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Specifications and qualification tests data are presented for over eleven hundred T3 case all-tantalum capacitors encompassing four ratings. The finalized product has all the advantages of the silver cased wet and is capable of withstanding some reverse potential ac ripple current.
An experimental investigation of adhesively bonded composite joint was conducted to characterize the debond growth mechanism under mode II static and fatigue loadings. For this purpose, end-notched flexure specimens of graphite/epoxy (T300/5208) adherends bonded with EC 3445 adhesive were tested. In all specimen tested, the fatigue failure occurred in the form of cyclic debonding. The present study confirmed the result of previous studies that total strain-energy-release rate is the driving parameter for cyclic debonding. Further, the debond growth resistance under cyclic loading with full shear reversal (i.e., stress ratio, R = -1) is drastically reduced in comparison to the case when subjected to cyclic shear loading with no shear reversal (i.e., R = 0.1).
The serious scientific debate about spontaneous generation which raged for centuries reached a climax in the nineteenth century with the work of Spallanzani, Schwann, Tyndall, and Pasteur. These investigators demonstrated that spontaneous generation from dead organic matter does not occur. Although no aspects of these experiments addressed the issue of whether organic compounds could be synthesized abiotically, the impact of the experiments was great enough to cause many investigators to assume that life and its organic compounds were somehow fundamentally different than inorganic compounds. Meanwhile, other nineteenth-century investigators were showing that organic compounds could indeed be synthesized from inorganic compounds. In 1828 Friedrich Wohler synthesized urea in an attempt to form ammonium cyanate by heating a solution containing ammonia and cyanic acid. This experiment is generally recognized to be the first to bridge the artificial gap between organic and inorganic chemistry, but it also showed the usefulness of heat in organic synthesis. Not only does an increase in temperature enhance the rate of urea synthesis, but Walker and Hambly showed that equilibrium between urea and ammonium cyanate was attainable and reversible at 100 C. Wohler's synthesis of urea, and subsequent syntheses of organic compounds from inorganic compounds over the next several decades dealt serious blows to the 'vital force' concept which held that: (1) organic compounds owe their formation to the action of a special force in living organisms; and (2) forces which determine the behavior of inorganic compounds play no part in living systems. Nevertheless, such progress was overshadowed by Pasteur's refutation of spontaneous generation which nearly extinguished experimental investigations into the origins of life for several decades. Vitalism was dealt a deadly blow in the 1950's with Miller's famous spark-discharge experiments which were undertaken in the framework of the Oparin and Haldane hypotheses concerning the origin of life. These hypotheses were constructed on some basic assumptions which included a reduced atmosphere, and a low surface temperature for the early Earth. These ideas meshed well with the prevailing hypothesis of the 1940's and 50's that the Earth had formed through heterogeneous accretion of dust from a condensing solar nebula. Miller's experiments were extremely successful, and were followed by numerous other experiments by various investigators who employed a wide variety of energy sources for abiotic synthesis including spark discharges, ultra-violet radiation, heat, shock waves, plasmas, gamma rays, and other forms of energy. The conclusion reached from this body of work is that energy inputs can drive organic synthesis from a variety of inorganic starting materials.
The cyclic deformation behavior of a wrought cobalt-base superalloy, Haynes 188, has been investigated over a range of temperatures between 25 and 1000 C under isothermal and in-phase thermomechanical fatigue (TMF) conditions. Constant mechanical strain rates (epsilon-dot) of 10(exp -3)/s and 10(exp -4)/s were examined with a fully reversed strain range of 0.8%. Particular attention was given to the effects of dynamic strain aging (DSA) on the stress-strain response and low cycle fatigue life. A correlation between cyclic deformation behavior and microstructural substructure was made through detailed transmission electron microscopy. Although DSA was found to occur over a wide temperature range between approximately 300 and 750 C the microstructural characteristics and the deformation mechanisms responsible for DSA varied considerably and were dependent upon temperature. In general, the operation of DSA processes led to a maximum of the cyclic stress amplitude at 650 C and was accompanied by pronounced planar slip, relatively high dislocation density, and the generation of stacking faults. DSA was evidenced through a combination of phenomena, including serrated yielding, an inverse dependence of the maximum cyclic hardening with epsilon-dot, and an instantaneous inverse epsilon-dot sensitivity verified by specialized epsilon-dot -change tests. The TMF cyclic hardening behavior of the alloy appeared to be dictated by the substructural changes occuring at the maximum temperature in the TMF cycle.
The Lorentz body force induced in electrically conducting fluids can be utilized for a number of materials processing technologies. An application of strong static magnetic fields can be beneficial for damping convection present during solidification. On the other hand, alternating magnetic fields can be used to reduce as well as to enhance convection. However, only special types of time dependent magnetic fields can induce a non-zero time averaged Lorentz force needed for convection control. One example is the rotating magnetic field. This field configuration induces a swirling flow in circular containers. Another example of a magnetic field configuration is the traveling magnetic field (TMF). It utilizes axisymmetric magnetostatic waves. This type of field induces an axial recirculating flow that can be advantageous for controlling axial mass transport, such as during solidification in long cylindrical tubes. Incidentally, this is the common geometry for crystal growth research. The Lorentz force induced by TMF can potentially counter-balance the buoyancy force, diminishing natural convection, or even setting up the flow in reverse direction. Crystal growth process in presence of TMF can be then significantly modified. Such properties as the growth rate, interface shape and macro segregation can be affected and optimized. Melt homogenization is the other potential application of TMF. It is a necessary step prior to solidification. TMF can be attractive for this purpose, as it induces a basic flow along the axis of the ampoule. TMF can be a practical alloy mixing method especially suited for solidification research in space. In the theoretical part of this work, calculations of the induced Lorentz force in the whole frequency range have been completed. The basic flow characteristics for the finite cylinder geometry are completed and first results on stability analysis for higher Reynolds numbers are obtained. A theoretical model for TMF mixing is also developed. In the experimental part, measurements of flow induced by TMF in a column of mercury (Hg) are presented. Also, an alloy mixing of Bi-Sn of the eutectic composition is demonstrated. A traveling magnetic field of 4mT at 3kHz applied for 120 minutes is found to be sufficient to homogenize an alloy enclosed in a 1cm diameter and 12 cm long tube.
Many DOE remediation sites have chemicals of concern that are compounds in higher oxidation states, which make them both more mobile and more toxic. The chemical reduction of these compounds both prevents the migration of these chemicals and in some cases reduces the toxicity. It has also been shown that zero-valent iron is a very effective substance to use in reducing oxygenated compounds in various treatment processes. These have included the treatment of halogenated hydrocarbons in the form volatile organic compounds used as solvents and pesticides. Zero-valent iron has also been used to reduce various oxidized metals such as chromium, arsenic, and mercury in order to immobilize them, decrease their toxicity, and prevent further transport. In addition, it has been used to immobilize or break down other non-metallic species such as selenium compounds and nitrates. Of particular interest at several DOE remediation sites is the fact that zero-valent iron is very effective in immobilizing several radioactive metals which are mobile in their oxidized states. These include both technetium and uranium. The main difficulty in using zero-valent iron has been its tendency to become inactive after relatively short periods of time. While it is advantageous to have the zero-valent iron particles as porous as possible in order to provide maximum surface area for reactions to take place, these pores can become clogged when the iron is oxidized. This is due to the fact that ferric oxide has a greater volume for a given mass than metallic iron. When the surfaces of the iron particles oxidize to ferric oxide, the pores become narrower and will eventually shut. In order to minimize the degradation of the chemical activity of the iron due to this process, a modification of zero-valent iron has been developed which prevents or slows this process, which decreases its effectiveness. It is called sulfur-modified iron, and it has been produced in high purity for applications in municipal water treatment applications. Sulfur-modified iron has been found to not only be an extremely economical treatment technology for municipal water supplies, where very large quantities of water must be treated economically, but it has also been demonstrated to immobilize technetium. It has the added benefit of eliminating several other harmful chemicals in water supplies. These include arsenic and selenium. In one large-scale evaluation study an integrated system implemented chemical reduction of nitrate with sulfur-modified iron followed by filtration for arsenic removal. The sulfur-modified iron that was used was an iron-based granular medium that has been commercially developed for the removal of nitrate, co-contaminants including uranium, vanadium and chromium, and other compounds from water. The independent study concluded that 'It is foreseen that the greatest benefit of this technology (sulfur-modified iron) is that it does not produce a costly brine stream as do the currently accepted nitrate removal technologies of ion exchange and reverse osmosis. This investigation confirmed that nitrate reduction via sulfur-modified iron is independent of the hydraulic loading rate. Future sulfur-modified iron treatment systems can be designed without restriction of the reactor vessel dimensions. Future vessels can be adapted to existing site constraints without being limited to height-to-width ratios that would exist if nitrate reduction were to depend on hydraulic loading rate'. Sulfur-modified iron was studied by the Pacific Northwest National Laboratory (PNNL) for its effectiveness in the reduction and permanent sequestration of technetium. The testing was done using Hanford Site groundwater together with sediment. The report stated, 'Under reducing conditions, TcO{sub 4} is readily reduced to TcIV, which forms highly insoluble oxides such at TcO{sub 2}.nH{sub 2}O. However, (re)oxidation of TcIV oxides can lead to remobilization. Under sulfidogenic conditions, most TcIV will be reduced and immobilized as Tc{sub 2}S{sub 7}, which is less readily re-mobilized, even under oxic conditions. This process should be favored by stimulation of sulfidogenic conditions'. The sulfur-modified iron provides the sulfur, together with the iron, to maintain this stable sequestration of technetium. As a result of these and other studies demonstrating the cost-effectiveness of sulfur-modified iron in treating technetium and other hazardous compounds in Hanford Site groundwater and its cost-effectiveness in reducing nitrate, the Richland Operations Office of the Department of Energy issued a change order to the Central Plateau Contractor providing for the testing of sulfur-modified iron in a mobile pilot unit at the Hanford Site. Further testing is anticipated to produce refinements in operating conditions and further optimization of the existing process. (authors)
The best solution to address the critical durability issue of solid oxide electrolytic cells (SOECs) for high-efficiency and high-rate H 2 production is to lower the operating temperature without sacrificing the performance. Developing high performance oxygen electrodes (OEs) is a key to capitalizing this solution. Here, in this paper, we report on a highly active OE for intermediate temperature ZrO 2 -based SOECs without a CeO 2 barrier layer. The new barrier-layer-free (BLF) OE is a composite of two materials, (Bi 0.75 Y 0.25 ) 0.93 Ce 0.07 O 1.5±δ (BYC) that exhibits high oxide-ion conductivity and La 0.8 Sr 0.2 MnO 3 (LSM) that possesses a high electronic conductivity to enable fast oxygen reduction/evolution reactions (ORR/OER). Featuring a microscale porous BYC scaffold decorated with high surface area LSM nanoparticles (NPs), the new BLF-OE exhibited a low area specific resistance (ASR) of 0.10 Ω cm 2 at 650 °C in air. With 50%H 2 -50%H 2 O as a feed to hydrogen electrode (HE) and air to OE, the single cell performance achieved 588 mA cm -2 at 0.80 V in the fuel cell mode and 688 mA cm -2 at 1.30 V in the electrolytic mode at 650 °C. Our in-house testing showed that this level of performance was ~3.5x higher than the cell with the benchmark La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ -Ce 0.9 Gd 0.1 O 2-δ OE. The long-term durability testing under alternating fuel cell and electrolytic modes showed a low degradation rate of 0.10 mA cm -2 h -1 over 550 hours. These encouraging results showed the great promise of the newly developed BYC-LSM to be an excellent OE candidate for intermediate temperature SOECs.
The Georgia Institute of Technology group has performed studies to characterize the thermal hydraulics of a single “finger” module of the helium-cooled modular divertor with multiple jets (HEMJ) proposed for long-pulse magnetic fusion reactors in a helium (He) loop designed with maximum mass flow rate of 10 g/s. However, testing divertor modules at prototypical heat fluxes and temperatures remains an engineering challenge. A new larger helium loop with a maximum mass flow rate of 100 g/s, suitable for evaluating helium-cooled divertors with larger surface areas such as a nine-finger HEMJ module, is currently being constructed. This work presents an experimental validation of a numerical model exploring the applicability of the “reversed heat flux approach,” which cools (versus heats) the plasma-facing surface of the divertor module to evaluate the helium-side heat transfer coefficient (HTC). The approach is to be used for performance evaluation of single and multiple modules of HEMJ in existing and future large helium loops. A cooling facility for producing a jet of water with a maximum mass flow rate of 1.4 kg/s at a maximum pressure of 0.4 MPa and temperature of 295 K (Re = 2.2 × 10 5 ) is described. Numerical and experimental results are presented for the heat flux and average helium impingement surface temperature over a range of water flow rates (0.5 to 1.4 kg/s) for heat fluxes as high as 5 MW/m 2 . The numerical model suggests that the HTC of the water impingement surface is comparable to or greater than that of the helium impingement surface. For given helium and water temperatures, the heat flux values are generally limited by conduction across the outer shell. These initial studies provide guidance on extending this approach to estimating the thermal-hydraulic performance of larger divertor module designs while reducing the challenges associated with studying such designs in the normal heating configuration at their extremely high prototypical temperatures and incident heat fluxes.
Previous work comparing power take-off (PTO) architectures for ocean wave-powered reverse osmosis suggests that variable displacement in the wave energy converter (WEC)-driven pump does not offer a significant performance advantage. A limitation of that study is that the WEC was subject to a constant load within a given sea state (“Coulomb damping”) and did not account for controlled, moment-to-moment variation of the PTO load enabled by a variable displacement pump. This study explores the potential performance advantage of a variable PTO load over Coulomb damping. Model predictive control is used to provide optimal load control with constraints on the PTO load. The constraints include minimum and maximum loads and a limit on the rate of load adjustment. Parameter studies on these constraints enable conclusions about PTO design requirements in addition to providing an estimated performance advantage over Coulomb damping. Numerical simulation of the Oyster 1 WEC is carried out with performance weighted by historical sea state data from Humboldt Bay, CA. The results show a performance advantage of up to 20% higher yearly-average power absorption over Coulomb damping. Additionally, the parameter studies suggest that the PTO load should be adjustable down to at least 25% of the maximum load and should be adjustable between the minimum and maximum loads within a few seconds.
Significance Catalytic hydrogenation and dehydrogenation reactions are extremely important in organic chemistry and recently for energy storage in the form of chemical bonds. Although catalysts are known which catalyze both reactions, the rates and conditions required for the two are frequently very different due to the differences associated with the bonds to be activated (C–H/O–H/N–H and C = O/C = N/H–H). The use of a bifunctional catalyst would substantially simplify the design of processes related to energy storage. In this work, organometallic complexes of iron and iridium are shown to act as catalysts for reversible dehydrogenation of alcohols to carbonyl compounds. This finding opens a pathway to the development of catalysts for direct reversible electrochemical dehydrogenation of organic fuels in energy generation and storage reactions.
Cellulase enzymes deconstruct recalcitrant cellulose into soluble sugars, making them a biocatalyst of biotechnological interest for use in the nascent lignocellulosic bioeconomy. Cellobiohydrolases (CBHs) are cellulases capable of liberating many sugar molecules in a processive manner without dissociating from the substrate. Within the complete processive cycle of CBHs, dissociation from the cellulose substrate is rate limiting, but the molecular mechanism of this step is unknown. Here, we present a direct comparison of potential molecular mechanisms for dissociation via Hamiltonian replica exchange molecular dynamics of the model fungal CBH, Trichoderma reesei Cel7A. Computational rate estimates indicate that stepwise cellulose dethreading from the binding tunnel is 4 orders of magnitude faster than a clamshell mechanism, in which the substrate-enclosing loops open and release the substrate without reversing. We also present the crystal structure of a disulfide variant that covalently links substrate-enclosing loops on either side of the substrate-binding tunnel, which constitutes a CBH that can only dissociate via stepwise dethreading. Biochemical measurements indicate that this variant has a dissociation rate constant essentially equivalent to the wild type, implying that dethreading is likely the predominant mechanism for dissociation.
Using Molecular Dynamics simulations, we investigate the effect of alternating (AC) electric field on static and dynamic properties of water. Here, the central question we address is how hydrogen bonds respond to perpetual field-induced dipole reorientations. We assess structural perturbations of water network and changes of hydrogen bond dynamics in a range of alternating electric field strengths and frequencies using a non-polarizable water model, SPC/E, and two distinct polarizable models: SWM4-NDP and BK3. We confirm that AC field causes only moderate structural perturbations. Dynamic properties, including the rates of bond breaking, switching of hydrogen-bonding partners, and diffusion, accelerate with the strength of AC fields. All models reveal a nonmonotonic frequency dependence with fastest dynamics at frequencies around 200 GHz where the period of the field oscillation is commensurate with the average time it takes a typical proton to switch from one acceptor to another. Higher frequencies result in smaller amplitudes of angle oscillations and in reduced probability to complete the switch to another acceptor before the field reversal restores the original configuration. As frequency increases, these effects gradually weaken the influence of the field on the kinetics of hydrogen bonding and the associated rates of translational and rotational diffusion in water.
Cells utilizing the organic electrolyte, NaI in triglyme, operated at approx. 130 C with Na(+) - intercalating cathodes. However, their rate and stability were inadequate. NaAlCl4 was found to be a highly useful electrolyte for cell operation at 165-190 C. Na(+) intercalating chalcogenides reacted with NaAlCl4 during cycling to form stable phases. Thus, VS2 became essentially VS2Cl, with reversible capacity of approx 2.8 e(-)/V, and a mid-discharge voltage of approx 2.5V and 100 deep discharge cycles were readily achieved. A positive electrode consisting of VCl3 and S plus NaAlCl4 was subjected to deep-discharge cycles 300 times and it demonstrated identity with the in-situ-formed BSxCly cathode. NiS2 and NiS which are not Na(+)-intercalating structures formed highly reversible electrodes in NaAlCl4. The indicated discharge mechanism implies a theoretical capacity 4e(-)/Ni for NiS2 and 2e(-)/Ni for NiS. The mid-discharge potentials are, respectively, 2.4V and 2.1V. A Na/NiS2 cell cycling at a C/5 rate has exceeded 500 deep discharge cycles with 2.5e(-)/Ni average utilization. A 4 A-hr nominal capacity prototype Na/NiS2 cell was tested at 190 C. It was voluntarily terminated after 80 cycles. Further development, particularly of cathode structure and hardware should produce a battery capable of at least 50-W-hr/lb and more than 1000 cycles.
Regarding new bipolar magnetic regions as sources of flux, the evolution of the radial component of the solar photospheric magnetic field is simulated during 1976-1984, and the corresponding evolution of the line-of-sight polar fields as seen from earth is derived. The observed timing and strength of the polar-field reversal during cycle 21 can be accounted for by supergranular diffusion alone, for a diffusion coefficient of 800 sq km/sec. For an assumed 300 sq km/sec rate of diffusion, on the other hand, a poleward meridional flow with a moderately broad profile and a peak speed of 10 m/s reached at about 5 deg latitude is required to obtain agreement between the simulated and observed fields. Such a flow accelerates the transport of following-polarity flux to the polar caps, but also inhibits the diffusion of leading-polarity flux across the equator. For flows faster than about 10 m/s, the latter effect dominates, and the simulated polar fields reverse increasingly later and more weakly than the observed fields.
Arctic sea ice extent decreased by 0.30 plus or minus 0.03 x 10(exp 6) square kilometers per decade from 1972 through 2002, but decreased by 0.36 plus or minus 0.05 x 10(exp 6) square kilometers per decade from 1979 through 2002, indicating an acceleration of 20% in the rate of decrease. In contrast to the Arctic, the Antarctic sea ice extent decreased dramatically over the period 1973-1977, then gradually increased, with an overall 30-year trend of -0.15 plus or minus 0.08 x 10(exp 6) square kilometers per 10yr. The trend reversal is attributed to a large positive anomaly in Antarctic sea ice extent observed in the early 1970's.
Abstract. One notable observation of enzymatic chemical reactions is that, for a given abundance of enzymes and substrates, temperature increases cause reaction rates to first increase consistent with the Arrhenius relationship, then plateau, and finally fall off quickly to zero at high temperatures. While many mathematical functions have been used to describe this pattern, we here propose a chemical kinetics theory which successfully replicates this observation and provides insights into the processes responsible for these dynamics. The chemical kinetics theory combines the law of mass action, von Smoluchowski's diffusion-limited chemical reaction theory, and Eyring's transition state theory. This new theory reveals that the thermally reversible enzyme denaturation ensured by the ceaseless thermal motion of molecules and ions in an enzyme solution explains the plateau and subsequent decrease in chemical reaction rates with increasing temperature. The temperature-dependent affinity parameter (K) that relates enzymes and substrates through their binding also affects the shape of the emergent temperature response. We demonstrate that with an increase in substrate availability, K shifts the optimal temperature, where reaction rates plateau, towards higher values. Further, we show that the chemical kinetics theory accurately represents 12 sets of published enzyme assay data and includes the popular mechanistic model by Ratkowsky et al. (2005) as a special case. Given its good performance and solid theoretical underpinning, we believe this new theory will facilitate the construction of more mechanistic-based environmental biogeochemical models.
Despite the 3–5 fold higher energy density than the conventional Li–ion cells at a lower cost, commercialization of Li–S batteries is hindered by the insulating nature of sulfur and the dissolution of intermediate polysulfides (Li 2 S X , 4 < X ≤ 8) into the electrolyte. The authors demonstrate here multichannel carbon nanofibers that are composed of parallel mesoporous channels connected with micropores as sulfur containment. In addition, hydroxyl functional groups are formed on the carbon surface through a chemical activation to enhance the interaction between sulfur and carbon. In the sulfur embedded composite, the mesoporous multichannel enhances the active material utilization and sulfur loading, while the micropores act as a reaction chamber for sulfur component and trap site for polysulfide with the assistance of the functional groups. Here, this sulfur–carbon composite electrode with 2.2 mg cm –2 sulfur displays excellent performance with high rate capability (initial capacity of 1351 mA h g –1 at C/5 rate and 847 mA h g –1 at 5C rate), maintaining 920 mA h g –1 even after 300 cycles (a decay of 0.07% per cycle). Furthermore, a stable reversible capacity of as high as ≈1100 mA h g –1 is realized with a higher sulfur loading of 4.6 mg cm –2 .
Here, a unique 3D hybrid sponge with chemically coupled nickel disulfide–reduced graphene oxide (NiS 2 –RGO) framework is rationally developed as an effective polysulfide reservoir through a biomolecule–assisted self–assembly synthesis. An optimized amount of NiS 2 (≈18 wt%) with porous nanoflower–like morphology is uniformly in situ grown on the RGO substrate, providing abundant active sites to adsorb and localize polysulfides. The improved polysulfide adsorptivity from sulfiphilic NiS 2 is confirmed by experimental data and first–principle calculations. Moreover, due to the chemical coupling between NiS 2 and RGO formed during the in situ synthesis, the conductive RGO substrate offers a 3D electron pathway to facilitate charge transfer toward the NiS 2 –polysulfide adsorption interface, triggering a fast redox kinetics of polysulfide conversion and excellent rate performance (C/20–4C). Therefore, the self–assembled hybrid structure simultaneously promotes static polysulfide–trapping capability and dynamic polysulfide–conversion reversibility. As a result, the 3D porous sponge enables a high sulfur content (75 wt%) and a remarkably high sulfur loading (up to 21 mg cm –2 ) and areal capacity (up to 16 mAh cm –2 ), exceeding most of the reported values in the literature involving either RGO or metal sulfides/other metal compounds (sulfur content of <60 wt% and sulfur loading of <3 mg cm –2 ).