature of spine 200 1.2 49 0.5 114 3.0 25 1.2 Contact dermatitis and other eczema

Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

NASA Technical Reports Server (NTRS)

Abel, Robert W.; Christiansen, Walter H.; Li, Jian-Guo

1988-01-01

A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

Nuclear factor erythroid 2-related factor 2 antioxidant response element pathways protect bovine mammary epithelial cells against H2O2-induced oxidative damage in vitro.

PubMed

Ma, Y F; Wu, Z H; Gao, M; Loor, J J

2018-06-01

The experiment was conducted to determine the role of nuclear factor (erythroid-derived 2)-like factor 2 (NFE2L2, formerly Nrf2) antioxidant response element (ARE) pathway in protecting bovine mammary epithelial cells (BMEC) against H 2 O 2 -induced oxidative stress injury. An NFE2L2 small interfering RNA (siRNA) interference or a pCMV6-XL5-NFE2L2 plasmid fragment was transfected to independently downregulate or upregulate expression of NFE2L2. Isolated BMEC in triplicate were exposed to H 2 O 2 (600 μM) for 6 h to induce oxidative stress before transient transfection with scrambled siRNA, NFE2L2-siRNA, pCMV6-XL5, and pCMV6-XL5-NFE2L2. Cell proliferation, apoptosis and necrosis rates, antioxidant enzyme activities, reactive oxygen species (ROS) and malondialdehyde (MDA) production, protein and mRNA expression of NFE2L2 and downstream target genes, and fluorescence activity of ARE were measured. The results revealed that compared with the control, BMEC transfected with NFE2L2-siRNA3 had proliferation rates that were 9 or 65% lower without or with H 2 O 2 , respectively. These cells also had apoptosis and necrosis rates that were 27 and 3.5 times greater with H 2 O 2 compared with the control group, respectively. In contrast, transfected pCMV6-XL5-NFE2L2 had proliferation rates that were 64.3% greater or 17% lower without or with H 2 O 2 compared with the control group, respectively. Apoptosis rates were 1.8 times lower with H 2 O 2 compared with the control. In addition, compared with the control, production of ROS and MDA and activities of superoxide dismutase (SOD), glutathione peroxidase (GSH-Px), catalase (CAT), and glutathione-S-transferase (GST) increased markedly in cells transfected with pCMV6-XL5-NFE2L2 and without H 2 O 2 . However, compared with the control, production of ROS and MDA and activity of CAT and GSH-Px increased markedly, whereas activities of SOD and GST decreased in cells transfected with pCMV6-XL5-NFE2L2 and incubated with H 2 O 2 . Compared with the control, cells transfected with NFE2L2-siRNA3 with or without H 2 O 2 had lower production of ROS and MDA and activity of SOD, CAT, GSH-Px, and GST. Cells transfected with pCMV6-XL5-NFE2L2 with or without H 2 O 2 had markedly higher protein and mRNA expression of NFE2L2, heme oxygenase-1 (HMOX-1), NADH quinone oxidoreductase 1, glutamate cysteine ligase catalytic subunit, and glutamyl cystine ligase modulatory subunit compared with the control incubations. Cells transfected with NFE2L2-siRNA3 without or with H 2 O 2 had markedly lower protein and mRNA expression of NFE2L2, HMOX-1, NADH quinone oxidoreductase 1, glutamyl cystine ligase modulatory subunit, and glutamate-cysteine ligase catalytic subunit compared with the control incubations. In addition, expression of HMOX-1 was 5.3-fold greater with H 2 O 2 compared with the control. Overall, results indicate that NFE2L2 plays an important role in the NFE2L2-ARE pathway via the control of HMOX-1. The relevant mechanisms in vivo merit further study. Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Aminotroponiminate calcium and strontium complexes.

PubMed

Datta, Simmi; Gamer, Michael T; Roesky, Peter W

2008-06-07

Heteroleptic aminotroponiminate complexes of calcium and strontium have been prepared. The monomeric calcium complex [((iPr)2ATI)CaI(THF)3] 1 ((iPr)2ATI = N-isopropyl-2-(isopropylamino)troponiminate) and the corresponding dimeric strontium compound [( (iPr)2ATI)SrI(THF)2]2 2 were obtained by reaction of [((iPr)2ATI)K] and MI2. Whereas the mixed ligand compound of composition [((iPr)2ATI)Ca(iPrAT)]2 3 (iPrAT = 2-(isopropylamino)troponate) was not obtained via a salt metathesis but by reaction of [Ca(N(SiMe3)2)2(THF)2] with ( (iPr)2ATI)H and (iPrAT)H, the diphosphanylamido complex [( (iPr)2ATI)Ca((Ph2P)2N)(THF)2] was obtained by reaction of CaI2 with the potassium compounds [( (iPr)2ATI)K] and [K(THF)n][N(PPh2)2]. The single crystal X-ray structures of all compounds were established and the latter compound shows a eta2-coordination mode of the ligand via the nitrogen and one phosphorus atom.

Synthesis and characterization of new fluoride-containing manganese vanadates A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F

NASA Astrophysics Data System (ADS)

Sanjeewa, Liurukara D.; McGuire, Michael A.; Smith Pellizzeri, Tiffany M.; McMillen, Colin D.; Ovidiu Garlea, V.; Willett, Daniel; Chumanov, George; Kolis, Joseph W.

2016-09-01

Large single crystals of A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO4F2 building blocks. The A2Mn2V2O7F2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb2Mn2V2O7F2: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs2Mn2V2O7F2: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed of zigzag chains of edge-sharing MnO4F2 units running along the a-axis, and interconnected through V2O7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn2+ indicated that Cs2Mn2V2O7F2 is antiferromagnetic with a Neél temperature, TN=~3 K and a Weiss constant, θ, of -11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V-O vibrational modes in Cs2Mn2V2O7F2. Mn2(VO4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn2+. These interpenetrating chains are additionally connected through isolated VO4 tetrahedra to form the condensed structure.

Synthesis and characterization of new fluoride-containing manganese vanadates A 2Mn 2V 2O 7F 2 (A=Rb, Cs) and Mn 2VO 4F

DOE PAGES

Sanjeewa, Liurukara D.; McGuire, Michael A.; Smith Pellizzeri, Tiffany M.; ...

2016-05-10

In large single crystals of A 2Mn 2V 2O 7F 2 (A=Rb, Cs) and Mn 2VO 4F were grown using a high-temperature (~600 °C) hydrothermal technique. We utilized single crystal X-ray diffraction and powder X-ray diffraction in order to characterize the structures, which both possess MnO 4F 2 building blocks. The A 2Mn 2V 2O 7F 2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb 2Mn 2V 2O 7F 2: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs 2Mn 2V 2O 7F 2: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed ofmore » zigzag chains of edge-sharing MnO 4F 2 units running along the a-axis, and interconnected through V 2O 7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn 2+ indicated that Cs 2Mn 2V 2O 7F 2 is antiferromagnetic with a Neél temperature, TN=~3 K and a Weiss constant, θ, of -11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs 2Mn 2V 2O 7F 2. Mn 2(VO 4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn 2+. Our interpenetrating chains are additionally connected through isolated VO 4 tetrahedra to form the condensed structure.« less

40 CFR 180.364 - Glyphosate; tolerances for residues.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., globe 0.2 Asparagus 0.5 Atemoya 0.2 Avocado 0.2 Bamboo, shoots 0.2 Banana 0.2 Barley, bran 30 Beet... 0.2 Ginger, white, flower 0.2 Gourd, buffalo, seed 0.1 Governor's plum 0.2 Gow kee, leaves 0.2 Grain... Mamey apple 0.2 Mango 0.2 Mangosteen 0.2 Marmaladebox 0.2 Mioga, flower 0.2 Noni 0.20 Nut, pine 1.0 Nut...

Prototype Software Assurance Framework (SAF): Introduction and Overview

DTIC Science & Technology

2017-04-05

Introduction 1 1 Process Management (Category 1) 6 1.1 Process Definition (Area 1.1) 6 1.2 Infrastructure Standards (Area 1.2) 6 1.3 Resources (Area 1.3) 7...1.4 Training (Area 1.4) 8 2 Project Management (Category 2) 9 2.1 Project Plans (Area 2.1) 9 2.2 Project Infrastructure (Area 2.2) 10 2.3 Project...Monitoring (Area 2.3) 10 2.4 Project Risk Management (Area 2.4) 11 2.5 Supplier Management (Area 2.5) 11 3 Engineering (Category 3) 13 3.1 Product

Study of Three Dimensional Transonic Flow Separations.

DTIC Science & Technology

1988-04-01

22222222222222222222222222222222222222 CD22 2 NN 22 0 2 2 C 22 .2 2 .2 .2 .2 .’ 22 . . . cD( C) DC)C DC D CC 222 2 22 2 2- C 2 22 22 22 - 22 02 N NT NL z...In1.0 INco (N -.- L’ c3 107 :-I--cnr -! - - N N 1 f;CC-7 cD c, 222 c222 cN -) H22 o cc -- -4 0,2222222" (D2 C22 22 D2 220 CD22 CD 2 CD CD N22 22D2

iMAST Quarterly, Number 2, 2000

DTIC Science & Technology

2000-01-01

Metal Iron N2 Metal Niobium N2 Metal Al12Si N2 Metal Al6061 N2 Metal CCC (Al 9Ce 5Cr 2.8 Co) N2 Metal Pech 1 (Al 12 Zn 3Mg 1 Cu 0.25Mn N2 Metal...Cu 38Ni N2 Metal Nichrome (80/20) N2 Metal Ni 5Al N2 Metal Cr3 C2 –25Ni Cr N2 Metal Co 29Cr 6Al 1Y (Amdry 920) N2 Metal Co 32Ni 20Cr 8Al N2 Metal 316...St. Steel N2 Metal Ancorsteel 1000 N2 Metal Ti 35Zr 10Nl N2 Metal Al Alloys + SiC (15%) (No. 12-17) N2 Metal Al, Zn + 10-15% HA N2 Metal (HA

Synthesis of magnetic Bi2O2CO3/ZnFe2O4 composite with improved photocatalytic activity and easy recyclability

NASA Astrophysics Data System (ADS)

Liu, Yumin; Ren, Hao; Lv, Hua; Guang, Jing; Cao, Yafei

2018-03-01

Magnetic Bi2O2CO3/ZnFe2O4 heterojunction photocatalysts with varying content of ZnFe2O4 were constructed by modifying Bi2O2CO3 nanosheets with mesoporous ZnFe2O4 nanoparticles. The photoactivity of the products was investigated by decomposing RhodamineB (RhB) and it was found that the photoactivity of Bi2O2CO3/ZnFe2O4 composite was closely related to the loading amount of ZnFe2O4. Under simulant sunlight irradiation, the optimum photoactivity of Bi2O2CO3/ZnFe2O4 composite was almost 2.3 and 2.1 times higher than that by bare ZnFe2O4 and Bi2O2CO3, respectively. The improved photoactivity resulted from the synergistic effect of Bi2O2CO3 and ZnFe2O4, which not only extended the photoabsorption region but also significantly facilitated the interfacial charge transfer. Besides the high photocatalytic performance, Bi2O2CO3/ZnFe2O4 composite also exhibited excellent stable and recycling properties, which enabled it have great potential in a long-term practical use.

Nitrate-to-nitrite-to-nitric oxide conversion modulated by nitrate-containing {Fe(NO)2}9 dinitrosyl iron complex (DNIC).

PubMed

Tsai, Fu-Te; Lee, Yu-Ching; Chiang, Ming-Hsi; Liaw, Wen-Feng

2013-01-07

Nitrosylation of high-spin [Fe(κ(2)-O(2)NO)(4)](2-) (1) yields {Fe(NO)}(7) mononitrosyl iron complex (MNIC) [(κ(2)-O(2)NO)(κ(1)-ONO(2))(3)Fe(NO)](2-) (2) displaying an S = 3/2 axial electron paramagnetic resonance (EPR) spectrum (g(⊥) = 3.988 and g(∥) = 2.000). The thermally unstable nitrate-containing {Fe(NO)(2)}(9) dinitrosyl iron complex (DNIC) [(κ(1)-ONO(2))(2)Fe(NO)(2)](-) (3) was exclusively obtained from reaction of HNO(3) and [(OAc)(2)Fe(NO)(2)](-) and was characterized by IR, UV-vis, EPR, superconducting quantum interference device (SQUID), X-ray absorption spectroscopy (XAS), and single-crystal X-ray diffraction (XRD). In contrast to {Fe(NO)(2)}(9) DNIC [(ONO)(2)Fe(NO)(2)](-) constructed by two monodentate O-bound nitrito ligands, the weak interaction between Fe(1) and the distal oxygens O(5)/O(7) of nitrato-coordinated ligands (Fe(1)···O(5) and Fe(1)···O(7) distances of 2.582(2) and 2.583(2) Å, respectively) may play important roles in stabilizing DNIC 3. Transformation of nitrate-containing DNIC 3 into N-bound nitro {Fe(NO)}(6) [(NO)(κ(1)-NO(2))Fe(S(2)CNEt(2))(2)] (7) triggered by bis(diethylthiocarbamoyl) disulfide ((S(2)CNEt(2))(2)) implicates that nitrate-to-nitrite conversion may occur via the intramolecular association of the coordinated nitrate and the adjacent polarized NO-coordinate ligand (nitrosonium) of the proposed {Fe(NO)(2)}(7) intermediate [(NO)(2)(κ(1)-ONO(2))Fe(S(2)CNEt(2))(2)] (A) yielding {Fe(NO)}(7) [(NO)Fe(S(2)CNEt(2))(2)] (6) along with the release of N(2)O(4) (·NO(2)) and the subsequent binding of ·NO(2) to complex 6. The N-bound nitro {Fe(NO)}(6) complex 7 undergoes Me(2)S-promoted O-atom transfer facilitated by imidazole to give {Fe(NO)}(7) complex 6 accompanied by release of nitric oxide. This result demonstrates that nitrate-containing DNIC 3 acts as an active center to modulate nitrate-to-nitrite-to-nitric oxide conversion.

Polyoxometal cations within polyoxometalate anions. Seven-coordinate uranium and zirconium heteroatom groups in [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14-

NASA Astrophysics Data System (ADS)

Gaunt, Andrew J.; May, Iain; Collison, David; Travis Holman, K.; Pope, Michael T.

2003-08-01

Two new composite polyoxotungstate anions with unprecedented structural features, [(UO2)12(μ3-O)4(μ2-H2O)12(P2W15O56)4]32- (1) and [Zr4(μ3-O)2(μ2-OH)2(H2O)4 (P2W16O59)2]14- (2) contain polyoxo-uranium and -zirconium clusters as bridging units. The anions are synthesized by reaction of Na12[P2W15O56] with solutions of UO2(NO3)2 and ZrCl4. The structure of 1 in the sodium salt contains four [P2W15O56]12- anions assembled into an overall tetrahedral cluster by means of trigonal bridging groups formed by three equatorial-edge-shared UO7 pentagonal bipyramids. The structure of anion 2 consists of a centrosymmetric assembly of two [P2W16O59]12- anions linked by a {Zr4O2(OH)2(H2O)4}10+ cluster. Both complexes in solution yield the expected two-line 31P-NMR spectra with chemical shifts of -2.95, -13.58 and -6.45, -13.69 ppm, respectively.

Computational Studies of Solubilities of LiO 2 and Li 2O 2 in Aprotic Solvents

DOE PAGES

Cheng, Lei; Redfern, Paul; Lau, Kah Chun; ...

2017-08-12

Knowledge of the solubilities of Li 2O 2 and LiO 2 in aprotic solvents is important for insight into the discharge and charge processes of Li-O 2 batteries, but these quantities are not well known. In this contribution, the solvation free energies of molecular LiO 2 and Li 2O 2 in various organic solvents were calculated using various explicit and implicit solvent models, as well as ab initio molecular dynamics (AIMD) methods. Best estimates for the solvation energies from these calculations along with calculated lattice energies of Li 2O 2 and LiO 2 were used to determine the solubility ofmore » bulk LiO 2 and Li 2O 2. The computed solubility of LiO 2 (1.8 × 10 -2 M) is about 15 orders higher than that of Li 2O 2 (2.0 × 10 -17 M) due to a much less negative lattice energy of bulk LiO 2 compared to that of Li 2O 2. The difference in solubilities between LiO 2 and Li 2O 2 likely will affect the nucleation and growth mechanisms and resulting morphologies of the products formed during battery discharge, influencing the performance of the battery cell. In conclusion, the calculated LiO 2 and Li 2O 2 solubilities provide important information for fundamental studies of discharge and charge chemistries in Li-O 2 batteries.« less

Computational Studies of Solubilities of LiO 2 and Li 2O 2 in Aprotic Solvents

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

Cheng, Lei; Redfern, Paul; Lau, Kah Chun

Knowledge of the solubilities of Li 2O 2 and LiO 2 in aprotic solvents is important for insight into the discharge and charge processes of Li-O 2 batteries, but these quantities are not well known. In this contribution, the solvation free energies of molecular LiO 2 and Li 2O 2 in various organic solvents were calculated using various explicit and implicit solvent models, as well as ab initio molecular dynamics (AIMD) methods. Best estimates for the solvation energies from these calculations along with calculated lattice energies of Li 2O 2 and LiO 2 were used to determine the solubility ofmore » bulk LiO 2 and Li 2O 2. The computed solubility of LiO 2 (1.8 × 10 -2 M) is about 15 orders higher than that of Li 2O 2 (2.0 × 10 -17 M) due to a much less negative lattice energy of bulk LiO 2 compared to that of Li 2O 2. The difference in solubilities between LiO 2 and Li 2O 2 likely will affect the nucleation and growth mechanisms and resulting morphologies of the products formed during battery discharge, influencing the performance of the battery cell. In conclusion, the calculated LiO 2 and Li 2O 2 solubilities provide important information for fundamental studies of discharge and charge chemistries in Li-O 2 batteries.« less

Metal aminocarboxylate coordination polymers with chain and layered structures.

PubMed

Dan, Meenakshi; Rao, C N R

2005-11-18

The synthesis and structures of metal aminocarboxylates prepared in acidic, neutral, or alkaline media have been explored with the purpose of isolating coordination polymers with linear chain and two-dimensional layered structures. Metal glycinates of the formulae [CoCl2(H2O)2(CO2CH2NH3)] (I), [MnCl2(CO2CH2NH3)2] (II), and [Cd3Cl6(CO2CH2NH3)4] (III) with one-dimensional chain structures have been obtained by the reaction of the metal salts with glycine in an acidic medium under hydro/solvothermal conditions. These chain compounds contain glycine in the zwitterionic form. 4-Aminobutyric acid transforms to a cyclic amide under such reaction conditions, and the amide forms a chain compound of the formula [CdBr2(C4H7NO)2] (IV). Glycine in the zwitterionic form also forms a two-dimensional layered compound of the formula [Mn(H2O)2(CO2CH2NH3)2]Br2 (V). 6-Aminocaproic acid under alkaline conditions forms layered compounds with metals at room temperature, the metal being coordinated both by the amino nitrogen and the carboxyl oxygen atoms. Of the two layered compounds [Cd{CO2(CH2)5NH2}2]2 H2O (VI) and [Cu{CO2(CH2)5NH2}2]2 H2O (VII), the latter has voids in which water molecules reside.

Structures of M2(SO2)6B12F12 (M = Ag or K) and Ag2(H2O)4B12F12: Comparison of the Coordination of SO2 versus H2O and of B12F122- versus Other Weakly Coordinating Anions to Metal Ions in the Solid State.

PubMed

Malischewski, Moritz; Peryshkov, Dmitry V; Bukovsky, Eric V; Seppelt, Konrad; Strauss, Steven H

2016-12-05

The structures of three solvated monovalent cation salts of the superweak anion B 12 F 12 2- (Y 2- ), K 2 (SO 2 ) 6 Y, Ag 2 (SO 2 ) 6 Y, and Ag 2 (H 2 O) 4 Y, are reported and discussed with respect to previously reported structures of Ag + and K + with other weakly coordinating anions. The structures of K 2 (SO 2 ) 6 Y and Ag 2 (SO 2 ) 6 Y are isomorphous and are based on expanded cubic close-packed arrays of Y 2- anions with M(OSO) 6 + complexes centered in the trigonal holes of one expanded close-packed layer of B 12 centroids (⊙). The K + and Ag + ions have virtually identical bicapped trigonal prism MO 6 F 2 coordination spheres, with M-O distances of 2.735(1)-3.032(2) Å for the potassium salt and 2.526(5)-2.790(5) Å for the silver salt. Each M(OSO) 6 + complex is connected to three other cationic complexes through their six μ-SO 2 -κ 1 O,κ 2 O' ligands. The structure of Ag 2 (H 2 O) 4 Y is unique [different from that of K 2 (H 2 O) 4 Y]. Planes of close-packed arrays of anions are offset from neighboring planes along only one of the linear ⊙···⊙···⊙ directions of the close-packed arrays, with [Ag(μ-H 2 O) 2 Ag(μ-H 2 O) 2 )] ∞ infinite chains between the planes of anions. There are two nearly identical AgO 4 F 2 coordination spheres, with Ag-O distances of 2.371(5)-2.524(5) Å and Ag-F distances of 2.734(4)-2.751(4) Å. This is only the second structurally characterized compound with four H 2 O molecules coordinated to a Ag + ion in the solid state. Comparisons with crystalline H 2 O and SO 2 solvates of other Ag + and K + salts of weakly coordinating anions show that (i) N[(SO 2 ) 2 (1,2-C 6 H 4 )] - , BF 4 - , SbF 6 - , and Al(OC(CF 3 ) 3 ) 4 - coordinate much more strongly to Ag + than does Y 2- , (ii) SnF 6 2- coordinates somewhat more strongly to K + than does Y 2- , and (iii) B 12 Cl 12 2- coordinates to K + about the same as, if not slightly weaker than, Y 2- .