Degradation kinetic modelling of ascorbic acid and colour intensity in pasteurised blood orange juice during storage.

PubMed

Remini, Hocine; Mertz, Christian; Belbahi, Amine; Achir, Nawel; Dornier, Manuel; Madani, Khodir

2015-04-15

The stability of ascorbic acid and colour intensity in pasteurised blood orange juice (Citrus sinensis [L.] Osbeck) during one month of storage was investigated at 4-37 °C. The effects of ascorbic acid fortification (at 100, 200 mg L(-1)) and deaeration, temperature/time storage on the kinetic behaviour were determined. Ascorbic acid was monitored by HPLC-DAD and colour intensity by spectrophotometric measurements. Degradation kinetics were best fitted by first-order reaction models for both ascorbic acid and colour intensity. Three models (Arrhenius, Eyring and Ball) were used to assess the temperature-dependent degradation. Following the Arrhenius model, activation energies were ranged from 51 to 135 kJ mol(-1) for ascorbic acid and from 49 to 99 kJ mol(-1) for colour intensity. The effect of storage temperature and deaeration are the most influent factors on kinetics degradation, while the fortification revealed no significant effect on ascorbic acid content and colour intensity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Modified Silicone-Rubber Tooling For Molding Composite Parts

NASA Technical Reports Server (NTRS)

Baucom, Robert M.; Snoha, John J.; Weiser, Erik S.

1995-01-01

Reduced-thermal-expansion, reduced-bulk-modulus silicone rubber for use in mold tooling made by incorporating silica powder into silicone rubber. Pressure exerted by thermal expansion reduced even further by allowing air bubbles to remain in silicone rubber instead of deaerating it. Bubbles reduce bulk modulus of material.

Catalytic two-electron reduction of dioxygen by ferrocene derivatives with manganese(V) corroles.

PubMed

Jung, Jieun; Liu, Shuo; Ohkubo, Kei; Abu-Omar, Mahdi M; Fukuzumi, Shunichi

2015-05-04

Electron transfer from octamethylferrocene (Me8Fc) to the manganese(V) imidocorrole complex (tpfc)Mn(V)(NAr) [tpfc = 5,10,15-tris(pentafluorophenyl)corrole; Ar = 2,6-Cl2C6H3] proceeds efficiently to give an octamethylferrocenium ion (Me8Fc(+)) and [(tpfc)Mn(IV)(NAr)](-) in acetonitrile (MeCN) at 298 K. Upon the addition of trifluoroacetic acid (TFA), further reduction of [(tpfc)Mn(IV)(NAr)](-) by Me8Fc gives (tpfc)Mn(III) and ArNH2 in deaerated MeCN. TFA also results in hydrolysis of (tpfc)Mn(V)(NAr) with residual water to produce a protonated manganese(V) oxocorrole complex ([(tpfc)Mn(V)(OH)](+)) in deaerated MeCN. [(tpfc)Mn(V)(OH)](+) is rapidly reduced by 2 equiv of Me8Fc in the presence of TFA to give (tpfc)Mn(III) in deaerated MeCN. In the presence of dioxygen (O2), (tpfc)Mn(III) catalyzes the two-electron reduction of O2 by Me8Fc with TFA in MeCN to produce H2O2 and Me8Fc(+). The rate of formation of Me8Fc(+) in the catalytic reduction of O2 follows zeroth-order kinetics with respect to the concentrations of Me8Fc and TFA, whereas the rate increases linearly with increasing concentrations of (tpfc)Mn(V)(NAr) and O2. These kinetic dependencies are consistent with the rate-determining step being electron transfer from (tpfc)Mn(III) to O2, followed by further proton-coupled electron transfer from Me8Fc to produce H2O2 and [(tpfc)Mn(IV)](+). Rapid electron transfer from Me8Fc to [(tpfc)Mn(IV)](+) regenerates (tpfc)Mn(III), completing the catalytic cycle. Thus, catalytic two-electron reduction of O2 by Me8Fc with (tpfc)Mn(V)(NAr) as a catalyst precursor proceeds via a Mn(III)/Mn(IV) redox cycle.

35. VIEW LOOKING EAST IN SOUTH END OF EAST BOILER ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

35. VIEW LOOKING EAST IN SOUTH END OF EAST BOILER ROOM. CYLINDRICAL TANKS ARE WORTHINGTON DEAERATORS. THESE REMOVED AIR FROM BOILER FEED WATER TO MINIMIZE CORROSION AND PITTING OF THE BOILER TUBES. AIR REMOVAL ALSO HELPED AVOID THE FORMATION OF FOAM IN THE SYSTEM. - New York, New Haven & Hartford Railroad, Cos Cob Power Plant, Sound Shore Drive, Greenwich, Fairfield County, CT

The influence of the Tbeta level upon fluorescence and laser properties of aromatic compounds.

PubMed

Nijegorodov, N; Winkoun, D P; Nkoma, J S

2004-07-01

The fluorescence and laser properties of seven specially chosen aromatic compounds are studied at 293 degrees C. The quantum yield of fluorescence, gamma, decay times, tauf, of the deaerated and non-deaerated solutions are measured. The oscillator strength, fe, fluorescence rate constants, kf, natural lifetimes, tauT0, and intersystem crossing rate constants, kST, are calculated. Some laser parameters are calculated or measured experimentally. It is found that the position of the Tbeta level plays an important role in the fluorescence and laser properties of aromatic compounds. If the Tbeta level is situated below the Sp level, it decreases the quantum yield of fluorescence and the decay time and increases the threshold of laser action. If, due to some structural changes of a molecule, the Tbeta level is situated higher than the Sp level, then the quantum yield of fluorescence and the decay times are increasing and the threshold of laser action is decreasing. Such influence of the position of the Tbeta level upon fluorescence and laser properties of aromatic compound is explained by the fact that the Sp level mixes with the Tbeta level more readily than with other taupipi* levels.

All-regime combined-cycle plant: Engineering solutions

NASA Astrophysics Data System (ADS)

Berezinets, P. A.; Tumanovskii, G. G.; Tereshina, G. E.; Krylova, I. N.; Markina, V. N.; Migun, E. N.

2016-12-01

The development of distributed power generation systems as a supplement to the centralized unified power grid increases the operational stability and efficiency of the entire power generation industry and improves the power supply to consumers. An all-regime cogeneration combined-cycle plant with a power of 20-25 mW (PGU-20/25T) and an electrical efficiency above 50% has been developed at the All-Russia Thermal Engineering Institute (ATEI) as a distributed power generation object. The PGU-20/25T two-circuit cogeneration plant provides a wide electrical and thermal power adjustment range and the absence of the mutual effect of electrical and thermal power output regimes at controlled frequency and power in a unified or isolated grid. The PGU-20/25T combined-cycle plant incorporates a gas-turbine unit (GTU) with a power of 16 MW, a heat recovery boiler (HRB) with two burners (before the boiler and the last heating stage), and a cogeneration steam turbine with a power of 6/9 MW. The PGU-20/25T plant has a maximum electrical power of 22 MW and an efficiency of 50.8% in the heat recovery regime and a maximum thermal power output of 16.3 MW (14 Gcal/h) in the cogeneration regime. The use of burners can increase the electrical power to 25 MW in the steam condensation regime at an efficiency of 49% and the maximum thermal power output to 29.5 MW (25.4 Gcal/h). When the steam turbine is shut down, the thermal power output can grow to 32.6 MW (28 Gcal/h). The innovative equipment, which was specially developed for PGU-20/25T, improves the reliability of this plant and simplifies its operation. Among this equipment are microflame burners in the heat recovery boiler, a vacuum system based on liquid-ring pumps, and a vacuum deaerator. To enable the application of PGU-20/25T in water-stressed regions, an air condenser preventing the heat-transfer tubes from the risk of covering with ice during operation in frost air has been developed. The vacuum system eliminates the need for an extraneous source of steam for the startup of the PGU-20/25T plant. The vacuum deaerator provides prestartup deaeration and the filling of the entire condensate feed pipeline with deaerated water and also enables the maintenance of the water temperature before the boiler at a level of no lower than 60°C and the oxygen content at a level of no higher than 10 μg/L during operation under load. The microflame burners in the heat recovery boiler enable the independent adjustment of the electrical power and the thermal power output from the PGU-20/25T plant. All the innovative equipment has been tested on experimental prototypes.

Electrochemical approach for passivating steel and other metals and for the simultaneous production of a biocide to render water potable

NASA Technical Reports Server (NTRS)

1972-01-01

Potentiostatic polarization curves indicated that the cathodic reactions in deaerated KI-I2 water solutions were due to iodine reduction and hydrogen evolution. In the presence of oxygen an additional reduction wave appeared. Anodic polarization curves revealed that iodine could be produced in the region of potential from +600 to +1000 nv vs. SCE.

USSR Report, Engineering and Equipment, No. 98.

DTIC Science & Technology

1983-11-09

Nonhomogeneous Cylinder During Convective Cooling (V. Ya. Belousov; PROBLEM PROCHNOSTI, No 5, May 83) 66 Deformation of Spherical Shells Under Wind...generator and turbine, condenser , deaerator, and tap-water or hot-water tank for heat storage. The electric power is regulated by varying the steam rate...indicators, relative to those of hybrid condensation - boiler atomic electric power plants already in existence, So far the VK-500 boiling^water

Photodegradation of naproxen and its photoproducts in aqueous solution at 254 nm: a kinetic investigation.

PubMed

Marotta, Raffaele; Spasiano, Danilo; Di Somma, Ilaria; Andreozzi, Roberto

2013-01-01

The kinetics of photodegradation of the non steroidal anti-inflammatory drug naproxen (+)-S-2-(6-methoxynaphthalen-2-yl)propanoic acid, an emerging organic pollutant, was studied in aqueous solutions under deaerated and aerated conditions. The photolysis experiments were carried out under monochromatic irradiation (λ = 254 nm) at pH = 7.0 and T = 25 °C. Simplified reaction schemes of photodegradation of naproxen are proposed in absence and in presence of oxygen respectively. The schemes take into account the photolysis of naproxen and its photoproducts and the reactions of the measured species with oxygen dissolved in the liquid bulk. According to these schemes, two kinetic models were developed which correlate the experimental data, for runs performed in absence and in presence of oxygen, with a fair accuracy and allowed to estimate the best values for the unknown kinetic parameters. The calculated quantum yield of direct photolysis of naproxen under deaerated media is in good agreement with the one previously reported. Under aerated conditions, the generation of singlet oxygen has also been taken into account. The obtained results, under the adopted conditions, indicated a marked influence of dissolved oxygen on the photodegradation rates of naproxen and the relative distribution of the major reaction intermediates. Copyright © 2012 Elsevier Ltd. All rights reserved.

Use of Electrochemical Noise (EN) Technique to Study the Effect of sulfate and Chloride Ions on Passivation and Pitting Corrosion Behavior of 316 Stainless Steel

NASA Astrophysics Data System (ADS)

Pujar, M. G.; Anita, T.; Shaikh, H.; Dayal, R. K.; Khatak, H. S.

2007-08-01

In the present paper, studies were conducted on AISI Type 316 stainless steel (SS) in deaerated solutions of sodium sulfate as well as sodium chloride to establish the effect of sulfate and chloride ions on the electrochemical corrosion behavior of the material. The experiments were conducted in deaerated solutions of 0.5 M sodium sulfate as well as 0.5 M sodium chloride using electrochemical noise (EN) technique at open circuit potential (OCP) to collect the correlated current and potential signals. Visual records of the current and potential, analysis of data to arrive at the statistical parameters, spectral density estimation using the maximum entropy method (MEM) showed that sulfate ions were incorporated in the passive film to strengthen the same. However, the adsorption of chloride ions resulted in pitting corrosion thereby adversely affecting noise resistance ( R N). Distinct current and potential signals were observed for metastable pitting, stable pitting and passive film build-up. Distinct changes in the values of the statistical parameters like R N and the spectral noise resistance at zero frequency ( R°SN) revealed adsorption and incorporation of sulfate and chloride ions on the passive film/solution interface.

Method for generating O.sub.2-rich gas from air using water

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

Nakano, Anna; Nakano, Jinichiro; Bennett, James P.

The present disclosure is directed to a method for enriching an inlet air stream utilizing a number of enrichment sub-units connected in series, where each enrichment sub-unit conducts both a dissolution and degasification cycle. Each enrichment sub-unit comprises a compressor, an aeration unit, a deaeration unit, and a pump for the recirculation of water between the aeration and deaeration units. The methodology provides a manner in which the relationship between the respective Henry's coefficients of the oxygen and nitrogen in water may be exploited to enrich the O.sub.2 volume percent and diminish the N.sub.2 volume percent over repeated dissolution andmore » degasification cycles. By utilizing a number of enrichment sub-units connected in series, the water contained in each enrichment sub-unit acts to progressively increase the O.sub.2 volume percent. Additional enrichment sub-units may be added and utilized until the O.sub.2 volume percent equals or exceeds a target O.sub.2 volume percent. In a particular embodiment, air having a general composition of about 78 vol. % N.sub.2 and 21 vol. % O.sub.2 is progressively enriched to provide a final mixture of about 92% vol. % O.sub.2 and 8% vol. % N.sub.2.« less

System for Continuous Deaeration of Hydraulic Oil

NASA Technical Reports Server (NTRS)

Anderson, Christopher W.

2006-01-01

A system for continuous, rapid deaeration of hydraulic oil has been built to replace a prior system that effected deaeration more slowly in a cyclic pressure/ vacuum process. Such systems are needed because (1) hydraulic oil has an affinity for air, typically containing between 10 and 15 volume percent of air and (2) in the original application for which these systems were built, there is a requirement to keep the proportion of dissolved air below 1 volume percent because a greater proportion can lead to pump cavitation and excessive softness in hydraulic-actuator force-versus-displacement characteristics. In addition to overcoming several deficiencies of the prior deaeration system, the present system removes water from the oil. The system (see figure) includes a pump that continuously circulates oil at a rate of 10 gal/min (38 L/min) between an 80-gal (303-L) airless reservoir and a tank containing a vacuum. When the circulation pump is started, oil is pumped, at a pressure of 120 psi (827 kPa), through a venturi tube below the tank with a connection to a stand-pipe in the tank. This action draws oil out of the tank via the standpipe. At the same time, oil is sprayed into the tank in a fine mist, thereby exposing a large amount of oil to the vacuum. When the oil level in the tank falls below the lower of two level switches, a vacuum pump is started, drawing a hard vacuum on the tank through a trap that collects any oil and water entrained in the airflow. When the oil level rises above higher of the two level switches or when the system is shut down, a solenoid valve between the tank and the vacuum pump is closed to prevent suction of oil into the vacuum pump. Critical requirements that the system is designed to satisfy include the following: 1) The circulation pump must have sufficient volume and pressure to operate the venturi tube and spray nozzles. 2) The venturi tube must be sized to empty the tank (except for the oil retained by the standpipe) and maintain a vacuum against the vacuum pump. 3) The tank must be strong enough to withstand atmospheric pressure against the vacuum inside and must have sufficient volume to enable exposure of a sufficiently large amount of sprayed oil to the vacuum. 4) The spray nozzles must be sized to atomize the oil and to ensure that the rate of flow of sprayed oil does not exceed the rate at which the venturi action can empty the tank. 5) The vacuum pump must produce a hard vacuum against the venturi tube and continue to work when it ingests some oil and water. 6) Fittings must be made vacuum tight (by use of O-rings) to prevent leakage of air into the system. The system is fully automatic, and can be allowed to remain in operation with very little monitoring. It is capable of reducing the air content of the oil from 11 to less than 1 volume percent in about 4 hours and to keep the water content below 100 parts per million.

Nonaggregating Microspheres Containing Aldehyde Groups

NASA Technical Reports Server (NTRS)

Rembaum, Alan

1989-01-01

Cobalt gamma irradiation of hydrophilic monomers in presence of acrolein yields exceptionally-stable, nonaggregating microspheres. Mixtures of 2-hydroxyethyl methacrylate (HEMA) and acrolein form homogeneous solutions in distilled water containing 0.4 percent polyethylene oxide (PEO). After deaeration with nitrogen, mixtures irradiated at room temperature with gamma rays from cobalt source; total exposure time 4 hours, at rate of 0.2 milliroentgen per hour. Reaction product centrifuged three times for purification and kept in distilled water.

The influence of EI-21 redox ion-exchange resins on the secondary-coolant circuit water chemistry of vehicular nuclear power installations

NASA Astrophysics Data System (ADS)

Moskvin, L. N.; Rakov, V. T.

2015-06-01

The results obtained from testing the secondary-coolant circuit water chemistry of full-scale land-based prototype bench models of vehicular nuclear power installations equipped with water-cooled water-moderated and liquid-metal reactor plants are presented. The influence of copper-containing redox ionexchange resins intended for chemically deoxygenating steam condensate on the working fluid circulation loop's water chemistry is determined. The influence of redox ion-exchange resins on the water chemistry is evaluated by generalizing an array of data obtained in the course of extended monitoring using the methods relating to physicochemical analysis of the quality of condensate-feedwater path media and the methods relating to metallographic analysis of the state of a faulty steam generator's tube system surfaces. The deoxygenating effectiveness of the normal state turbine condensate vacuum deaeration system is experimentally determined. The refusal from applying redox ion-exchange resins in the condensate polishing ion-exchange filters is formulated based on the obtained data on the adverse effect of copper-containing redox ionexchange resins on the condensate-feedwater path water chemistry and based on the data testifying a sufficient effect from using the normal state turbine condensate vacuum deaeration system. Data on long-term operation of the prototype bench model of a vehicular nuclear power installation without subjecting the turbine condensate to chemical deoxygenation are presented.

Hollow fiber membrane systems for advanced life support systems

NASA Technical Reports Server (NTRS)

Roebelen, G. J., Jr.; Lysaght, M. J.

1976-01-01

The practicability of utilizing hollow fiber membranes in vehicular and portable life support system applications is described. A preliminary screening of potential advanced life support applications resulted in the selection of five applications for feasibility study and testing. As a result of the feasibility study and testing, three applications, heat rejection, deaeration, and bacteria filtration, were chosen for breadboard development testing; breadboard hardware was manufactured and tested, and the physical properties of the hollow fiber membrane assemblies are characterized.

The interaction of radiation-generated radicals with myoglobin in aqueous solution—V. The indirect action of 2-methyl-2-hydroxypropyl radicals on oxymyoglobin

NASA Astrophysics Data System (ADS)

Whitburn, Kevin D.; Hoffman, Morton Z.

The interaction of radiation-generated 2-methyl-2-hydroxypropyl radicals (derived from t-butyl alcohol) with oxymyoglobin has been examined at pH 7.3. In N 2O-saturated solutions, oxymyoglobin is converted to the ferri and ferryl derivatives of myoglobin; the production of ferrylmyoglobin is essentially eliminated when catalase is present in solution during irradiation. In deaerated solutions containing catalase, oxymyoglobin is converted to both ferro- and ferrimyoglobin during irradiation. When added O 2 is initially present, all compositional changes occur after irradiation; the presence of catalase diminishes, but does not eliminate, the extent of these postirradiation conversions of oxymyoglobin to the ferri and ferryl derivatives. These observations are interpreted in terms of the scavenging of the 2-methyl-2-hydroxypropyl radicals by O 2 to generate their peroxy analogs, which causes a displacement of the equilibrium between oxy- and ferromyoglobin. The peroxy radicals decay to produce H 2O 2, an organic peroxide, and other products. These peroxides subsequently react with ferromyoglobin to produce the ferryl form; the rate of the reaction increases with decreasing [O 2] as [ferromyoglobin] increases. This reaction is sufficiently fast in deaerated solution that substantial conversion of ferromyoglobin to ferrylmyoglobin occurs during the time of irradiation. The formation of the ferryl derivative in the presence of unconverted ferromyoglobin drives a concurrent synproportion reaction which produces ferrimyoglobin. Overall, no direct interaction of 2-methyl-2-hydroxypropyl radicals, nor their peroxy analogs, with myoglobin is indicated; all reactivity is accountable by the peroxide products of these radicals.

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

Grachev, S.A.; Chakchir, B.A.; Ryabykh, L.D.

The feasibility of radiation sterilization was studied on ephedrine hydrochloride, atropine sulfate, scopolamine hydrobromide, strychnine nitrate, morphine hydrochloride, codeine phosphate, proserine, cysteamine hydrochloride, and unithiol in form of injectable solutions and as powders. It was shown that the sterilizing dose of radioactivity results in a breakdown of the solutions as shown by changes in the pH, color, and loss of biological activity. Alkaloid powders exhibited no changes after radiation sterilization. Deaerated solutions were also stable to the radiation but such solutions could not be prepared easily under industrial conditions. Temperature had no effect on the stability of test samples exceptmore » for very low temperatures. (JPRS)« less

Hollow fiber membranes for advanced life support systems. [permeable capillaries for medical filtration

NASA Technical Reports Server (NTRS)

Roebelen, G. J., Jr.; Lysaght, M. J.

1977-01-01

This paper describes an investigation of the practicability of utilizing hollow fiber membranes in vehicular and portable life support system applications. A preliminary screening of potential advanced life support applications resulted in the selection of five applications for feasibility study and testing. As a result of the feasibility study and testing, three applications, heat rejection, deaeration, and bacteria filtration, were chosen for breadboard development testing. Breadboard hardware has been manufactured and tested, and the physical properties of the three hollow fiber membrane assemblies applicable to use aboard future spacecraft have been characterized.

Exhaled breath condensate pH in mechanically ventilated patients.

PubMed

Nannini, L J; Quintana, R; Bagilet, D H; Druetta, M; Ramírez, M; Nieto, R; Guelman Greta, G

2013-12-01

In this prospective clinical trial we aimed to answer if spontaneous exhaled breath condensate (EBC) in the trap of the expiratory arm of the ventilator could replace EBC collected by coolant chamber standardized with Argon as an inert gas. Second, if EBC pH could predict ventilator associated pneumonia (VAP) and mortality. We included 34 critically ill patients (males = 26), aged = 54.85 ± 19.86 (mean ± SD) yrs, that required mechanical ventilation due to non-pulmonary direct cause (APACHE II score = 23.58 ± 14.7; PaO(2)/FiO(2) = 240.00 ± 98.29). ICU with 9 beds from a regional teaching hospital. The patients were followed up until development of VAP, successful weaning or death. There were significant differences between mean EBC pH from the 4 procedures with the exception of spontaneous EBC de-aerated with Argon (n = 79; 6.74 ± 0.28) and coolant chamber deaerated with Argon (n = 79; 6.70 ± 0.36; p = NS by Tukey's Multiple Comparison Test). However, none of the procedures were extrapolated between each other according to Bland & Altman method. The mean EBC pH from the trap without Argon was 6.50 ± 0.28. From the total of 34 patients, 22 survived and were discharged and 12 patients died in the ICU. Spontaneous EBC pH could not be extrapolated to EBC pH from coolant chamber and it did not change in subjects who dead, neither subject with VAP in comparison with baseline data. The lack of other biomarker in EBC and the lack of a control group determinate the need for further studies in this setting. Copyright © 2012 Elsevier España, S.L. and SEMICYUC. All rights reserved.

Corrosion behavior of surface films on boron-implanted high purity iron and stainless steels

NASA Technical Reports Server (NTRS)

Kim, H. J.; Carter, W. B.; Hochman, R. F.; Meletis, E. I.

1985-01-01

Boron (dose, 2 x 10 to the 17th ions/sq cm) was implanted into high purity iron, AISI 316 austenitic stainless steel, and AISI 440C martensitic stainless steel, at 40 keV. The film structure of implanted samples was examined and characterized by contrast and diffraction analyses utilizing transmission electron microscopy. The effect of B(+) ion implantation on the corrosion behavior was studied using the potentiodynamic polarization technique. Tests were performed in deaerated 1 N H2SO4 and 0.1 M NaCl solutions. Scanning electron microscopy was used to examine the morphology of the corroded surfaces after testing.

Study and Optimization on graft polymerization under normal pressure and air atmospheric conditions, and its application to metal adsorbent

NASA Astrophysics Data System (ADS)

Ueki, Yuji; Chandra Dafader, Nirmal; Hoshina, Hiroyuki; Seko, Noriaki; Tamada, Masao

2012-07-01

Radiation-induced graft polymerization of glycidyl methacrylate (GMA) onto non-woven polyethylene (NWPE) fabric was achieved under normal pressure and air atmospheric conditions, without using unique apparatus such as glass ampoules or vacuum lines. To attain graft polymerization under normal pressure and air atmospheric conditions, the effects of the pre-irradiation dose, pre-irradiation atmosphere, pre-irradiation temperature, de-aeration of GMA-emulsion, grafting atmosphere in a reactor, and dissolved oxygen (DO) concentration in GMA-emulsion on the degree of grafting (Dg) were investigated in detail. It was found that the DO concentration had the strongest influence, the pre-irradiation dose, de-aeration of emulsion and grafting atmosphere had a relatively strong impact, and the pre-irradiation atmosphere and pre-irradiation temperature had the least effect on Dg. The optimum DO concentration before grafting was 2.0 mg/L or less. When a polyethylene bottle was used as a reactor instead of a glass ampoule, graft polymerization under normal pressure and air atmospheric conditions could be achieved under the following conditions; the pre-irradiation dose was more than 50 kGy, the volume ratio of GMA-emulsion to air was 50:1 or less, and the DO concentration in GMA-emulsion during grafting was below 2.0 mg/L. Under these grafting conditions, Dg was controlled within a range of up to 362%. The prepared GMA-grafted NWPE (GMA-g-NWPE) fabric was modified with a phosphoric acid to obtain an adsorbent for heavy metal ions. In the column-mode adsorption tests of Pb(II), the adsorption performance of the produced phosphorylated GMA-g-NWPE fabric (fibrous metal adsorbent) was not essentially dependent on the flow rate of the feed. The breakthrough points of 200, 500, and 1000 h-1 in space velocity were 483, 477 and 462 bed volumes, and the breakthrough capacities of the three flow rates were 1.16, 1.15 and 1.16 mmol-Pb(II)/g-adsorbent.

Flowability of granular materials with industrial applications - An experimental approach

NASA Astrophysics Data System (ADS)

Torres-Serra, Joel; Romero, Enrique; Rodríguez-Ferran, Antonio; Caba, Joan; Arderiu, Xavier; Padullés, Josep-Manel; González, Juanjo

2017-06-01

Designing bulk material handling equipment requires a thorough understanding of the mechanical behaviour of powders and grains. Experimental characterization of granular materials is introduced focusing on flowability. A new prototype is presented which performs granular column collapse tests. The device consists of a channel whose design accounts for test inspection using visualization techniques and load measurements. A reservoir is attached where packing state of the granular material can be adjusted before run-off to simulate actual handling conditions by fluidisation and deaeration of the pile. Bulk materials on the market, with a wide range of particle sizes, can be tested with the prototype and the results used for classification in terms of flowability to improve industrial equipment selection processes.

The photochemistry of manganese and the origin of banded iron formations

NASA Technical Reports Server (NTRS)

Anbar, A. D.; Holland, H. D.

1992-01-01

The origin of the deposition of superior-type Precambrian banded iron formations (BIFs) is investigated in experiments where the effect of UV radiation on dissolved manganese was studied to determine if the commonly accepted photochemical model for BIF formation is consistent with the distribution of Mn in BIFs. Solutions containing 0.56 M NaCl and about 180 microM MnCl2, with or without 3 to 200 microM FeCl2 were irradiated with filtered and unfiltered UV light for up to 8 hrs; the solutions were deaerated and buffered to a pH of 7, and the experiments were conducted under oxygen-free atmosphere. Data on the rate of manganese photooxidation confirmed that a photochemical model for the origin of oxide facies BIFs is consistent with field observations.

New amine-type inhibitors for protecting low-carbon steels in hydrogen sulfide-containing neutral media

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

Podobaev, N.I.; Atanasyan, T.K.; Lyashenko, L.F.

The protecting action of polethylenepolyamine (PEPA) products was carried out by gravimetric and electrochemical methods in aerated and de-aerated 35 NaCl solutions and simulated waste water containing CaCl/sub 2/, NaCl, NaHCO/sub 3/, Na/sub 2/SO/sub 4/, and KBr, with addition of H/sub 2/S. Gravimetric and electrochemical measurements were carried out and results are presented. The influence on tanning agents on the physicomechanical and photographic properties of the positive emulsion Unibrom, Normal at thermostated aging for two days was shown. The results lead to the conclusion that the use of animals as tanning agents of the emulsion lead to improvement of themore » physicomechanical properties of the emulsion light sensitive layers.« less

Radiolytic decomposition of ammonium halides

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

Orlov, S.L.; Gromov, V.V.; Saunin, E.I.

1988-11-01

Chromatographic analyses were made of the gaseous products of the radiolysis of polycrystalline NH/sub 4/F, NH/sub 4/Cl, NH/sub 4/Br, and NH/sub 4/I, of particle size 0.25-0.5 mm. The irradiation was performed with /sup 60/Co ..sigma..-quanta, at room temperature in previously evacuated and sealed glass ampules. Determination was made of the amount of gas liberated into the space of the ampule during the irradiation, and of the amount retained in the crystal matrix and evolved on dissolution of the resulting samples in deaerated water. At the same time quantitative determinations of halogen were made by the thiosulfate method. It was shownmore » that hydrogen and nitrogen were formed in the radiolysis of all the compounds investigated. The yields are listed.« less

A diffusion-free and linear-energy-transfer-independent nanocomposite Fricke gel dosimeter

NASA Astrophysics Data System (ADS)

Maeyama, T.; Fukunishi, N.; Ishikawa, K. L.; Furuta, T.; Fukasaku, K.; Takagi, S.; Noda, S.; Himeno, R.; Fukuda, S.

2014-03-01

We report a new magnetic-resonance-imaging (MRI) based nanocomposite Fricke gel (NC-FG) dosimeter system, which is free from two main drawbacks of conventional Fricke gel dosimeters, namely, the diffusion of the radiation products and the linear-energy-transfer (LET) dependence of the radiation sensitivity when used for ion beams. The NC-FG dosimeter was prepared by incorporating 1% (w/w) clay nanoparticles into deaerated Fricke gel. We have dosimetrically characterized the NC-FG by using MRI measurements after irradiation with a monoenergetic 290 MeV/nucleon carbon beam. No diffusion of the radiation products was observed during nine days after the irradiation. Moreover, its response faithfully reproduced the depth-dose distribution measured by an ionization chamber, which indicates the absence of the LET dependence. Also, the NC-FG dosimeter exhibited a good linearity up to 800 Gy.

Process for making a noble metal on tin oxide catalyst

NASA Technical Reports Server (NTRS)

Upchurch, Billy T. (Inventor); Davis, Patricia (Inventor); Miller, Irvin M. (Inventor)

1989-01-01

A quantity of reagent grade tin metal or compound, chloride-free, and high-surface-area silica spheres are placed in deionized water, followed by deaerating the mixture by boiling and adding an oxidizing agent, such as nitric acid. The nitric acid oxidizes the tin to metastannic acid which coats the spheres because the acid is absorbed on the substrate. The metastannic acid becomes tin oxide upon drying and calcining. The tin-oxide coated silica spheres are then placed in water and boiled. A chloride-free precious metal compound in aqueous solution is then added to the mixture containing the spheres, and the precious metal compound is reduced to a precious metal by use of a suitable reducing agent such as formic acid. Very beneficial results were obtained using the precious metal compound tetraammine platinum(II) hydroxide.

Photochemistry of copper(II) complexes with macrocyclic amine ligands

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

Muralidharan, S.; Ferraudi, G.

1981-07-01

The photochemical properties of Cu(dl-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ and Cu(rac-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ in the presence and absence of axially coordinated ligands have been investigated by continuous and flash irradiations. Flash photolysis of the complexes in deaerated aqueous solutions revealed the presence of copper-ligand radical complexes with closed- and open-cycle ligands. Flash photolysis of methanolic solutions of the complexes, in the presence of halides and pseudohalides, shows Cu(III) macrocyclic intermediates. The experimental observations can be explained in terms of two primary photoprocesses with origins in distinctive charge transfer to metal states. These states have been assigned as aminomore » to copper(II) charge-transfer state and acido to copper(II) charge-transfer state.« less

Open-cycle systems performance analysis programming guide

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

Olson, D.A.

1981-12-01

The Open-Cycle OTEC Systems Performance Analysis Program is an algorithm programmed on SERI's CDC Cyber 170/720 computer to predict the performance of a Claude-cycle, open-cycle OTEC plant. The algorithm models the Claude-cycle system as consisting of an evaporator, a turbine, a condenser, deaerators, a condenser gas exhaust, a cold water pipe and cold and warm seawater pumps. Each component is a separate subroutine in the main program. A description is given of how to write Fortran subroutines to fit into the main program for the components of the OTEC plant. An explanation is provided of how to use the algorithm.more » The main program and existing component subroutines are described. Appropriate common blocks and input and output variables are listed. Preprogrammed thermodynamic property functions for steam, fresh water, and seawater are described.« less

Effects of hydroxylated benzaldehyde derivatives on radiation-induced reactions involving various organic radicals

NASA Astrophysics Data System (ADS)

Ksendzova, G. A.; Samovich, S. N.; Sorokin, V. L.; Shadyro, O. I.

2018-05-01

In the present paper, the effects of hydroxylated benzaldehyde derivatives and gossypol - the known natural occurring compound - on formation of decomposition products resulting from radiolysis of ethanol and hexane in deaerated and oxygenated solutions were studied. The obtained data enabled the authors to make conclusions about the effects produced by the structure of the compounds under study on their reactivity towards oxygen- and carbon-centered radicals. It has been found that 2,3-dihydroxybenzaldehyde, 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde and 4,6-di-tert-butyl-3-(1,3-dioxane-2-yl)-1,2-dihydroxybenzene are not inferior in efficiency to butylated hydroxytoluene - the industrial antioxidant - as regards suppression of the radiation-induced oxidation processes occurring in hexane. The derivatives of hydroxylated benzaldehydes were shown to have a significant influence on radiation-induced reactions involving α-hydroxyalkyl radicals.

Corrosion of Titanium Matrix Composites

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

Covino, B.S., Jr.; Alman, D.E.

2002-09-22

The corrosion behavior of unalloyed Ti and titanium matrix composites containing up to 20 vol% of TiC or TiB{sub 2} was determined in deaerated 2 wt% HCl at 50, 70, and 90 degrees C. Corrosion rates were calculated from corrosion currents determined by extrapolation of the tafel slopes. All curves exhibited active-passive behavior but no transpassive region. Corrosion rates for Ti + TiC composites were similar to those for unalloyed Ti except at 90 degrees C where the composites were slightly higher. Corrosion rates for Ti + TiB{sub 2} composites were generally higher than those for unalloyed Ti and increasedmore » with higher concentrations of TiB{sub 2}. XRD and SEM-EDS analyses showed that the TiC reinforcement did not react with the Ti matrix during fabrication while the TiB{sub 2} reacted to form a TiB phase.« less

Production of gaseous fuel by pyrolysis of municipal solid waste

NASA Technical Reports Server (NTRS)

Crane, T. H.; Ringer, H. N.; Bridges, D. W.

1975-01-01

Pilot plant tests were conducted on a simulated solid waste which was a mixture of shredded newspaper, wood waste, polyethylene plastics, crushed glass, steel turnings, and water. Tests were conducted at 1400 F in a lead-bath pyrolyser. Cold feed was deaerated by compression and was dropped onto a moving hearth of molten lead before being transported to a sealed storage container. About 80 percent of the feed's organic content was converted to gaseous products which contain over 90 percent of the potential waste energy; 12 percent was converted to water; and 8 percent remained as partially pyrolyzed char and tars. Nearly half of the carbon in the feed is converted to benzene, toluene and medium-quality fuel gas, a potential credit of over $25 per ton of solid waste. The system was shown to require minimal preprocessing and less sorting then other methods.

Research on simulation of supercritical steam turbine system in large thermal power station

NASA Astrophysics Data System (ADS)

Zhou, Qiongyang

2018-04-01

In order to improve the stability and safety of supercritical steam turbine system operation in large thermal power station, the body of the steam turbine is modeled in this paper. And in accordance with the hierarchical modeling idea, the steam turbine body model, condensing system model, deaeration system model and regenerative system model are combined to build a simulation model of steam turbine system according to the connection relationship of each subsystem of steam turbine. Finally, the correctness of the model is verified by design and operation data of the 600MW supercritical unit. The results show that the maximum simulation error of the model is 2.15%, which meets the requirements of the engineering. This research provides a platform for the research on the variable operating conditions of the turbine system, and lays a foundation for the construction of the whole plant model of the thermal power plant.

Open-cycle OTEC system performance analysis. [Claude cycle

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

Lewandowski, A.A.; Olson, D.A.; Johnson, D.H.

1980-10-01

An algorithm developed to calculate the performance of Claude-Cycle ocean thermal energy conversion (OTEC) systems is described. The algorithm treats each component of the system separately and then interfaces them to form a complete system, allowing a component to be changed without changing the rest of the algorithm. Two components that are subject to change are the evaporator and condenser. For this study we developed mathematical models of a channel-flow evaporator and both a horizontal jet and spray director contact condenser. The algorithm was then programmed to run on SERI's CDC 7600 computer and used to calculate the effect onmore » performance of deaerating the warm and cold water streams before entering the evaporator and condenser, respectively. This study indicates that there is no advantage to removing air from these streams compared with removing the air from the condenser.« less

Bubble coalescence in a power-law fluid

NASA Astrophysics Data System (ADS)

Kamat, Pritish; Thete, Sumeet; Basaran, Osman

2015-11-01

As two spherical gas bubbles in a liquid are slowly brought together, the liquid film or sheet between them drains and ultimately ruptures, forming a circular hole that connects them. The high curvature near the edge of the liquid sheet drives flow radially outward, causing the film to retract and the radius of the hole to increase with time. Recent experimental and theoretical work in this area has uncovered self-similarity and universal scaling regimes when two bubbles coalesce in a Newtonian fluid. Motivated by applications such as polymer and composites processing, food and drug manufacture, and aeration/deaeration systems where the liquids often exhibit deformation-rate thinning rheology, we extend the recent Newtonian studies to bubble coalescence in power-law fluids. In our work, we use a combination of thin-film theory and full 3D, axisymmetric computations to probe the dynamics in the aftermath of the singularity.

A XPS Study of the Passivity of Stainless Steels Influenced by Sulfate-Reducing Bacteria.

NASA Astrophysics Data System (ADS)

Chen, Guocun

The influence of sulfate-reducing bacteria (SRB) on the passivity of type 304 and 317L stainless steels (SS) was investigated by x-ray photoelectron spectroscopy (XPS), microbiological and electrochemical techniques. Samples were exposed to SRB, and then the resultant surfaces were analyzed by XPS, and the corrosion resistance by potentiodynamic polarization in deaerated 0.1 M HCl. To further understand their passivity, the SRB-exposed samples were analyzed by XPS after potentiostatic polarization at a passive potential in the hydrochloric solution. The characterization was performed under two surface conditions: unrinsed and rinsed by deaerated alcohol and deionized water. Comparisons were made with control samples immersed in uninoculated medium. SRB caused a severe loss of the passivity of 304 SS through sulfide formation and possible additional activation to form hexavalent chromium. The sulfides included FeS, FeS_2, Cr_2S _3, NiS and possibly Fe_ {rm 1-x}S. The interaction took place nonuniformly, resulting in undercutting of the passive film and preferential hydration of inner surface layers. The bacterial activation of the Cr^{6+ }^ecies was magnified by subsequent potentiostatic polarization. In contrast, 317L SS exhibited a limited passivity. The sulfides were formed mainly in the outer layers. Although Cr^{6+}^ecies were observed after the exposure, they were dissolved upon polarization. Since 317L SS has a higher Mo content, its higher passivity was ascribed to Mo existing as molybdate on the surface and Mo^{5+} species in the biofilm. Consequently, the interaction of SRB with Mo was studied. It was observed that molybdate could be retained on the surfaces of Mo coupons by corrosion products. In the presence of SRB, however, a considerable portion of the molybdate interacted with intermediate sulfur -containing proteins, forming Mo(V)-S complexes and reducing bacterial growth and sulfate reduction. The limited insolubility of the Mo(V)-S complexes in 0.1 M HCl provided a certain protection so that the pitting potential of the SRB-exposed Mo coupons was not considerably decreased. The interaction of the sulfur-containing proteins with Mo also provided mechanistic information about the adhesion of biofilm to Mo-bearing steels. Additionally, the interactions of SRB with other alloying elements, Cr and Ni, were investigated.

Field performance of a geosynthetic clay liner landfill capping system under simulated waste subsidence

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

Weiss, W.; Siegmund, M.; Alexiew, D.

1995-10-01

A flexible landfill capping system consisting of a 3-D-geocore composite for gas vent, a Geosynthetic Clay Liner (GCL) for sealing and a 3-D-geocore composite for drainage of the vegetation soil was built on a test field at Michelshoehe landfill near Weimar, Germany. At four locations airbags were installed underneath the thin capping system to simulate subsidences. On top of three of these airbags overlaps of the GCL were positioned, for comparison there was no overlap at the fourth location. After hydratation of the GCL the airbags were de-aerated and subsidences occurred with app. 5 % tensile strain in the GCL.more » For three weeks the test field was intensively sprinkled in intervals. Then horizontal and vertical deformations were measured, but not displacements were registered in the overlaps. The evaluation of the GCL`s permeability showed no significant difference between the locations with and without overlaps.« less

Bactericidal Effect of Zero-Valent Iron Nanoparticles on Escherichia coli

PubMed Central

Lee, Changha; Kim, Jee Yeon; Lee, Won Il; Nelson, Kara L.; Yoon, Jeyong; Sedlak, David L.

2008-01-01

Zero-valent iron nanoparticles (nano-Fe0) in aqueous solution rapidly inactivated Escherichia coli (E. coli). A strong bactericidal effect of nano-Fe0 was found under deaerated conditions, with a linear correlation between log inactivation and nano-Fe0 dose (0.82 log inactivation / mg/L nano-Fe0 · hr). The inactivation of E. coli under air saturation required much higher nano-Fe0 doses due to the corrosion and surface oxidation of nano-Fe0 by dissolved oxygen. Significant physical disruption of the cell membranes was observed in E. coli exposed to nano-Fe0, which may have caused the inactivation, or enhanced the biocidal effects of dissolved iron. The reaction of Fe(II) with intracellular oxygen or hydrogen peroxide also may have induced oxidative stress by producing reactive oxygen species. The bactericidal effect of nano-Fe0 was a unique property of nano-Fe0, which was not observed in other types of iron-based compounds. PMID:18678028

The effects of temperature and aeration on the corrosion of A508III low alloy steel in boric acid solutions at 25-95 °C

NASA Astrophysics Data System (ADS)

Xiao, Qian; Lu, Zhanpeng; Chen, Junjie; Yao, Meiyi; Chen, Zhen; Ejaz, Ahsan

2016-11-01

The effects of temperature, solution composition and dissolved oxygen on the corrosion rate and electrochemical behavior of an A508III low alloy steel in boric acid solution with lithium hydroxide at 25-95 °C are investigated. In aerated solutions, increasing the boric acid concentration increases the corrosion rate and the anodic current density. The corrosion rate in deaerated solutions increases with increasing temperature. A corrosion rate peak value is found at approximately 75 °C in aerated solutions. Increasing temperature increases the oxygen diffusion coefficient, decreases the dissolved oxygen concentration, accelerates the hydrogen evolution reaction, and accelerates both the active dissolution and the film forming reactions. Increasing dissolved oxygen concentration does not significantly affect the corrosion rate at 50 and 60 °C, increases the corrosion rate at 70 and 80 °C, and decreases the corrosion rate at 87.5 and 95 °C in a high concentration boric acid solution with lithium hydroxide.

Development of Technologies on Innovative-Simplified Nuclear Power Plant using High-Efficiency Steam Injectors

NASA Astrophysics Data System (ADS)

Ohmori, Shuichi; Narabayashi, Tadashi; Mori, Michitsugu; Iwaki, Chikako; Asanuma, Yutaka; Goto, Shoji

A Steam Injector (SI) is a simple, compact and passive pump and also acts as a high-performance direct-contact heater. This provides SI with capability to serve also as a direct-contact feed-water heater that heats up feed-water by using extracted steam from turbine. Our technology development aims to significantly simplify equipment and reduce physical quantities by applying "High-Efficiency SI", which are applicable to a wide range of operation regimes beyond the performance and applicable range of existing SIs and enables unprecedented multistage and parallel operation, to the low-pressure feed-water heaters and Emergency Core Cooling System of nuclear power plants, as well as achieve high inherent safety to prevent severe accidents by keeping the core covered with water (a Severe Accident-Free Concept). This paper describes the results of the endurance and performance tests of low-pressure SIs for feed-water heaters with Jet-deaerator and core injection system.

Vacuum-sealed microcavity formed from suspended graphene by using a low-pressure dry-transfer technique

NASA Astrophysics Data System (ADS)

Takahashi, K.; Ishida, H.; Sawada, K.

2018-01-01

We report the development of a microcavity drum sealed by suspended graphene. The drum is fabricated by using a low-pressure dry-transfer technique, which involves vacuum de-aeration between a graphene sheet and a substrate and raising the temperature to above the glass transition of the supporting poly(methyl methacrylate) film, which serves to increase the real contact area. The result is a suspended graphene sheet with a maximum diameter of 48.6 μm. The Raman spectrum of the suspended graphene has a 2D/G ratio of 1.79 and a few D peaks, which suggests that the material is high-quality single-layer graphene. The dry-transfer technique yields a vacuum-sealed microcavity drum 1.1 μm deep up to 4.5 μm in diameter. The Raman shift indicates that the suspended graphene is subjected to a tensile strain of 0.05%, which is attributed to the pressure difference between the evacuated cavity and the exterior gas.

The influence of molecular symmetry and topological factors on the internal heavy atom effect in aromatic and heteroaromatic compounds

NASA Astrophysics Data System (ADS)

Nijegorodov, N.; Mabbs, R.

2001-06-01

The absorption and fluorescence properties of 26 specially selected aromatic and heteroaromatic compounds, from different classes, are studied quantum chemically and experimentally at room temperature (293 K). Seven of these compounds have not been studied before. The compounds are arranged in seven groups, which illustrate different cases of the internal heavy atom effect. The quantum yield of fluorescence, γ and fluorescence decay time, τf of deaerated and non-deaerated cyclohexane or ethanol solutions are measured. The oscillator strength, fe, fluorescence rate constant, kf, natural lifetime, τ0t, and intersystem crossing rate constant, kST, were calculated for each compound. The orbital nature of the lowest excited singlet state and direction of polarization of the S0→ S1 transitions are determined using the PPP-CI method for each molecule. The investigation shows that substitution of a heavy atom(s) (Cl, S, Br, I etc.) into an aromatic or heteroaromatic molecule may produce different changes in all the fluorescence parameters (sometimes dramatically) and not necessarily lead to the quenching of fluorescence. Substitution of a heavy atom(s) may increase the value of the spin-orbit operator, \\Hcirc SO, if the S0→ S1 excitation is localized to some extent on a carbon atom bonded to a heavy atom(s) or on the heavy atom itself (Ö or S). Such substitution may change the symmetry of a molecule and hence the values of the ΨS 1\\HcircsoΨT i' matrix elements would change (in molecules of higher symmetry groups not all Ti states are able to mix with the perturbing S1 state). Such substitution may change the arrangement of Ti states below the S1, state and hence, the Franck-Condon factors would change. Such substitution may also change the value of the ΨS 0M jΨS 1 matrix element and, consequently, the oscillator strength of the S0→ S1 transition would change. A combination of all these possible changes determines the value of kf and kST and, consequently, determines the value of γ and τf. It is observed that in many cases, the value of the spin-orbit operator is related to the dipole moment operator, e.g. if the introduction of a heavy atom increases kST then, as a rule, it decreases fe( 1A→ 1La).

Instrumented roll technology for the design space development of roller compaction process.

PubMed

Nesarikar, Vishwas V; Vatsaraj, Nipa; Patel, Chandrakant; Early, William; Pandey, Preetanshu; Sprockel, Omar; Gao, Zhihui; Jerzewski, Robert; Miller, Ronald; Levin, Michael

2012-04-15

Instrumented roll technology on Alexanderwerk WP120 roller compactor was developed and utilized successfully for the measurement of normal stress on ribbon during the process. The effects of process parameters such as roll speed (4-12 rpm), feed screw speed (19-53 rpm), and hydraulic roll pressure (40-70 bar) on normal stress and ribbon density were studied using placebo and active pre-blends. The placebo blend consisted of 1:1 ratio of microcrystalline cellulose PH102 and anhydrous lactose with sodium croscarmellose, colloidal silicon dioxide, and magnesium stearate. The active pre-blends were prepared using various combinations of one active ingredient (3-17%, w/w) and lubricant (0.1-0.9%, w/w) levels with remaining excipients same as placebo. Three force transducers (load cells) were installed linearly along the width of the roll, equidistant from each other with one transducer located in the center. Normal stress values recorded by side sensors and were lower than normal stress values recorded by middle sensor and showed greater variability than middle sensor. Normal stress was found to be directly proportional to hydraulic pressure and inversely to screw to roll speed ratio. For active pre-blends, normal stress was also a function of compressibility. For placebo pre-blends, ribbon density increased as normal stress increased. For active pre-blends, in addition to normal stress, ribbon density was also a function of gap. Models developed using placebo were found to predict ribbon densities of active blends with good accuracy and the prediction error decreased as the drug concentration of active blend decreased. Effective angle of internal friction and compressibility properties of active pre blend may be used as key indicators for predicting ribbon densities of active blend using placebo ribbon density model. Feasibility of on-line prediction of ribbon density during roller compaction was demonstrated using porosity-pressure data of pre-blend and normal stress measurements. Effect of vacuum to de-aerate pre blend prior to entering the nip zone was studied. Varying levels of vacuum for de-aeration of placebo pre blend did not affect the normal stress values. However, turning off vacuum completely caused an increase in normal stress with subsequent decrease in gap. Use of instrumented roll demonstrated potential to reduce the number of DOE runs by enhancing fundamental understanding of relationship between normal stress on ribbon and process parameters. Copyright © 2012 Elsevier B.V. All rights reserved.

Early Onset of Nucleate Boiling on Gas-covered Biphilic Surfaces.

PubMed

Shen, Biao; Yamada, Masayuki; Hidaka, Sumitomo; Liu, Jiewei; Shiomi, Junichiro; Amberg, Gustav; Do-Quang, Minh; Kohno, Masamichi; Takahashi, Koji; Takata, Yasuyuki

2017-05-17

For phase-change cooling schemes for electronics, quick activation of nucleate boiling helps safeguard the electronics components from thermal shocks associated with undesired surface superheating at boiling incipience, which is of great importance to the long-term system stability and reliability. Previous experimental studies show that bubble nucleation can occur surprisingly early on mixed-wettability surfaces. In this paper, we report unambiguous evidence that such unusual bubble generation at extremely low temperatures-even below the boiling point-is induced by a significant presence of incondensable gas retained by the hydrophobic surface, which exhibits exceptional stability even surviving extensive boiling deaeration. By means of high-speed imaging, it is revealed that the consequently gassy boiling leads to unique bubble behaviour that stands in sharp contrast with that of pure vapour bubbles. Such findings agree qualitatively well with numerical simulations based on a diffuse-interface method. Moreover, the simulations further demonstrate strong thermocapillary flows accompanying growing bubbles with considerable gas contents, which is associated with heat transfer enhancement on the biphilic surface in the low-superheat region.

Formation of combustible hydrocarbons and H2 during photocatalytic decomposition of various organic compounds under aerated and deaerated conditions.

PubMed

Mozia, Sylwia; Kułagowska, Aleksandra; Morawski, Antoni W

2014-11-26

A possibility of photocatalytic production of useful aliphatic hydrocarbons and H2 from various organic compounds, including acetic acid, methanol, ethanol and glucose, over Fe-modified TiO2 is discussed. In particular, the influence of the reaction atmosphere (N2, air) was investigated. Different gases were identified in the headspace volume of the reactor depending on the substrate. In general, the evolution of the gases was more effective in air compared to a N2 atmosphere. In the presence of air, the gaseous phase contained CO2, CH4 and H2, regardless of the substrate used. Moreover, formation of C2H6 and C3H8 in the case of acetic acid and C2H6 in the case of ethanol was observed. In case of acetic acid and methanol an increase in H2 evolution under aerated conditions was observed. It was concluded that the photocatalytic decomposition of organic compounds with simultaneous generation of combustible hydrocarbons and hydrogen could be a promising method of "green energy" production.

Development and validation of a discriminating in vitro dissolution method for a poorly soluble drug, olmesartan medoxomil: comparison between commercial tablets.

PubMed

Bajerski, Lisiane; Rossi, Rochele Cassanta; Dias, Carolina Lupi; Bergold, Ana Maria; Fröehlich, Pedro Eduardo

2010-06-01

A dissolution test for tablets containing 40 mg of olmesartan medoxomil (OLM) was developed and validated using both LC-UV and UV methods. After evaluation of the sink condition, dissolution medium, and stability of the drug, the method was validated using USP apparatus 2, 50 rpm rotation speed, and 900 ml of deaerated H(2)O + 0.5% sodium lauryl sulfate (w/v) at pH 6.8 (adjusted with 18% phosphoric acid) as the dissolution medium. The model-independent method using difference factor (f(1)) and similarity factor (f(2)), model-dependent method, and dissolution efficiency were employed to compare dissolution profiles. The kinetic parameters of drug release were also investigated. The obtained results provided adequate dissolution profiles. The developed dissolution test was validated according to international guidelines. Since there is no monograph for this drug in tablets, the dissolution method presented here can be used as a quality control test for OLM in this dosage form, especially in a batch to batch evaluation.

Corrosion behavior of ceramic-coated ZIRLO™ exposed to supercritical water

NASA Astrophysics Data System (ADS)

Mandapaka, Kiran K.; Cahyadi, Rico S.; Yalisove, Steven; Kuang, Wenjun; Sickafus, K.; Patel, Maulik K.; Was, Gary S.

2018-01-01

The corrosion behavior of ceramic coated ZIRLO™ tubing was evaluated in a supercritical water (SCW) environment to determine its behavior in high temperature water. Two coating architectures were analyzed; a 4 bi-layer TiAlN/TiN coating with Ti bond coat, and a TiN monolithic coating with Ti bond layer on ZIRLO™ tubes using cathodic arc physical vapor deposition (CA-PVD) technique. Femtosecond laser ablation was used to introduce reproducible defects in some of the coated tubes. On exposure to deaerated supercritical water at 542 °C for 48 h, coated tubes exhibited significantly higher weight gain compared to uncoated ZIRLO™. Examination revealed formation of a uniform ZrO2 layer beneath the coating of a thickness similar to that on the uncoated tube inner surface. The defects generated during the coating process acted as preferential paths for diffusion of oxygen resulting in the oxidation of substrate ZIRLO™. However, there was no delamination of the coating. There were insignificant differences in the oxidation weight gain between laser ablated and non-ablated tubes and the laser induced defects did not spread beyond their original size.

Influence of Postbuild Microstructure on the Electrochemical Behavior of Additively Manufactured 17-4 PH Stainless Steel

NASA Astrophysics Data System (ADS)

Stoudt, M. R.; Ricker, R. E.; Lass, E. A.; Levine, L. E.

2017-03-01

The additive manufacturing build process produces a segregated microstructure with significant variations in composition and phases that are uncommon in traditional wrought materials. As such, the relationship between the postbuild microstructure and the corrosion resistance is not well understood. Stainless steel alloy 17-4 precipitation hardened (SS17-4PH) is an industrially relevant alloy for applications requiring high strength and good corrosion resistance. A series of potentiodynamic scans conducted in a deaerated 0.5-mol/L NaCl solution evaluated the influence of these microstructural differences on the pitting behavior of SS17-4. The pitting potentials were found to be higher in the samples of additively processed material than in the samples of the alloy in wrought form. This indicates that the additively processed material is more resistant to localized corrosion and pitting in this environment than is the wrought alloy. The results also suggest that after homogenization, the additively produced SS17-4 could be more resistant to pitting than the wrought SS17-4 is in an actual service environment.

The Influence of Post-Build Microstructure on the Electrochemical Behavior of Additively Manufactured 17-4 PH Stainless Steel.

PubMed

Stoudt, M R; Ricker, R E; Lass, E A; Levine, L E

2017-03-01

The additive manufacturing (AM) build process produces a segregated microstructure with significant variations in composition and phases that are uncommon in traditional wrought materials. As such, the relationship between the post-build microstructure and the corrosion resistance is not well understood. Stainless steel alloy 17-4PH is an industrially-relevant alloy for applications requiring high-strength and good corrosion resistance. A series of potentiodynamic scans conducted in a deaerated 0.5 mol/L NaCl solution evaluated the influence of these microstructural differences on the pitting behavior of SS17-4. The pitting potentials were found to be higher in the samples of additively-processed material than in samples of the alloy in wrought form. This indicates that the additively-processed material is more resistant to localized corrosion and pitting in this environment than the wrought alloy. The results also suggest that after homogenization, the additively-produced SS17-4 could be more resistant to pitting than wrought SS17-4 in an actual service environment.

The Influence of Post-Build Microstructure on the Electrochemical Behavior of Additively Manufactured 17-4 PH Stainless Steel

PubMed Central

Stoudt, M. R.; Ricker, R. E.; Lass, E. A.; Levine, L. E.

2017-01-01

The additive manufacturing (AM) build process produces a segregated microstructure with significant variations in composition and phases that are uncommon in traditional wrought materials. As such, the relationship between the post-build microstructure and the corrosion resistance is not well understood. Stainless steel alloy 17-4PH is an industrially-relevant alloy for applications requiring high-strength and good corrosion resistance. A series of potentiodynamic scans conducted in a deaerated 0.5 mol/L NaCl solution evaluated the influence of these microstructural differences on the pitting behavior of SS17-4. The pitting potentials were found to be higher in the samples of additively-processed material than in samples of the alloy in wrought form. This indicates that the additively-processed material is more resistant to localized corrosion and pitting in this environment than the wrought alloy. The results also suggest that after homogenization, the additively-produced SS17-4 could be more resistant to pitting than wrought SS17-4 in an actual service environment. PMID:28757787

Transient species in the pulse radiolysis of methylene chloride and the self-reaction of chloromethyl radicals

NASA Astrophysics Data System (ADS)

Emmi, S. S.; Beggiato, G.; Casalbore-Miceli, G.

Chlorine atoms formed during the pulse radiolysis of deaerated methylene chloride at room temperature react with the solvent in the first 70 ns from the pulse at a bimolecular rate constant k4 ≈ 6 × 10 6 M -1s -1 and are available to otther reactions only at solute concentrations higher than 10 -3M. A u.v.-vis. spectrum is detected, the main features of which are a peak at 350 nm, a broad absorption in the vis. and a remarkable band in the u.v. The "350" species undertakes a fast first order decay ( k = 9.0 × 10 7s -1) which is followed by a slower decay ( k = 5.3 × 10 4s -1). The "u.v." species is a mixing of mono-and dichloromethyl radicals. These radicals recombine and cross-combine as if they were a single species; a rate constant 2 k 9 = 2 k 10 less than 2.4 × 10 9M -1s -1 for the combination reactions can be evaluated from the observed decay rate. Configurational factors are considered in connection with the reactivity of chlorosubstituted methyl radicals.

Cracking characteristics of alloy 690 in thiosulfate containing chloride solution

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

Huang, H.H.; Tsai, W.T.

1999-07-01

The cracking characteristics of Alloy 690 in deaerated 1wt% NaCl solution with different Na{sub 2}S{sub 2}O{sub 2} concentrations, namely 0.01, 0.1, 0.2 and 0.5 M, at controlled anodic potentials was investigated by using slow strain rate testing (SSRT) with a strain rate of 1 x 10{sup {minus}6} s{sup {minus}1}. The results showed that the ultimate tensile strength and the ductility increased with increasing the concentration of Na{sub 2}S{sub 2}O{sub 3} at the same anodic potential, but decreased with increasing potential at a fixed concentration of Na{sub 2}S{sub 2}O{sub 3}. Pitting corrosion could occur on Alloy 690 in 1wt% NaCl solutionmore » with the concentration of Na{sub 2}S{sub 2}O{sub 3} {le} 0.1 M, depending on the potential. The susceptibilities of Alloy 690 to pitting corrosion and environmentally-assisted cracking in 1wt% NaCl solution were inhibited with the concentration of Na{sub 2}S{sub 2}O{sub 3} {ge} 0.2M, regardless of the potential.« less

Effect of different thermal treatments on the corrosion resistance of alloy 690 tubing

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

Crum, J.R.; Heck, K.A.; Angeliu, T.M.

1990-03-01

A comparison of the carbide precipitation characteristics and corrosion resistance of commercially produced alloy 690 steam generator tubing from various sources, with different thermal treatments, was made. Four thermal treatments within the ranges of 700--720{degree}C (1292--1328{degree}F)/5--5.75 hrs and 871--927{degree}C (1600--1700{degree}F)/10 min were compared to one another and to two as-mill annealed tubes. All tubes were characterized with respect to chemical composition, mechanical properties, and microstructure. Overall carbide precipitation was determined by etching with phosphoric acid/nital, bromine-methanol and glyceregia/oxalic etchants. Scanning transmission electron microscope analysis provided detailed chromium depletion profiles across the grain boundary and carbide composition. Nitric acid intergranular attackmore » (IGA) tests were also conducted. C-ring stress corrosion cracking (SCC) tests, with stresses above the yield strength were then conducted in 350{degree}C (662{degree}F) deaerated 1, 10, and 50% NaOH and unstressed IGA tests were conducted in a NaOH-Na{sub 2}SO{sub 4}--Fe{sub 3}O{sub 4}--Fe{sub 2}O{sub 3} environment, also at 350{degree}C (662{degree}F). 2 tabs.« less

Porous Teflon ring-solid disk electrode arrangement for differential mass spectrometry measurements in the presence of convective flow generated by a jet impinging electrode in the wall-jet configuration.

PubMed

Treufeld, Imre; Jebaraj, Adriel Jebin Jacob; Xu, Jing; Martins de Godoi, Denis; Scherson, Daniel

2012-06-19

A porous Teflon ring|solid disk electrode is herein described specifically designed for acquiring online mass spectrometric measurements under well-defined forced convection created by liquid emerging from a circular nozzle impinging on the disk under wall-jet conditions. Measurements were performed for the oxidation of hydrazine, N(2)H(4), in a deaerated phosphate buffer electrolyte (pH 7) on Au, a process known to yield dinitrogen as the product. The N(2)(+) ion currents, measured by the mass spectrometer, i(N(2)(+)), as well as the corresponding polarization curves recorded simultaneously displayed very similar s-like shapes when plotted as a function of the potential applied to the Au disk. In fact, the limiting currents observed both electrochemically and spectrometrically were found to be proportional to [N(2)H(4)]. However, the limiting values of i(N(2)(+)) did not increase monotonically with the flow rate, ν(f), reaching instead a maximum and then decreasing to values independent of ν(f). This behavior has been attributed in part to hindrances in the mass transport of gases through the porous materials.

Structure, adhesive strength and electrochemical performance of nitrogen doped diamond-like carbon thin films deposited via DC magnetron sputtering.

PubMed

Khun, N W; Liu, E; Krishna, M D

2010-07-01

Nitrogen doped diamond-like carbon (DLC:N) thin films were deposited on p-Si (100) substrates by DC magnetron sputtering with different nitrogen flow rates at a substrate temperature of about 100 degrees C. The chemical bonding structure of the films was characterized by X-ray photoelectron spectroscopy (XPS) and micro-Raman spectroscopy. The adhesive strength and surface morphology of the films were studied using micro-scratch tester and scanning electron microscope (SEM), respectively. The electrochemical performance of the films was evaluated by potentiodynamic polarization testing and linear sweep voltammetry. The electrolytes used for the electrochemical tests were deaerated and unstirred 0.47 M KCl aqueous solution for potentiodynamic polarization testing and 0.2 M KOH and 0.1 M KCl solutions for voltammetric analysis. It was found that the DLC:N films could well passivate the underlying substrates though the corrosion resistance of the films decreased with increased nitrogen content in the films. The DLC:N films showed wide potential windows in the KOH solution, in which the detection ability of the DLC:N films to trace lead of about 1 x 10(-3) M Pb(2+) was also tested.

Use of electrochemical potential noise to detect initiation and propagation of stress corrosion cracks in a 17-4 PH steel

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

Gonzalez-Rodriguez, J.G.; Salinas-Bravo, V.M.; Garcia-Ochoa, E.

1997-09-01

Corrosion potential transients were associated with nucleation and propagation of stress corrosion cracks in a 17-4 precipitation-hardenable (PH) martensitic stainless steel (SS) during slow strain rate tests (SSRT) at 90 C in deaerated sodium chloride (NaCl) solutions, Test solutions included 20 wt% NaCl at pH 3 and 7, similar to normal and faulted steam turbine environments, respectively. Time series were analyzed using the fast Fourier transform method. At the beginning of straining, the consistent noise behavior was perturbed with small potential transients, probably associated with rupture of the surface oxide layer. After yielding, these transients increased in intensity. At maximummore » load, the transients were still higher in intensity and frequency. These potential transients were related to crack nucleation and propagation. When the steel did not fail by stress corrosion cracking (SCC), such transients were found only at the beginning of the test. The power spectra showed some differences in all cases in roll-off slope and voltage magnitude, but these were not reliable tools to monitor the initiation and propagation of stress corrosion cracks.« less

Ni and Cr addition to alloy waste forms to reduce radionuclide environmental releases

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

Olson, L.

2016-10-11

Reference alloy waste forms (RAW) were fabricated and underwent hybrid corrosion/immersion testing to parameterize the ANL analytical oxidative-dissolution model to enable the calculation of fractional release rates and to determine the effectiveness of Ni and Cr trim additions in reducing release rates of radionuclide surrogates. Figure 1 shows the prototypical multiphase microstructure of the alloys with each phase type contributing about equally to the exposed surface area. The waste forms tested at SRNL were variations of the RAW-6 formulation that uses HT9 as the main alloy component, and are meant to enable evaluation of the impact of Ni and Crmore » trim additions on the release rates of actinides and Tc-99. The test solutions were deaerated alkaline and acidic brines, ranging in pH 3 to pH 10, representing potential repositories with those conditions. The testing approach consisted of 4 major steps; 1) bare surface corrosion measurements at pH values of 3, 5, 8, and 10, 2) hybrid potentiostatic hold/exposure measurements at pH 3, 3) measurement of radionuclide concentrations and relations to anodic current from potentiostatic holds, and 4) identification of corroding phases using SEM/EDS of electrodes.« less

Derivatization of single-walled carbon nanotubes with redox mediator for biocatalytic oxygen electrodes.

PubMed

Sadowska, K; Stolarczyk, K; Biernat, J F; Roberts, K P; Rogalski, J; Bilewicz, R

2010-11-01

Single-walled carbon nanotubes (SWCNTs) were covalently modified with a redox mediator derived from 2,2'-azino-bis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS), and implemented in the construction of electrodes for biocatalytic oxygen reduction. The procedure is based on: covalent bonding of mediator to nanotubes, placing the nanotubes directly on the carbon electrode surface and covering the nanostructured electrode with a Nafion film containing laccase as the biocatalyst. The modified electrode is stable and the problem of mediator (ABTS) leaking from the film is eliminated by binding it covalently to the nanotubes. Three different synthetic approaches were used to obtain ABTS-modified carbon nanotubes. Nanotubes were modified at ends/defect sites or on the nanotube sidewalls and characterized by Raman spectroscopy, TGA and electrochemistry. The accessibility of differently located ABTS units by the laccase active center and mediation of electron transfer were studied by cyclic voltammetry. The surface concentrations of ABTS groups electrically connected with the electrode were compared for each of the electrodes based on the charges of the voltammetric peaks recorded in the deaerated solution. The nanotube modification procedure giving the best parameters of the catalytic process was selected. Copyright © 2010 Elsevier B.V. All rights reserved.

[Optimization of blood gas analysis in intensive care units : Reduction of preanalytical errors and improvement of workflow].

PubMed

Kieninger, M; Zech, N; Mulzer, Y; Bele, S; Seemann, M; Künzig, H; Schneiker, A; Gruber, M

2015-05-01

Point of care testing with blood gas analysis (BGA) is an important factor for intensive care medicine. Continuous efforts to optimize workflow, improve safety for the staff and avoid preanalytical mistakes are important and should reflect quality management standards. In a prospective observational study it was investigated whether the implementation of a new system for BGA using labeled syringes and automated processing of the specimens leads to improvements compared to the previously used procedure. In a 4-week test period the time until receiving the final results of the BGA with the standard method used in the clinical routine (control group) was compared to the results in a second 4-week test period using the new labeled syringes and automated processing of the specimens (intervention group). In addition, preanalytical mistakes with both systems were checked during routine daily use. Finally, it was investigated whether a delay of 10 min between taking and analyzing the blood samples alters the results of the BGA. Preanalytical errors were frequently observed in the control group where non-deaerated samples were recorded in 87.3 % but in the intervention group almost all samples (98.9 %) were correctly deaerated. Insufficient homogenization due to omission of manual pivoting was seen in 83.2 % in the control group and in 89.9 % in the intervention group; however, in the intervention group the samples were homogenized automatically during the further analytical process. Although a survey among the staff revealed a high acceptance of the new system and a subjective improvement of workflow, a measurable gain in time after conversion to the new procedure could not be seen. The mean time needed for a complete analysis process until receiving the final results was 244 s in the intervention group and 201 s in the control group. A 10-min delay between taking and analyzing the blood samples led to a significant and clinically relevant elevation of the values for partial pressure of oxygen (pO2) in both groups compared to the results when analyzing the samples immediately (118.4 vs. 148.6 mmHg in the control group and 115.3 vs. 123.7 mmHg in the intervention group). When using standard syringes the partial pressure of carbon dioxide (pCO2) was significantly lower (40.5 vs. 38.3 mmHg) whereas no alterations were seen when using the labeled syringes. The implementation of a new BGA system with labeled syringes and automated processing of the specimens was possible without any difficulties under daily clinical routine conditions in this 10-bed intensive care unit (ICU). A gain of time could not be measured but a reduction in preanalytical errors using the labeled syringes with automated processing was found. Delayed analysis of blood samples can lead to significant changes in pO2 and pCO2 depending on the type of syringe used.

Thermally activated delayed fluorescence of fluorescein derivative for time-resolved and confocal fluorescence imaging.

PubMed

Xiong, Xiaoqing; Song, Fengling; Wang, Jingyun; Zhang, Yukang; Xue, Yingying; Sun, Liangliang; Jiang, Na; Gao, Pan; Tian, Lu; Peng, Xiaojun

2014-07-09

Compared with fluorescence imaging utilizing fluorophores whose lifetimes are in the order of nanoseconds, time-resolved fluorescence microscopy has more advantages in monitoring target fluorescence. In this work, compound DCF-MPYM, which is based on a fluorescein derivative, showed long-lived luminescence (22.11 μs in deaerated ethanol) and was used in time-resolved fluorescence imaging in living cells. Both nanosecond time-resolved transient difference absorption spectra and time-correlated single-photon counting (TCSPC) were employed to explain the long lifetime of the compound, which is rare in pure organic fluorophores without rare earth metals and heavy atoms. A mechanism of thermally activated delayed fluorescence (TADF) that considers the long wavelength fluorescence, large Stokes shift, and long-lived triplet state of DCF-MPYM was proposed. The energy gap (ΔEST) of DCF-MPYM between the singlet and triplet state was determined to be 28.36 meV by the decay rate of DF as a function of temperature. The ΔE(ST) was small enough to allow efficient intersystem crossing (ISC) and reverse ISC, leading to efficient TADF at room temperature. The straightforward synthesis of DCF-MPYM and wide availability of its starting materials contribute to the excellent potential of the compound to replace luminescent lanthanide complexes in future time-resolved imaging technologies.

Electron Microscopic Observations of the Carotid Body of the Cat

PubMed Central

Ross, Leonard L.

1959-01-01

Carotid bodies were removed from cats, fixed in buffered 1 per cent osmic acid, embedded in deaerated, nitrogenated methacrylate, and cut into thin sections for electron microscopic study. The carotid body is seen to be composed of islands of chemoreceptor and sustentacular cells surrounded by wide irregular sinusoids. These cells are separated from the sinusoids by relatively broad interstitial spaces which are filled with collagen, fibroblasts, and many unmyelinated nerve fibers with their Schwann cell sheaths. The chemoreceptor cells are surrounded by the flattened, multiprocessed sustentacular cells which serve to convey the axons from an interstitial to a pericellular location. These sustentacular cells are assumed to be lemmoblastic in origin. Relatively few axons are seen to abut on the chemoreceptor cells. The cytoplasm of the chemoreceptor cell is characterized by numerous small mitochondria, units of granular endoplasmic reticulum, a small Golgi complex, and a variety of vesicles. There are many small vesicles diffusely scattered throughout the cytoplasm. In addition, there is a small number of dark-cored vesicles of the type which has been previously described in the adrenal medulla. These are usually associated with the Golgi complex. These findings are discussed in relation to the concepts of the origin of the chemoreceptor cell and the nature of the synapse. PMID:14439171

In Vivo and In Vitro Nitinol Corrosion Properties

NASA Astrophysics Data System (ADS)

Lonn, Melissa K.; Metcalf, Justin M.; Choules, Brian D.

2015-09-01

Regulatory authorities often require in vitro testing on medical devices prior to approval. Current standardized corrosion testing methods (ASTM F2129) require testing in a non-physiologic, de-oxygenated solution for a pre-exposure time of ≤1 h; however, no correlations between the prescribed simulated environment and whole blood conditions have been elucidated. This study compared open circuit potential (OCP), breakdown potentials (Eb), Eb - OCP, and cyclic polarization curves tested in vivo (OCP only) and in vitro in whole blood to those tested in phosphate-buffered saline (PBS). Two oxide thicknesses of Nitinol, two solution oxygen contents (deaerated and aerated solutions), and two pre-exposure durations (acute and chronic) were investigated. The in vitro OCP in whole blood was not significantly different than the in vivo OCP, suggesting that whole blood in vitro can be used to determine baseline corrosion behavior of medical implants. Eb - OCP tested per ASTM F2129 was comparable to acute whole blood and was conservative compared to chronic whole blood for both oxide thicknesses. However, OCP, Eb, and cyclic polarization curves were not always comparable to whole blood. Testing in aerated PBS achieved Eb, Eb - OCP, and cyclic polarization curves that were comparable to or more conservative than whole blood testing, regardless of pre-exposure duration and oxide thickness.

A new trinuclear complex of platinum and iron efficiently promotes cleavage of plasmid DNA.

PubMed Central

Lempers, E L; Bashkin, J S; Kostić, N M

1993-01-01

The compound [[Pt(trpy)]2Arg-EDTA]+ is synthesized in five steps, purified, and characterized by 1H, 13C, and 195Pt NMR spectroscopy, mass spectrometry, UV-vis spectrophotometry, and elemental analysis. The binuclear [[(Pt(trpy)]2Arg]3+ moiety binds to double-stranded DNA, and the chelating EDTA moiety holds metal cations. In the presence of ferrous ions and the reductant dithiothreitol, the new compound cleaves DNA. It cleaves a single strand in the pBR322 plasmid nearly as efficiently as methidiumrpropyl-EDTA (MPE), and it cleaves a restriction fragment of the XP10 plasmid nonselectively and more efficiently than [Fe(EDTA)]2-. The mechanism of cleavage was studied in control experiments involving different transition-metal ions, superoxide dismutase, catalase, glucose oxidase with glucose, metal-sequestering agents, and deaeration. These experiments indicate that adventitious iron and copper ions, superoxide anion, and hydrogen peroxide are not involved and that dioxygen is required. The cleavage apparently is done by hydroxyl radicals generated in the vicinity of the DNA molecule. The reagent [[Pt(trypy)]2Arg-EDTA]+ differs from methidiumpropyl-EDTA in not containing an intercalator. This difference in binding modes between the binuclear platinum(II) complex and the planar heterocycle may cause useful differences between the two reagents in cleavage of nucleic acids. Images PMID:8493109

Corrosion evaluation of heat recovery steam generator superheater tube in two methods of testing: Tafel polarization and electrochemical impedance spectroscopy (EIS)

NASA Astrophysics Data System (ADS)

Santoso, Rio Pudjidarma; Riastuti, Rini

2018-05-01

The purpose of this research is to evaluate the corrosion process which occurs on the water side of Heat Recovery Steam Generator (HRSG) superheater tube. The tube was 13CrMo44 and divided into 3 types of specimen: new tube, used tube (with oxide layer on surface), cleaned-used tube (without oxide layer on surface). The evaluation of corrosion parameters wasperformed using deaerated ultra-high purity water (boiler feed water) in two methods of testing: Tafel polarization and Electrochemical Impedance Spectroscopy (EIS). Tafel polarization was excellent as its capability to show the value of corrosion current and the corrosion rate explicitly, on the other hand, EIS was excellent as its capability to explain for corrosion mechanism on metal interface in detail. Both methods showed that the increase of electrolyte temperature from 25°C to 55°C would increase the corrosion rate with the mechanism of decreasing polarization resistance due to thinning out the passive film thickness and enlarge the area of reduction reaction of cathode. Magnetite oxide scale which is laid on the surface of used tube specimen shows protective nature to reduce the corrosion rate, and clear up this oxide would increase the corrosion rate back as new tube.

Interaction of Black Phosphorus with Oxygen and Water

DOE PAGES

Huang, Yuan; Qiao, Jingsi; He, Kai; ...

2016-10-24

Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. Chemical reactions with different ambient species, notably oxygen and water, are important as they govern key properties such as stability in air, electronic structure and charge transport, wetting by aqueous solutions, etc. Here, we report experiments combined with ab-initio calculations that address the effects of oxygen and water in contact with BP. Our results show that the reaction with oxygen is primarily responsible for changing properties of BP. Oxidation involving the dissociative chemisorption of O 2 causes the decomposition of BPmore » and continuously lowers the conductance of BP field-effect transistors (FETs). In contrast, BP is stable in contact with deaerated (i.e., O 2 depleted) water and the carrier mobility in BP FETs gated by H 2O increases significantly due to efficient dielectric screening of scattering centers by the high-k dielectric. Isotope labeling experiments, contact angle measurements and calculations show that the pristine BP surface is hydrophobic, but is turned progressively hydrophilic by oxidation. Lastly, our results open new avenues for exploring applications that require contact of BP with aqueous solutions including solution gating, electrochemistry, and solution-phase approaches for exfoliation, dispersion, and delivery of BP.« less

Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination

PubMed Central

Sun, Huihui; Liu, Zhuang; Wu, Chao; Xu, Ping; Wang, Xia

2016-01-01

As a well-known toxic pollutant, sulfide is harmful to human health. In this study, a simple and sensitive amperometric inhibitive biosensor was developed for the determination of sulfide in the environment. By immobilizing nanoporous gold (NPG) on glassy carbon electrode (GCE), and encapsulating horseradish peroxidase (HRP) onto NPG, a HRP/NPG/GCE bioelectrode for sulfide detection was successfully constructed based on the inhibition of sulfide on HRP activity with o-Phenylenediamine (OPD) as a substrate. The resulted HRP/NPG/GCE bioelectrode achieved a wide linear range of 0.1–40 μM in sulfide detection with a high sensitivity of 1720 μA mM−1 cm−2 and a low detection limit of 0.027 μM. Additionally, the inhibition of sulfide on HRP is competitive inhibition with OPD as a substrate by Michaelis-Menten analysis. Notably, the recovery of HRP activity was quickly achieved by washing the HRP/NPG/GCE bioelectrode using differential pulse voltammetry (DPV) technique in deaerated PBS (50 mM, pH 7.0) for only 60 s. Furthermore, the real sample analysis of sulfide by the HRP/NPG/GCE bioelectrode was achieved. Based on above results, the HRP/NPG/GCE bioelectrode could be a better choice for the real determination of sulfide compared to inhibitive biosensors previously reported. PMID:27515253

Immobilization of glucose oxidase into a nanoporous TiO₂ film layered on metallophthalocyanine modified vertically-aligned carbon nanotubes for efficient direct electron transfer.

PubMed

Cui, Hui-Fang; Zhang, Kuan; Zhang, Yong-Fang; Sun, Yu-Long; Wang, Jia; Zhang, Wei-De; Luong, John H T

2013-08-15

Glucose oxidase (GOD) was adsorbed into a nanoporous TiO₂ film layered on the surface of an iron phthalocyanine (FePc) vertically-aligned carbon nanotube (CNT) modified electrode. A Nafion film was then dropcast on the electrode's surface to improve operational and storage stabilities of the GOD-based electrode. Scanning electron microscopy (SEM) micrographs revealed the formation of FePc and nanoporous TiO₂ nanoparticles along the sidewall and the tip of CNTs. Cyclic voltammograms of the GOD electrode in neutral PBS exhibited a pair of well-defined redox peaks, attesting the direct electron transfer of GOD (FAD/FADH₂) with the underlying electrode. The potential of glucose electro-oxidation under nitrogen was ∼+0.12 V with an oxidation current density of 65.3 μA cm(-2) at +0.77 V. Voltammetric and amperometric responses were virtually unaffected by oxygen, illustrating an efficient and fast direct electron transfer. The modification of the CNT surface with FePc resulted in a biosensor with remarkable detection sensitivity with an oxygen-independent bioelectrocatalysis. In deaerated PBS, the biosensor displayed average response time of 12 s, linearity from 50 μM to 4 mM, and a detection limit of 30 μM (S/N=3) for glucose. Copyright © 2013 Elsevier B.V. All rights reserved.

Impact of different welding techniques on biological effect markers in exhaled breath condensate of 58 mild steel welders.

PubMed

Hoffmeyer, Frank; Raulf-Heimsoth, Monika; Lehnert, Martin; Kendzia, Benjamin; Bernard, Sabine; Berresheim, Hans; Düser, Maria; Henry, Jana; Weiss, Tobias; Koch, Holger M; Pesch, Beate; Brüning, Thomas

2012-01-01

Total mass and composition of welding fumes are predominantly dependent on the welding technique and welding wire applied. The objective of this study was to investigate the impact of welding techniques on biological effect markers in exhaled breath condensate (EBC) of 58 healthy welders. The welding techniques applied were gas metal arc welding with solid wire (GMAW) (n=29) or flux cored wire (FCAW) (n=29). Welding fume particles were collected with personal samplers in the breathing zone inside the helmets. Levels of leukotriene B(4) (LTB(4)), prostaglandin E(2) (PGE(2)), and 8-isoprostane (8-iso-PGF(2α)) were measured with immunoassay kits and the EBC pH was measured after deaeration. Significantly higher 8-iso-PGF(2α) concentrations and a less acid pH were detected in EBC of welders using the FCAW than in EBC of welders using the GMAW technique. The lowest LTB(4) concentrations were measured in nonsmoking welders applying a solid wire. No significant influences were found in EBC concentrations of PGE(2) based upon smoking status or type of welding technique. This study suggests an enhanced irritative effect in the lower airways of mild steel welders due to the application of FCAW compared to GMAW, most likely associated with a higher emission of welding fumes.

Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination

NASA Astrophysics Data System (ADS)

Sun, Huihui; Liu, Zhuang; Wu, Chao; Xu, Ping; Wang, Xia

2016-08-01

As a well-known toxic pollutant, sulfide is harmful to human health. In this study, a simple and sensitive amperometric inhibitive biosensor was developed for the determination of sulfide in the environment. By immobilizing nanoporous gold (NPG) on glassy carbon electrode (GCE), and encapsulating horseradish peroxidase (HRP) onto NPG, a HRP/NPG/GCE bioelectrode for sulfide detection was successfully constructed based on the inhibition of sulfide on HRP activity with o-Phenylenediamine (OPD) as a substrate. The resulted HRP/NPG/GCE bioelectrode achieved a wide linear range of 0.1-40 μM in sulfide detection with a high sensitivity of 1720 μA mM-1 cm-2 and a low detection limit of 0.027 μM. Additionally, the inhibition of sulfide on HRP is competitive inhibition with OPD as a substrate by Michaelis-Menten analysis. Notably, the recovery of HRP activity was quickly achieved by washing the HRP/NPG/GCE bioelectrode using differential pulse voltammetry (DPV) technique in deaerated PBS (50 mM, pH 7.0) for only 60 s. Furthermore, the real sample analysis of sulfide by the HRP/NPG/GCE bioelectrode was achieved. Based on above results, the HRP/NPG/GCE bioelectrode could be a better choice for the real determination of sulfide compared to inhibitive biosensors previously reported.

Enhanced Inactivation of Escherichia coli and MS2 Coliphage by Cupric Ion in the Presence of Hydroxylamine: Dual Microbicidal Effects.

PubMed

Kim, Hyung-Eun; Nguyen, Thuy T M; Lee, Hongshin; Lee, Changha

2015-12-15

The inactivation of Escherichia coli and MS2 coliphage by Cu(II) is found to be significantly enhanced in the presence of hydroxylamine (HA). The addition of a small amount of HA (i.e., 5-20 μM) increased the inactivation efficacies of E. coli and MS2 coliphage by 5- to 100-fold, depending on the conditions. Dual effects were anticipated to enhance the biocidal activity of Cu(II) by the addition of HA, viz. (i) the accelerated reduction of Cu(II) into Cu(I) (a stronger biocide) and (ii) the production of reactive oxidants from the reaction of Cu(I) with dissolved oxygen (evidenced by the oxidative transformation of methanol into formaldehyde). Deaeration enhanced the inactivation of E. coli but slightly decreased the inactivation efficacy of MS2 coliphage. The addition of 10 μM hydrogen peroxide (H2O2) greatly enhanced the MS2 inactivation, whereas the same concentration of H2O2 did not significantly affect the inactivation efficacy of E. coli Observations collectively indicate that different biocidal actions lead to the inactivation of E. coli and MS2 coliphage. The toxicity of Cu(I) is dominantly responsible for the E. coli inactivation. However, for the MS2 coliphage inactivation, the oxidative damage induced by reactive oxidants is as important as the effect of Cu(I).

Effect of temperature and dissolved oxygen on stress corrosion cracking behavior of P92 ferritic-martensitic steel in supercritical water environment

NASA Astrophysics Data System (ADS)

Zhang, Z.; Hu, Z. F.; Zhang, L. F.; Chen, K.; Singh, P. M.

2018-01-01

The effect of temperature and dissolved oxygen (DO) on stress corrosion cracking (SCC) of P92 martensitic steel in supercritical water (SCW) was investigated using slow strain rate test (SSRT) and fractography analysis. The SSRT was carried out at temperatures of 400, 500, 600 °C in deaerated supercritical water and at DO contents of 0, 200, 500 ppb at the temperature of 600 °C, respectively. The results of SSRT show that the decrease of ductility at the temperature of 400 °C may be related to the dynamic strain aging (DSA) of P92 steel. The degradation of the mechanical properties in SCW is the joint effect of temperature and SCC. Compared with the effect of temperature, DO in SCW has no significant effect on the SCC susceptibility of P92 steel. The observation of oxide layer shows that large numbers of pores are nucleated in the oxide layer, which is related to vacancy accumulation and hydrogen generated in the oxide layer. Under the combined action of the growth stress and tensile stress, micro cracks, nucleated from the pores in the oxide layer, are easily propagated intergranularly outward to the surface of specimen, and fewer cracks can extend inward along the intrinsic pores to the inner oxide/metal interface, which is the reason for the exfoliation of oxide films.

Homogeneous reduction of CO2 by photogenerated pyridinyl radicals.

PubMed

Riboni, Francesca; Selli, Elena; Hoffmann, M R; Colussi, A J

2015-05-14

We report that 1-hydropyridinyl radicals (1-PyH(•)) photogenerated in solution react with dissolved CO2 en route to its 2e(-) reduction into carboxylic acids. The 254 nm excitation of pyridine (Py) in deaerated 2-PrOH/H2O mixtures saturated with 1 atm of CO2 yields a suite of products, among which we identified Na(HCOO)2(-) (m/z(-) = 113), C5H6NCOO(-) (m/z(-) = 124), and C5H10O2NCOO(-) (m/z(-) = 160) species by electrospray ionization mass spectrometry. These products demonstrably contain carboxylate functionalities that split CO2 neutrals via collisionally induced dissociation. We infer that 1-PyH(•) [from (1) (3)Py* + 2-PrOH → 1-PyH(•) + (•)PrOH] adds to CO2, in competition with radical-radical reactions, leading to intermediates that are in turn reduced by (•)PrOH into the observed species. The formation of carboxylates in this system, which is shown to require CO2, Py, 2-PrOH, and actinic radiation, amounts to the homogeneous 2e(-) reduction of CO2 by 2-PrOH initiated by Py*. We evaluate a rate constant (2) k2(1-PyH(•) + CO2 → (•)Py-1-COOH) ≈ O (10) M(-1) s(-1) and an activation energy E2 ≥ 9 kcal mol(-1) that are compatible with thermochemical estimates for this reaction.

The effects of zinc addition on the environmental stability of Al-Li alloys

NASA Technical Reports Server (NTRS)

Kilmer, Raymond J.; Stoner, Glenn E.

1990-01-01

It was found that relatively small addition of Zn can improve the stress corrosion cracking (SCC) resistance of Al-Li alloys. However, the mechanism by which this is accomplished is unclear. The role that Zn plays in altering the behavior of Alloy 8090 is investigated. Early results suggest that Zn additions increase the volume fraction of delta(Al3Li) precipitation and differential scanning calorimetry (DSC) on these alloys confirms this. The four alloys studied each had initial compositions lying in the 8090 window and had varying amounts of Zn added to them. Alloy 8090, like other Al-Li alloys, displays a delta' precipitate free zone (PFZ) upon artificial aging along the grain and subgrain boundaries. However Zn additions greatly decreased or eliminated a delta' PFZ after 100 hours at 160 C. This implies that the subgrain boundary precipitation kinetics are being altered and suppressed. Furthermore, there appears to be a window of Zn concentration above which a delta ' PFZ can reappear with the nucleation and growth of a currently unidentified precipitate on the boundaries. Polarization experiments were performed and the results presented. The experiments were performed in deaerated 3.5 w/o NaCl in both as received (T3) condition and at peak aging of 100 hours at 160 C. The aging profile was determined via Vickers Hardness tests.

Response surface methodology as a tool for modeling and optimization of Bacillus subtilis spores inactivation by UV/ nano-Fe0 process for safe water production.

PubMed

Yousefzadeh, Samira; Matin, Atiyeh Rajabi; Ahmadi, Ehsan; Sabeti, Zahra; Alimohammadi, Mahmood; Aslani, Hassan; Nabizadeh, Ramin

2018-04-01

One of the most important aspects of environmental issues is the demand for clean and safe water. Meanwhile, disinfection process is one of the most important steps in safe water production. The present study aims at estimating the performance of UV, nano Zero-Valent Iron particles (nZVI, nano-Fe 0 ), and UV treatment with the addition of nZVI (combined process) for Bacillus subtilis spores inactivation. Effects of different factors on inactivation including contact time, initial nZVI concentration, UV irradiance and various aerations conditions were investigated. Response surface methodology, based on a five-level, two variable central composite design, was used to optimize target microorganism reduction and the experimental parameters. The results indicated that the disinfection time had the greatest positive impact on disinfection ability among the different selected independent variables. According to the results, it can be concluded that microbial reduction by UV alone was more effective than nZVI while the combined UV/nZVI process demonstrated the maximum log reduction. The optimum reduction of about 4 logs was observed at 491 mg/L of nZVI and 60 min of contact time when spores were exposed to UV radiation under deaerated condition. Therefore, UV/nZVI process can be suggested as a reliable method for Bacillus subtilis spores inactivation. Copyright © 2018. Published by Elsevier Ltd.

Measuring the Degree of Sensitization (DOS) Using an Electrochemical Technique

NASA Astrophysics Data System (ADS)

Abuzriba, Mokhtar B.; Musa, Salem M.

Sensitization can be simply defined as the susceptibility of an alloy, specifically austenitic stainless steel, to corrosion at grain boundaries. A detailed study on types 304 stainless steel has been carried out to correlate the degree of sensitization measured by electrochemical potentiokinetic reactivation test (EPR) with the susceptibility to intergranular corrosion. In this study four different heat treatments were given to alloys, i.e., solution annealed (SA) at 1020 °C for 1 h, then quenched in water; also then heat-treated in air at 620 °C for 15, 30, and 60 min. The electrolyte for the EPR tests was 1.0 N H2SO4 solution containing 0.01 M KSCN. Potentiodynamic curves from passive to active regions in deaerated solution at room temperature were obtained at a scan rate of 1.67 mV/s (6 V/h), after the passivation at 200 mV versus (SCE) for 2 min then the polarization was conducted. The criterion used to distinguish between sensitized and non-sensitized specimens is the activation charge Pa, the peak current density, Ph, in the active state, and Flade potential Ef at which the active curve breaks upward. The results indicated that the longer the sensitization time the higher the activation charge (Pa), and the higher the peak current density in the active state (Ph). The results indicated that, the EPR is more sensitive than the chemical method for measuring the degree of sensitization.

Photochemical redox reactions of copper(II)-alanine complexes in aqueous solutions.

PubMed

Lin, Chen-Jui; Hsu, Chao-Sheng; Wang, Po-Yen; Lin, Yi-Liang; Lo, Yu-Shiu; Wu, Chien-Hou

2014-05-19

The photochemical redox reactions of Cu(II)/alanine complexes have been studied in deaerated solutions over an extensive range of pH, Cu(II) concentration, and alanine concentration. Under irradiation, the ligand-to-metal charge transfer results in the reduction of Cu(II) to Cu(I) and the concomitant oxidation of alanine, which produces ammonia and acetaldehyde. Molar absorptivities and quantum yields of photoproducts for Cu(II)/alanine complexes at 313 nm are characterized mainly with the equilibrium Cu(II) speciation where the presence of simultaneously existing Cu(II) species is taken into account. By applying regression analysis, individual Cu(I) quantum yields are determined to be 0.094 ± 0.014 for the 1:1 complex (CuL) and 0.064 ± 0.012 for the 1:2 complex (CuL2). Individual quantum yields of ammonia are 0.055 ± 0.007 for CuL and 0.036 ± 0.005 for CuL2. Individual quantum yields of acetaldehyde are 0.030 ± 0.007 for CuL and 0.024 ± 0.007 for CuL2. CuL always has larger quantum yields than CuL2, which can be attributed to the Cu(II) stabilizing effect of the second ligand. For both CuL and CuL2, the individual quantum yields of Cu(I), ammonia, and acetaldehyde are in the ratio of 1.8:1:0.7. A reaction mechanism for the formation of the observed photoproducts is proposed.

Corrosion behavior of cast Ti-6Al-4V alloyed with Cu.

PubMed

Koike, Marie; Cai, Zhuo; Oda, Yutaka; Hattori, Masayuki; Fujii, Hiroyuki; Okabe, Toru

2005-05-01

It has recently been found that alloying with copper improved the inherently poor grindability and wear resistance of titanium. This study characterized the corrosion behavior of cast Ti-6Al-4V alloyed with copper. Alloys (0.9 or 3.5 mass % Cu) were cast with the use of a magnesia-based investment in a centrifugal casting machine. Three specimen surfaces were tested: ground, sandblasted, and as cast. Commercially pure titanium and Ti-6Al-4V served as controls. Open-circuit potential measurement, linear polarization, and potentiodynamic cathodic polarization were performed in aerated (air + 10% CO(2)) modified Tani-Zucchi synthetic saliva at 37 degrees C. Potentiodynamic anodic polarization was conducted in the same medium deaerated by N(2) + 10% CO(2). Polarization resistance (R(p)), Tafel slopes, and corrosion current density (I(corr)) were determined. A passive region occurred for the alloy specimens with ground and sandblasted surfaces, as for CP Ti. However, no passivation was observed on the as-cast alloys or on CP Ti. There were significant differences among all metals tested for R(p) and I(corr) and significantly higher R(p) and lower I(corr) values for CP Ti compared to Ti-6Al-4V or the alloys with Cu. Alloying up to 3.5 mass % Cu to Ti-6Al-4V did not change the corrosion behavior. Specimens with ground or sandblasted surfaces were superior to specimens with as-cast surfaces. (c) 2005 Wiley Periodicals, Inc.

[TiO2-Induced Photodegradation of Levofloxacin by Visible Light and Its Mechanism].

PubMed

Guo, Hong-sheng; Liu, Ya-nan; Qiao, Qi; Wei, Hong; Dong, Cheng-xing; Xue, Jie; Li, Ke-bin

2015-05-01

Levofloxacin is an emerging pollutant. Single levofloxacin and TiO2 have no visible-light activity. However, photodegradation of levofloxacin dramatically enhanced in the presence of TiO2 under visible light irradiation. Considering this finding, he photodegradation of levofloxacin over TiO2 was investigated under visible light irradiation. Effects of TiO2 dosage, levofloxacin concentration, and solution pH on levofloxacin photodegradation were examined by monitoring its concentration decay with time. The results showed that levofloxacin photodegradation fitted the Langmuir-Hinshelwood kinetic model. Solution pH, TiO2 dose, and levofloxacin concentration had significant effects on the photodegradation rates. In addition, batch adsorption experiments revealed that adsorption of levofloxacin on TiO2 conformed to the pseudo-second-order kinetics and the Langmuir isotherm. DRS spectrum of levofloxacin-adsorbed TiO2 suggested that a surface complex was formed between levofloxacin and TiO2. Addition of radical scavengers and N2-degassing affecting levofloxacin photodegradation indicated that the superoxide ion radical was mainly active species. UV-Vis spectra of a deaerated TiO2 and levofloxacin suspensions further confirmed that the electron injection into TiO2 conduction band took place under visible light irradiation. Based on these results, a charge-transfer mechanism initiated by photoexcitation of TiO2/ levofloxacin surface complex was proposed for levofloxacin photocatalytic degradation over TiO2 under visible light. This study indicates that the charge-transfer-complex-mediated photocatalytic technique has promising applications in the removal of colorless organic pollutants.

The effect of long-term nitrate treatment on SRB activity, corrosion rate and bacterial community composition in offshore water injection systems.

PubMed

Bødtker, Gunhild; Thorstenson, Tore; Lillebø, Bente-Lise P; Thorbjørnsen, Bente E; Ulvøen, Rikke Helen; Sunde, Egil; Torsvik, Terje

2008-12-01

Biogenic production of hydrogen sulphide (H(2)S) is a problem for the oil industry as it leads to corrosion and reservoir souring. Continuous injection of a low nitrate concentration (0.25-0.33 mM) replaced glutaraldehyde as corrosion and souring control at the Veslefrikk and Gullfaks oil field (North Sea) in 1999. The response to nitrate treatment was a rapid reduction in number and activity of sulphate-reducing bacteria (SRB) in the water injection system biofilm at both fields. The present long-term study shows that SRB activity has remained low at < or =0.3 and < or =0.9 microg H(2)S/cm(2)/day at Veslefrikk and Gullfaks respectively, during the 7-8 years with continuous nitrate injection. At Veslefrikk, 16S rRNA gene based community analysis by PCR-DGGE showed that bacteria affiliated to nitrate-reducing sulphide-oxidizing Sulfurimonas (NR-SOB) formed major populations at the injection well head throughout the treatment period. Downstream of deaerator the presence of Sulfurimonas like bacteria was less pronounced, and were no longer observed 40 months into the treatment period. The biofilm community during nitrate treatment was highly diverse and relative stable for long periods of time. At the Gullfaks field, a reduction in corrosion of up to 40% was observed after switch to nitrate treatment. The present study show that nitrate injection may provide a stable long-term inhibition of SRB in sea water injection systems, and that corrosion may be significantly reduced when compared to traditional biocide treatment.

NASA Tech Briefs, October 2006

NASA Technical Reports Server (NTRS)

2006-01-01

Topics covered include: Protein Sensors Based on Optical Ring Resonators; Phase Sensor for Aligning a Segmented Telescope Mirror; Control Software for Advanced Video Guidance Sensor; Generating Control Commands From Gestures Sensed by EMG; Multiple-Flat-Panel System Displays Multidimensional Data; 3D X-Ray Luggage-Screening System; Probe Station and Near-Field Scanner for Testing Antennas; Photodetector Arrays for Multicolor Visible/Infrared Imaging; Semiconductor Bolometers Give Background-Limited Performance; Multichannel X-Band Dielectric-Resonator Oscillator; Automatic Alignment of Displacement-Measuring Interferometer; Earth Observing System Data Gateway; Power User Interface; Mercury Shopping Cart Interface; Cassini Archive Tracking System; Architecture Adaptive Computing Environment; Computing Fault Displacements from Surface Deformations; Oxygen-Permeable, Hydrophobic Membranes of Silanized alpha-Al2O3; SiC Composite Turbine Vanes; Retaining Device for the Interior Structure of a Spacecraft Payload; Tool for Torquing Circular Electrical-Connector Collars; System for Continuous Deaeration of Hydraulic Oil; Solar-Powered Cooler and Heater for an Automobile Interior; Improved Oxygen-Beam Texturing of Glucose-Monitoring Optics; Tool for Two Types of Friction Stir Welding; Stationary Apparatus Would Apply Forces of Walking to Feet; Instrument Would Detect and Collect Biological Aerosols; Boundary Condition for Modeling Semiconductor Nanostructures; Miniature Distillation Column for Producing LOX From Air; Even Illumination from Fiber-Optic-Coupled Laser Diodes; Optically Driven Deformable Mirrors; Algorithm for Automated Detection of Edges of Clouds; Exploiting Quantum Resonance to Solve Combinatorial Problems; Hybrid Terrain Database; On Release of Microbe-Laden Particles from Mars Landers; A Concept for Run-Time Support of the Chapel Language; Thermoelectric Inhomogeneities in (Ag(sub 1-y)SbTe2)(sub x)(PbTe)(sub 1-x); and Spacecraft Escape Capsule.

Process for Making a Noble Metal on Tin Oxide Catalyst

NASA Technical Reports Server (NTRS)

Davis, Patricia; Miller, Irvin; Upchurch, Billy

2010-01-01

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Characterization of activated titanium solid reference electrodes for corrosion testing of steel in concrete

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

Castro, P.; Maldonado, L.; Saguees, A.A.

1996-08-01

Small bars of Ti activated with mixed-metal oxide (commercially produced for permanent impressed-current anodes in cathodic protection) were used as embedded reference electrodes (RE) in concrete. Their electrochemical behavior was evaluated through measurements and analyses of potential, electrochemical impedance spectroscopy (EIS), cyclic polarization (CP), and galvanostatic tests in buffer solutions of pH 4, 7, and 10, saturated calcium hydroxide, simulated concrete pore solution (SPS) with pH = 13.5, and various concrete mixes with and without pozzolanic additions as cement replacement. Effects of deaeration and sodium chloride additions were evaluated. The potential of the activated Ti rod (ATR) electrodes resembled themore » expected dependence for the system Ir{sub 2}O{sub 3} + H{sub 2}O = 2IrO{sub 2} + 2H{sup +} + 2e{sup {minus}} in aqueous solutions. The ATR electrode presented generally good stability with time in concrete for up to 900 days. Anomalous behavior was found in two concrete mixes with the highest pozzolanic content. Results from EIS tests revealed a constant phase element (CPE) behavior, which agreed with results of CP tests that showed a very large apparent interfacial capacitance. The apparent capacitance was on the order of 10{sup {minus}2} F/cm{sup 2}, resulting in very low impedance, which is advantageous when using ATR electrodes to conduct EIS or polarization resistance tests. Galvanostatic application of 0.075 {mu}A/cm{sup 2} caused little variation of potential with time, indicating the presence of a finite polarization resistance. Little short-term susceptibility of the ATR electrode potential to NaCl additions was found. The ATR electrode potential also showed little short-term sensitivity to variations in oxygen partial pressure.« less

Post-depositional fracturing and subsidence of pumice flow deposits: Lascar Volcano, Chile.

PubMed

Whelley, Patrick L; Jay, J; Calder, E S; Pritchard, M E; Cassidy, N J; Alcaraz, S; Pavez, A

Unconsolidated pyroclastic flow deposits of the 1993 eruption of Lascar Volcano, Chile, have, with time, become increasingly dissected by a network of deeply penetrating fractures. The fracture network comprises orthogonal sets of decimeter-wide linear voids that form a pseudo-polygonal grid visible on the deposit surface. In this work, we combine shallow surface geophysical imaging tools with remote sensing observations and direct field measurements of the deposit to investigate these fractures and their underlying causal mechanisms. Based on ground penetrating radar images, the fractures are observed to have propagated to depths of up to 10 m. In addition, orbiting radar interferometry shows that deposit subsidence of up to 1 cm/year -1 occurred between 1993 and 1996 with continued subsidence occurring at a slower rate thereafter. In situ measurements show that 1 m below the surface, the 1993 deposits remain 5°C to 15°C hotter, 18 years after emplacement, than adjacent deposits. Based on the observed subsidence as well as estimated cooling rates, the fractures are inferred to be the combined result of deaeration, thermal contraction, and sedimentary compaction in the months to years following deposition. Significant environmental factors, including regional earthquakes in 1995 and 2007, accelerated settling at punctuated moments in time. The spatially variable fracture pattern relates to surface slope and lithofacies variations as well as substrate lithology. Similar fractures have been reported in other ignimbrites but are generally exposed only in cross section and are often attributed to formation by external forces. Here we suggest that such interpretations should be invoked with caution, and deformation including post-emplacement subsidence and fracturing of loosely packed ash-rich deposits in the months to years post-emplacement is a process inherent in the settling of pyroclastic material.

Second law analysis of a conventional steam power plant

NASA Technical Reports Server (NTRS)

Liu, Geng; Turner, Robert H.; Cengel, Yunus A.

1993-01-01

A numerical investigation of exergy destroyed by operation of a conventional steam power plant is computed via an exergy cascade. An order of magnitude analysis shows that exergy destruction is dominated by combustion and heat transfer across temperature differences inside the boiler, and conversion of energy entering the turbine/generator sets from thermal to electrical. Combustion and heat transfer inside the boiler accounts for 53.83 percent of the total exergy destruction. Converting thermal energy into electrical energy is responsible for 41.34 percent of the total exergy destruction. Heat transfer across the condenser accounts for 2.89 percent of the total exergy destruction. Fluid flow with friction is responsible for 0.50 percent of the total exergy destruction. The boiler feed pump turbine accounts for 0.25 percent of the total exergy destruction. Fluid flow mixing is responsible for 0.23 percent of the total exergy destruction. Other equipment including gland steam condenser, drain cooler, deaerator and heat exchangers are, in the aggregate, responsible for less than one percent of the total exergy destruction. An energy analysis is also given for comparison of exergy cascade to energy cascade. Efficiencies based on both the first law and second law of thermodynamics are calculated for a number of components and for the plant. The results show that high first law efficiency does not mean high second law efficiency. Therefore, the second law analysis has been proven to be a more powerful tool in pinpointing real losses. The procedure used to determine total exergy destruction and second law efficiency can be used in a conceptual design and parametric study to evaluate the performance of other steam power plants and other thermal systems.

THE FINE STRUCTURE OF MEISSNER's TOUCH CORPUSCLES OF HUMAN FINGERS

PubMed Central

Cauna, Nikolajs; Ross, Leonard L.

1960-01-01

Thin slices of the finger pads of six individuals were fixed in buffered 1 per cent osmic acid, embedded in deaerated, nitrogenated methacrylate, and cut into thin sections for electron microscopic study. Before embedding, the slices were trimmed so as to include several digital tactile corpuscles. Some thin sections were stained in 10 per cent aqueous phosphotungstic acid solution. The principal part of Meissner's corpuscle is made up of flattened laminar cells stretching across the corpuscle in irregular layers. The perinuclear cytoplasm of these cells contains numerous small mitochondria, a sparse granular endoplasmic reticulum, and a large number of small vesicles. Nerve fibers enter the side or base of the corpuscle, lose their myelin sheaths, and follow a meandering course between the laminar cell plates. The nerve endings enter into a close appositional relationship with the flattened portions of the laminar cells. In some areas the apposed axolemma and cell membranes are slightly thickened with small vesicles located along the cell membrane or on both surfaces. These regions are interpreted as synapses. The most prominent feature of the nerve endings is an extraordinary accumulation of small mitochondria which vary in size and internal density. The nerve endings also contain vacuoles, groups of dense concentric membranes, and small dense vesicles of irregular distribution. The laminar cells are separated from one another by a dense intercellular substance of uniform thickness which also envelops the entire corpuscle. This material contains randomly oriented collagen fibers and fine fibrils bound together by a dense material at nodal points recurring at regular intervals of approximately 120 mµ. These findings are discussed in relation to the problems of the function of Meissner's corpuscle, neural material loss and replacement, and the presence of synapses. PMID:13691669

Breckinridge Project, initial effort

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

None

1982-01-01

The project cogeneration plant supplies electric power, process steam and treated boiler feedwater for use by the project plants. The plant consists of multiple turbine generators and steam generators connected to a common main steam header. The major plant systems which are required to produce steam, electrical power and treated feedwater are discussed individually. The systems are: steam, steam generator, steam generator fuel, condensate and feedwater deaeration, condensate and blowdown collection, cooling water, boiler feedwater treatment, coal handling, ash handling (fly ash and bottom ash), electrical, and control system. The plant description is based on the Phase Zero design basismore » established for Plant 31 in July of 1980 and the steam/condensate balance as presented on Drawing 31-E-B-1. Updating of steam requirements as more refined process information becomes available has generated some changes in the steam balance. Boiler operation with these updated requirements is reflected on Drawing 31-D-B-1A. The major impact of updating has been that less 600 psig steam generated within the process units requires more extraction steam from the turbine generators to close the 600 psig steam balance. Since the 900 psig steam generation from the boilers was fixed at 1,200,000 lb/hr, the additional extraction steam required to close the 600 psig steam balance decreased the quantity of electrical power available from the turbine generators. In the next phase of engineering work, the production of 600 psig steam will be augmented by increasing convection bank steam generation in the Plant 3 fired heaters by 140,000 to 150,000 lb/hr. This modification will allow full rated power generation from the turbine generators.« less

Method to Estimate the Dissolved Air Content in Hydraulic Fluid

NASA Technical Reports Server (NTRS)

Hauser, Daniel M.

2011-01-01

In order to verify the air content in hydraulic fluid, an instrument was needed to measure the dissolved air content before the fluid was loaded into the system. The instrument also needed to measure the dissolved air content in situ and in real time during the de-aeration process. The current methods used to measure the dissolved air content require the fluid to be drawn from the hydraulic system, and additional offline laboratory processing time is involved. During laboratory processing, there is a potential for contamination to occur, especially when subsaturated fluid is to be analyzed. A new method measures the amount of dissolved air in hydraulic fluid through the use of a dissolved oxygen meter. The device measures the dissolved air content through an in situ, real-time process that requires no additional offline laboratory processing time. The method utilizes an instrument that measures the partial pressure of oxygen in the hydraulic fluid. By using a standardized calculation procedure that relates the oxygen partial pressure to the volume of dissolved air in solution, the dissolved air content is estimated. The technique employs luminescent quenching technology to determine the partial pressure of oxygen in the hydraulic fluid. An estimated Henry s law coefficient for oxygen and nitrogen in hydraulic fluid is calculated using a standard method to estimate the solubility of gases in lubricants. The amount of dissolved oxygen in the hydraulic fluid is estimated using the Henry s solubility coefficient and the measured partial pressure of oxygen in solution. The amount of dissolved nitrogen that is in solution is estimated by assuming that the ratio of dissolved nitrogen to dissolved oxygen is equal to the ratio of the gas solubility of nitrogen to oxygen at atmospheric pressure and temperature. The technique was performed at atmospheric pressure and room temperature. The technique could be theoretically carried out at higher pressures and elevated temperatures.

Some perspective decisions for the regeneration system equipment of the thermal and nuclear power plants decreasing the probability of water ingress into the turbine and rotor acceleration by return steam flow

NASA Astrophysics Data System (ADS)

Trifonov, N. N.; Svyatkin, F. A.; Sintsova, T. G.; Ukhanova, M. G.; Yesin, S. B.; Nikolayenkova, E. K.; Yurchenko, A. Yu.; Grigorieva, E. B.

2016-03-01

The regeneration system heaters are one of the sources of possible ingress of the water into the turbine. The water penetrates into the turbine either at the heaters overflow or with the return flow of steam generated when the water being in the heater boils up in the dynamic operation modes or at deenergization of the power-generating unit. The return flow of steam and water is dangerous to the turbine blades and can result in the rotor acceleration. The known protective devices used to prevent the overflow of the low-pressure and high-pressure heaters (LPH and HPH), of the horizontal and vertical heaters of heating-system water (HWH and VWH), as well as of the deaerators and low-pressure mixing heaters (LPMH) were considered. The main protective methods of the steam and water return flows supplied by the heaters in dynamic operation modes or at deenergization of the power-generating unit are described. Previous operating experience shows that the available protections do not fully prevent water ingress into the turbine and the rotor acceleration and, therefore, the development of measures to decrease the possibility of ingress of the water into the turbine is an actual problem. The measures allowing eliminating or reducing the water mass in the heaters are expounded; some of them were designed by the specialists of OAO Polzunov Scientific and Development Association on Research and Design of Power Equipment (NPO CKTI) and are efficiently introduced at heat power plants and nuclear power plants. The suggested technical solutions allow reducing the possibility of the water ingress into the turbine and rotor acceleration by return steam flow in the dynamic operation modes or in the case of power generating unit deenergization. Some of these solutions have been tested in experimental-industrial exploitation and can be used in industry.

Fullerene-nitrogen doped carbon nanotubes for the direct electrochemistry of hemoglobin and its application in biosensing.

PubMed

Sheng, Qinglin; Liu, Ruixiao; Zheng, Jianbin

2013-12-01

The direct electrochemistry of hemoglobin (Hb) immobilized by a fullerene-nitrogen doped carbon nanotubes and chitosan (C60-NCNTs/CHIT) composite matrix is demonstrated. The cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the modified electrode. In the deaerated buffer solution, the cyclic voltammogram of the Hb/C60-NCNTs/CHIT composite film modified electrode showed a pair of well-behaved redox peaks with the E°'=-0.335 (± 0.3) V (vs. SCE). The redox peaks are assigned to the redox reaction of Hb(Fe(III)/Fe(II)) and confirm the effective immobilization of Hb on the composite film. The large value of ks = 1.8 (± 0.2)s(-1) suggests that the immobilized Hb achieved a relative fast electron transfer process. The fast electron transfer interaction between protein and electrode surface suggested that the C60-NCNTs/CHIT composite film may mimic some physiological process and further elucidate the relationship between protein structures and biological functions. Moreover, the resulting electrode exhibited excellent electrocatalytic ability towards the reduction of hydrogen peroxide (H2O2) with the linear dynamic range of 2.0-225.0 μM. The linear regression equation was Ip/μA=7.35 (± 0.08)+0.438 (± 0.007)C/μM with the correlation coefficient of 0.9993. The detection limit was estimated at about 1 μM (S/N=3). The sensitivity was 438.0 (± 2.5) μA mM(-1). It is expected that the method presented here can not only be easily extended to other redox enzymes or proteins, but also be used as an electrochemical sensing devices for the determination of H2O2 in cell extracts or urine. Copyright © 2013 Elsevier B.V. All rights reserved.

Energy Efficiency and Performance Limiting Effects in Thermo-Osmotic Energy Conversion from Low-Grade Heat.

PubMed

Straub, Anthony P; Elimelech, Menachem

2017-11-07

Low-grade heat energy from sources below 100 °C is available in massive quantities around the world, but cannot be converted to electricity effectively using existing technologies due to variability in the heat output and the small temperature difference between the source and environment. The recently developed thermo-osmotic energy conversion (TOEC) process has the potential to harvest energy from low-grade heat sources by using a temperature difference to create a pressurized liquid flux across a membrane, which can be converted to mechanical work via a turbine. In this study, we perform the first analysis of energy efficiency and the expected performance of the TOEC technology, focusing on systems utilizing hydrophobic porous vapor-gap membranes and water as a working fluid. We begin by developing a framework to analyze realistic mass and heat transport in the process, probing the impact of various membrane parameters and system operating conditions. Our analysis reveals that an optimized system can achieve heat-to-electricity energy conversion efficiencies up to 4.1% (34% of the Carnot efficiency) with hot and cold working temperatures of 60 and 20 °C, respectively, and an operating pressure of 5 MPa (50 bar). Lower energy efficiencies, however, will occur in systems operating with high power densities (>5 W/m 2 ) and with finite-sized heat exchangers. We identify that the most important membrane properties for achieving high performance are an asymmetric pore structure, high pressure resistance, a high porosity, and a thickness of 30 to 100 μm. We also quantify the benefits in performance from utilizing deaerated water streams, strong hydrodynamic mixing in the membrane module, and high heat exchanger efficiencies. Overall, our study demonstrates the promise of full-scale TOEC systems to extract energy from low-grade heat and identifies key factors for performance optimization moving forward.

The Nickel(111)/Alkaline Electrolyte Interface

NASA Technical Reports Server (NTRS)

Wang, Kuilong; Chottiner, G. S.; Scherson, D. A.; Reid, Margaret A.

1991-01-01

The electrochemical properties of Ni (111) prepared and characterized in ultra high vacuum, UHV, by surface analytical techniques have been examined in alkaline media by cyclic voltammetry using an UHV-electrochemical cell transfer system designed and built in this laboratory. Prior to the transfer, the Ni(111) surfaces were exposed to saturation coverages of CO in UHV in an attempt to protect the surface from possible contamination with other gases during the transfer. Temperature Programmed Desorption, TPD, of CO-dosed Ni (111) surfaces displaying sharp c(4x2), LEED patterns, subsequently exposed to water-saturated Ar at atmospheric pressure in an auxiliary UHV compatible chamber and finally transferred back to the main UHV chamber, yielded CO2 and water as the only detectable products. This indicates that the CO-dosed surfaces react with water and/or bicarbonate and hydroxide as the most likely products. Based on the integration of the TPD peaks, the combined amounts of H2O and CO2 were found to be on the order of a single monolayer. The reacted c(4x2)CO/Ni(111) layer seems to protect the surface from undergoing spontaneous oxidation in strongly alkaline solutions. This was evidenced by the fact that the open circuit potential observed immediately after contact with deaerated 0.1 M KOH was about 0.38 V vs. DHE, drifting slightly towards more negative values prior to initiating the voltametric scans. The average ratio of the integrated charge obtained in the first positive linear scan in the range of 0.35 to 1.5 V vs. DHE (initiated at the open circuit potential) and the first (and subsequent) linear negative scans in the same solution yielded for various independent runs a value of 3.5 +/- 0.3. Coulometric analysis of the cyclic voltammetry curves indicate that the electrochemically formed oxyhydroxide layer involves a charge equivalent to 3.2 +/- 0.4 layers of Ni metal.

Environmentally induced crack propagation in Inconel alloys 600 and 690 under hydrogen supersaturated steam

NASA Astrophysics Data System (ADS)

Ali, Mehboob Muzzammil

Intergranular stress corrosion cracking (IGSCC) of Inconel alloys 600 and 690 was investigated by exposing them to 300--400°C in deaerated hydrogen supersaturated steam. Crack growth rates were measured in-situ for the above alloys using modified wedge-opening-loaded (M-WOL) linear elastic fracture specimens under constant displacement conditions. The applied stress intensity factors (K) used varied from 29--90 MPam1/2. An activation energy of 120 kJ/mol was found for crack growth rates as a function of temperature. This activation energy is close to the one corresponding to grain boundary self diffusion of nickel. In addition, it was found that the apparent crack growth rates (da/dt) exhibited a linear dependence with KI, given by (da/dt) = A.KIn, where n = 1 in our case. Microstructurally, crack propagation in both the alloys was predominantly along the grain boundaries. It is suggested that high fugacity hydrogen was generated at the tip of the crack, as a result of the reaction of H2O with Cr2O3 on the fracture surface leading to IGSCC. It was found that the rates of crack propagation in both alloys 600 and 690 are very similar. Moreover, under the applied KIs, both alloys 600 and 690 show a similar tendency to crack intergranularly in a direction perpendicular to the applied stress. Crack branching was also exhibited by both the alloys 600 as well as 690. The difference in the crack growth rates of alloys 600 and 690 was found to be only about 2%, which indicates that the crack growth rates in these alloys is independent of the alloy chromium content and that, possibly very similar crack growth mechanisms are active in both the alloys 600 and 690 under similar conditions of KI and temperature. HREM images at the crack tip of alloy 690 exhibit two distinct regions---a crystalline region, and an adjacent amorphous region, which is likely to be either a hydroxide or an amorphous oxide layer. This layer is expected to result from passivation reactions as the crack surface is exposed to the corrosive environment.

Exhaled breath condensate pH assays are not influenced by oral ammonia

PubMed Central

Wells, K; Vaughan, J; Pajewski, T; Hom, S; Ngamtrakulpanit, L; Smith, A; Nguyen, A; Turner, R; Hunt, J

2005-01-01

Background: Measurement of pH in exhaled breath condensate (EBC) is robust and simple. Acidic source fluid (airway lining fluid) traps bases while volatilising acids, leading to EBC acidification in many lung diseases. Lower airway ammonia is one determinant of airway lining fluid pH, raising the concern that addition of the base ammonia by contamination from the mouth might confound EBC pH assays. Methods: Three discrete methods were used to limit oral ammonia contamination of EBC collections: endotracheal intubation, oral rinsing, and –40°C condenser temperatures. Separately, ammonia was removed from collected EBC samples by lyophilisation and resuspension. Intraweek and intraday variability of ammonia concentration was determined in 76 subjects, and ammonia and pH from a further 235 samples were graphically compared. Ammonia was assayed spectrophotometrically and pH was assessed after deaeration. Results: Data from 1091 samples are presented. Ammonia was reduced in EBC by all methods. Endotracheal intubation decreased EBC ammonia from a mean (SD) of 619 (124) µM to 80 (24) µM (p<0.001, n = 32). Oral rinsing before collection also led to a decline in EBC ammonia from 573 (307) µM to 224 (80) µM (p = 0.016, n = 7). The colder the condensation temperature used, the less ammonia was trapped in the EBC. Lyophilisation removed 99.4 (1.9)% of ammonia. Most importantly, the pH of EBC never decreased after removal of ammonia by any of these methods. Intraweek and intraday coefficients of variation for ammonia were 64 (27)% and 60 (32)%, which is substantially more variable than EBC pH assays. Conclusions: Although ammonia and pH appear to correlate in EBC, the oral ammonia concentration is not an important determinant of EBC pH. No precautions need to be taken to exclude oral ammonia when EBC pH is of interest. The low pH and low ammonia found in EBC from patients with lung diseases appear to be independent effects of volatile compounds arising from the airway. PMID:15618579

Changes in exhaled breath condensate pH in healthy and asthmatic pregnant women.

PubMed

Eszes, Noémi; Bikov, András; Lázár, Zsófia; Bohács, Anikó; Müller, Veronika; Stenczer, Balázs; Rigó, János; Losonczy, György; Horváth, Ildikó; Tamási, Lilla

2013-05-01

Asthma is a common chronic disease complicating pregnancy with a risk for perinatal complications. Control of airway inflammation in the asthmatic pregnancy improves pregnancy outcomes. Our aim was to evaluate pH of exhaled breath condensate (EBC), a non-invasive method for the assessment of asthmatic airway inflammation, in healthy and asthmatic pregnancies. Cross-sectional study. Hungarian university clinics. Seventeen healthy pregnant women, 21 asthmatic pregnant women, 23 healthy non-pregnant women and 22 asthmatic non-pregnant women. EBC samples were collected using a portable condenser, EBC pH was measured after argon deaeration. EBC pH. EBC pH (mean ± SD) of healthy non-pregnant and asthmatic non-pregnant women was similar (7.75 ± 0.27 vs. 7.54 ± 0.57; p = 0.118), probably indicating an optimal control of airway inflammation in asthmatic women. On the other hand, EBC pH was higher in healthy pregnant women compared with healthy non-pregnant women (8.02 ± 0.43 vs. 7.75 ± 0.27; p = 0.017). Higher EBC pH accompanying healthy pregnancy was absent in asthmatic pregnant patients whose EBC pH was lower (7.65 ± 0.38) than that of healthy pregnant women (p = 0.006), and it was similar to that in asthmatic and healthy non-pregnant women (p = 0.470 and p = 0.300, respectively). The EBC pH in asthmatic pregnant women correlated positively with birthweight (r = 0.49, p = 0.047) and negatively with forced vital capacity (r = 0.45, p = 0.039). EBC pH was not related to blood pH. EBC pH is higher in healthy pregnant women but not in asthmatic pregnant women compared with data from healthy non-pregnant women, indicating that oxidative inflammatory processes induced by asthma may compromise the regulatory mechanisms causing alkaline pH in the airways during pregnancy. © 2013 The Authors Acta Obstetricia et Gynecologica Scandinavica © 2013 Nordic Federation of Societies of Obstetrics and Gynecology.

Functionally graded scaffolds for the engineering of interface tissues using hybrid twin screw extrusion/electrospinning technology

NASA Astrophysics Data System (ADS)

Erisken, Cevat

Tissue engineering is the application of the principles of engineering and life sciences for the development of biological alternatives for improvement or regeneration of native tissues. Native tissues are complex structures with functions and properties changing spatially and temporally, and engineering of such structures requires functionally graded scaffolds with composition and properties changing systematically along various directions. Utilization of a new hybrid technology integrating the controlled feeding, compounding, dispersion, deaeration, and pressurization capabilities of extrusion process with electrospinning allows incorporation of liquids and solid particles/nanoparticles into polymeric fibers/nanofibers for fabrication of functionally graded non-woven meshes to be used as scaffolds in engineering of tissues. The capabilities of the hybrid technology were demonstrated with a series of scaffold fabrication and cell culturing studies along with characterization of biomechanical properties. In the first study, the hybrid technology was employed to generate concentration gradations of beta-tricalcium phosphate (beta-TCP) nanoparticles in a polycaprolactone (PCL) binder, between two surfaces of nanofibrous scaffolds. These scaffolds were seeded with pre-osteoblastic cell line (MC3T3-E1) to attempt to engineer cartilage-bone interface, and after four weeks, the tissue constructs revealed formation of continuous gradations in extracellular matrix akin to cartilage-bone interface in terms of distributions of mineral concentrations and biomechanical properties. In a second demonstration of the hybrid technology, graded differentiation of stem cells was attempted by using insulin, a known stimulator of chondrogenic differentiation, and beta-glycerol phosphate (beta-GP), for mineralization. Concentrations of insulin and beta-GP in PCL were controlled to monotonically increase and decrease, respectively, along the length of scaffolds, which were then seeded with adipose derived stromal cells (h-ADSCs). Analysis of resulting tissue constructs revealed chondrocytic differentiation of h-ADSCs, with both the chondrocytic cell concentration and mineralization varying as a function of distributions of concentrations of insulin and beta-GP, respectively. The investigation also covered characterization of biomechanical properties of native bovine osteochondral tissue samples, which were then compared with biomechanical properties of tissue constructs at different stages of development. The hybrid technology developed in this thesis should provide another enabling platform for the fabrication of functionally graded scaffolds that aim to mimic the elegant gradations found in myriad native tissues.

Magnesium-DNA interactions and the possible relation of magnesium to carcinogenesis. Irradiation and free radicals.

PubMed

Anastassopoulou, J; Theophanides, T

2002-04-01

Magnesium deficiency causes renal complications. The appearance of several diseases is related to its depletion in the human body. In radiotherapy, as well as in chemotherapy, especially in treatment of cancers with cis-platinum, hypomagnesaemia is observed. The site effects of chemotherapy that are due to hypomagnesaemia are decreased using Mg supplements. The role of magnesium in DNA stabilization is concentration dependent. At high concentrations there is an accumulation of Mg binding, which induces conformational changes leading to Z-DNA, while at low concentration there is deficiency and destabilization of DNA. The biological and clinical consequences of abnormal concentrations are DNA cleavage leading to diseases and cancer. Carcinogenesis and cell growth are also magnesium-ion concentration dependent. Several reports point out that the interaction of magnesium in the presence of other metal ions showed that there is synergism with Li and Mn, but there is magnesium antagonism in DNA binding with the essential metal ions in the order: Zn>Mg>Ca. In the case of toxic metals such as Cd, Ga and Ni there is also antagonism for DNA binding. It was found from radiolysis of deaerated aqueous solutions of the nucleoside 5'-guanosine monophosphate (5'-GMP) in the presence as well as in the absence of magnesium ions that, although the addition of hydroxyl radicals (*OH) has been increased by 2-fold, the opening of the imidazole ring of the guanine base was prevented. This effect was due to the binding of Mg2+ ions to N7 site of the molecule by stabilizing the five-member ring imitating cis-platinum. It was also observed using Fourier Transform Infrared spectroscopy, Raman spectroscopy and Fast Atom Bombardment mass spectrometry that *OH radicals subtract H atoms from the C1', C4' and C5' sites of the nucleotide. Irradiation of 5'-GMP in the presence of oxygen (2.5 x 10(-4) M) shows that magnesium is released from the complex. There is spectroscopic evidence that superoxide anions (O2-*) react with magnesium ions leading to magnesium release from the complex. From radiolysis data it was suggested that magnesium ions can act as radiosensitizers in the absence of oxygen, while in the presence of oxygen they act as protectors and stabilizers of DNA.

The use of designed experiments in the process development of continuous propellant mixing

NASA Technical Reports Server (NTRS)

Campbell, J. A.; Clemons, K. T.; Wong, M. K.

1993-01-01

A continuous mix pilot plant was constructed at Aerojet Propulsion Division in Sacramento, California to develop a robust propellant mixing process for the full scale plant that was to be built at the NASA Advanced Solid Rocket Motor facility Yellow Creek, Mississippi. The plant was used to conduct dozens of subsystem and full system mixing tests for evaluation of equipment, processing methods, and control schemes for later use at the production plant. As a culmination to this work, a series of designed experiments were conducted using an eight run Taguchi analysis with four factors at two levels each to determine the primary effect of processing parameters on propellant ballistic and mechanical properties. The factors examined in these runs included the propellant production rate (454 (1000) and 622 kg/hr (1371 Ib/hr)), the product temperature out of the mixer (49 (120) and 63 deg C (145 deg F)), mixer screw speed (75 and 90 rpm), and the deaerator excess capacity (20 and 80 percent). Measured response variables included the uncured and cured density, Crawford Bomb liquid strand burning rates, and selected mechanical properties. The experiment revealed that several of the response variables displayed significant changes from run-to-run with the product temperature being the single most important factor. After concluding this experiment, a twenty-six hour confirmation run was conducted to verify the conclusions reached in the designed experiment. The extended run produced over 12,250 kgs (27,000 lbs) of propellant meeting all of the pre-run targeted properties including density (1.803 g/cc (0.065 lb/in(exp 3)) with a 0.12 percent coefficient of variation (CV) at 25 deg C (77 deg F)), liquid strand burn rate (0.889 cm/s (0.350 in/s) with a 0.69 percent CV at 4210 KPa (610 psig), 15.6 deg C (60 deg F)), nominal maximum stress (828 KPa (120 psig) with a 2.84 percent CV, S&E at 25 deg C (77 deg F), 5.08 cm/min (2 in/min)), strain at nominal maximum (47.4 percent with a 3.96 percent CV), and initial tangent modulus (5349 KPa (775 psig) with a 7.26 percent CV).

Potentiodynamic polarization study of the in vitro corrosion behavior of 3 high-palladium alloys and a gold-palladium alloy in 5 media.

PubMed

Sun, Desheng; Monaghan, Peter; Brantley, William A; Johnston, William M

2002-01-01

Corrosion of cast alloy restorations may lead to their failure or adversely affect their biocompatibility. Although some documentation of the corrosion behavior of the high-palladium dental alloys exists, questions remain about their corrosion resistance and mechanisms. This study compared the in vitro corrosion characteristics of 3 high-palladium alloys and 1 gold-palladium alloy in simulated body fluid and oral environments. Two Pd-Cu-Ga alloys and 1 Pd-Ga alloy were selected; an Au-Pd alloy served as the control. The corrosion behavior for the as-cast and simulated porcelain-firing (heat-treated) conditions of each alloy (N = 5) was evaluated in 0.9% NaCl, 0.09% NaCl, and Fusayama solutions. Heat-treated specimens of each alloy (N = 5) were also tested in N(2)-deaerated 0.09% NaCl and Fusayama solutions (pH 4). After immersion in the electrolyte for 24 hours, the open-circuit potential (OCP) was measured, and linear polarization was performed from -20 mV to +20 mV (vs. OCP) at a scanning rate of 0.125 mV/s. Cyclic polarization was performed from -300 mV to +1000 mV and back to -300 mV (vs. OCP) at a scanning rate of 1 mV/s. Data were evaluated with analysis of variance and the Ryan-Einot-Gabriel-Welsch multiple-range test (alpha=.05). The OCP of each alloy varied with the condition (as-cast or heat-treated) and electrolyte used. Corrosion resistance was similar for the 4 alloys tested. For cyclic polarization, all alloys showed active-passive or spontaneous passive behavior in nearly all electrolytes. During some reverse scans, the 3 high-palladium alloys displayed 3 or 5 anodic peaks. No positive hysteresis was observed for any of the alloy/electrolyte combinations evaluated. The corrosion resistances of the 3 high-palladium alloys in simulated body fluid and oral environments were comparable to that of the gold-palladium alloy. The similar corrosion resistance for the 3 high-palladium alloys was attributed to their high noble metal content and theorized stable structure at the submicron level. Selective corrosion of different phases and elements, surface enrichment of palladium, and adsorption of species are possible corrosion mechanisms. The cyclic polarization results suggest that none of the 4 alloys would be prone to pitting or crevice corrosion under in vivo conditions, but crevice conditions should nonetheless be avoided for these alloys in the oral environment.

Surface Studies of Ultra Strength Drilling Steel after Corrosion Fatigue in Simulated Sour Environment

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

M. Ziomek-Moroz; J.A. Hawk; R. Thodla

2012-05-06

The Unites States predicted 60% growth in energy demand by 2030 makes oil and natural gas primary target fuels for energy generation. The fact that the peak of oil production from shallow wells (< 5000 m) is about to be reached, thereby pushing the oil and natural gas industry into deeper wells. However, drilling to depths greater than 5000 m requires increasing the strength-to weight ratio of the drill pipe materials. Grade UD-165 is one of the ultra- high yield strength carbon steels developed for ultra deep drilling (UDD) activities. Drilling UDD wells exposes the drill pipes to Cl{sup -},more » HCO{sub 3}{sup -}/CO{sub 3}{sup 2-}, and H{sub 2}S-containig corrosive environments (i.e., sour environments) at higher pressures and temperatures compared to those found in conventional wells. Because of the lack of synergism within the service environment, operational stresses can result in catastrophic brittle failures characteristic for environmentally assisted cracking (EAC). Approximately 75% of all drill string failures are caused by fatigue or corrosion fatigue. Since there is no literature data on the corrosion fatigue performance of UD-165 in sour environments, research was initiated to better clarify the fatigue crack growth (FCGR) behavior of this alloy in UDD environments. The FCGR behavior of ultra-strength carbon steel, grade UD-165, was investigated by monitoring crack growth rate in deaerated 5%NaCl solution buffered with NaHCO{sub 3}/Na{sub 2}CO{sub 3} and in contact with H{sub 2}S. The partial pressure of H{sub 2}S (p{sub H2S}) was 0.83 kPa and pH of the solution was adjusted by NaOH to 12. The fatigue experiments were performed at 20 and 85 C in an autoclave with surface investigations augmented by scanning electron microscopy (SEM) and energy dispersive x-ray (EDX) spectroscopy. In this study, research focused on surface analyses supported by the fatigue crack growth rate measurements. Fig. 1 shows an SEM micrograph of the crack that propagated from the notch in the solution at 20 C. Accumulation of the corrosion products is visible along the crack. The EDX chemical analysis near the crack tip found iron, sulfur and oxygen in the passive layer. The surface of the sample after the fatigue test in the sour environment at 85{sup o}, Fig. 2, C looks different from that fatigued surface at 20 C. The crack propagates across the passive film that covers the surface fairly uniformly. Some spallation of the passive film is observed near the notch. The EDX chemical analysis of the passive film near the crack tip identified mainly iron, carbon and oxygen. It appears that temperature plays a very important role in formation of the passive film. This may be associated with different solubility of H{sub 2}S in the solution, which will be further studied.« less

The perfect ash-storm: large-scale Pyroclastic Density Current experiments reveal highly mobile, self-fluidising and air-cushioned flow transport regime

NASA Astrophysics Data System (ADS)

Lube, G.; Cronin, S. J.; Breard, E.; Valentine, G.; Bursik, M. I.; Hort, M. K.; Freundt, A.

2013-12-01

We report on the first systematic series of large-scale Pyroclastic Density Current (PDC) experiments using the New Zealand PDC Generator, a novel international research facility in Physical Volcanology recently commissioned at Massey University. Repeatable highly energetic and hot PDCs are synthesized by the controlled ';eruption column-collapse' of up to 3500 kg of homogenously aerated Taupo ignimbrite material from a 15 m-elevated hopper onto an instrumented inclined flume. At discharge rates between 250-1300 kg/s and low- to moderate gas injection rates (yielding initial solids concentration of 15-70 vol%) channelized gas-particle mixture flows life-scaled to dense PDCs can be generated. The flow fronts of the currents reach velocities of up to 9.5 m/s over their first 12 m of travel and rapidly develop strong vertical density stratification. The PDCs typically form a highly mobile, <60 cm-thick dense and channel-confined underflow, with an overriding dilute and turbulent ash cloud surge that also laterally escapes the flume boundaries. Depending on the PDC starting conditions underflows with 1-45 vol% solids concentration are formed, while the upper surge contains <<1 vol.% solids. A characteristic feature of the underflow is the occurrence of 'ignitive' front breakouts, producing jetted lobes that accelerate outward from the flow front, initially forming a lobe-cleft structure, followed by segregation downslope into multiple flow pulses. Depending on initial solids concentration and discharge rate, stratified, dune-bedded and inversely graded bedforms are created whose thicknesses are remarkably uniform along the medial to distal runout path characterising highly mobile flow runout. Along with high-speed video footage we present time-series data of basal arrays of load- and gas-pore pressure transducers to characterise the mobile dense underflows. Data shows that the PDCs are comprised of a turbulent coarse-grained and air-ingesting front with particle-solids concentrations of 1-5 vol%. The front shows a brief phase of negative pore pressure due to the entrainment and upward elutriation of ambient air inside this front. It is immediately followed by the fine-ash rich and highly impermeable main flow body. Passage of the flow body is accompanied by strongly increasing pore-pressures of 1-3 kPa that almost fully supports the weight of the entire underflow - depicting flow-induced fluidisation of the main flow part. The remainder of the flow body shows further increases in pore-pressure aside with strong reductions in flow mass. This suggests the occurrence of zones of air-cushions forming at the base of the underflow that largely aid its inviscid runout. This sequence is repeated during arrival and passage of up to three more flow pulses. The low-permeability deposits maintain high internal gas pore pressures for several minutes after emplacement, before sudden deaeration, settling and gas loss is caused by fracturing. Flow-induced fluidisation and basal air-cushioning provide key processes behind the enigmatic long runout behaviour of dense PDCs.

Corrosion inhibition by inorganic cationic inhibitors on the high strength alumunium alloy, 2024-T3

NASA Astrophysics Data System (ADS)

Chilukuri, Anusha

The toxicity and carcinogenic nature of chromates has led to the investigation of environmentally friendly compounds that offer good corrosion resistance to AA 2024-T3. Among the candidate inhibitors are rare earth metal cationic (REM) and zinc compounds, which have received much of attention over the past two decades. A comparative study on the corrosion inhibition caused by rare earth metal cations, Ce3+, Pr3+, La3+ and Zn2+ cations on the alloy was done. Cathodic polarization showed that these inhibitor ions suppress the oxygen reduction reaction (ORR) to varying extents with Zn2+ providing the best inhibition. Pr3+ exhibited windows of concentration (100-300 ppm) in which the corrosion rate is minimum; similar to the Ce3+ cation. Scanning Electron Microscopy (SEM) studies showed that the mechanism of inhibition of the Pr3+ ion is also similar to that of the Ce3+ ion. Potentiodynamic polarization experiments after 30 min immersion time showed greatest suppression of oxygen reduction reaction in neutral chloride solutions (pH 7), which reached a maximum at a Zn2+ ion concentration of 5 mM. Anodic polarization experiments after 30 min immersion time, showed no anodic inhibition by the inhibitor in any concentration (0.1 mM - 10 mM) and at any pH. However, anodic polarization of samples immersed after longer immersion times (upto 4 days) in mildly acidic Zn2+ (pH 4) solutions showed significant reduction in anodic kinetics indicating that zinc also acts as a “slow anodic inhibitor”. In contrast to the polarization experiments, coupons exposed to inhibited acidic solutions at pH 4 showed complete suppression of dissolution of Al2CuMg particles compared to zinc-free solutions in the SEM studies. Samples exposed in pH 4 Zn2+-bearing solution exhibited highest polarization resistance which was also observed to increase with time. In deaerated solutions, the inhibition by Zn2+ at pH 4 is not observed as strongly. The ability to make the interfacial electrolyte alkaline is retarded in the absence of oxygen. As a result precipitation of Zn oxides and hydroxides was suppressed. Impedance in decarbonated chloride solutions showed that the absence of CO 2 reduces inhibition by Zn2+ at pH 4. The carbonate protective layer formed in aerated solutions is essential for providing better protection of the substrate at pH 4. Inhibitor cations were exchanged into insoluble ion-exchanging sodium bentonites and incorporated as pigments in organic coatings applied to AA 2024-T3 substrates. XRD of the pigments ensured ion exchange and UV-visible spectroscopy was used to characterize inhibitor ion release from the bentonites. Salt spray exposure tests on scribed panels were preformed and results were compared to those from SrCrO4 pigmented coatings. Zn-exchanged bentonite pigmented coatings showed better performance compared to the other exchanged bentonites when incorporated into epoxy coatings with total impedance magnitude in the same order as SrCrO4. PVB (Polyvinyl Butyral) coatings containing Zn bentonite, however, did not show superior behaviour in the impedance response due to less or no water uptake. Salt spray exposures for a period of 336 h, showed that Zn bentonite incorporated into PVB suppressed blistering compared to the neat PVB and other pigmented bentonites.

Optimisation multi-objectif des systemes energetiques

NASA Astrophysics Data System (ADS)

Dipama, Jean

The increasing demand of energy and the environmental concerns related to greenhouse gas emissions lead to more and more private or public utilities to turn to nuclear energy as an alternative for the future. Nuclear power plants are then called to experience large expansion in the coming years. Improved technologies will then be put in place to support the development of these plants. This thesis considers the optimization of the thermodynamic cycle of the secondary loop of Gentilly-2 nuclear power plant in terms of output power and thermal efficiency. In this thesis, investigations are carried out to determine the optimal operating conditions of steam power cycles by the judicious use of the combination of steam extraction at the different stages of the turbines. Whether it is the case of superheating or regeneration, we are confronted in all cases to an optimization problem involving two conflicting objectives, as increasing the efficiency imply the decrease of mechanical work and vice versa. Solving this kind of problem does not lead to unique solution, but to a set of solutions that are tradeoffs between the conflicting objectives. To search all of these solutions, called Pareto optimal solutions, the use of an appropriate optimization algorithm is required. Before starting the optimization of the secondary loop, we developed a thermodynamic model of the secondary loop which includes models for the main thermal components (e.g., turbine, moisture separator-superheater, condenser, feedwater heater and deaerator). This model is used to calculate the thermodynamic state of the steam and water at the different points of the installation. The thermodynamic model has been developed with Matlab and validated by comparing its predictions with the operating data provided by the engineers of the power plant. The optimizer developed in VBA (Visual Basic for Applications) uses an optimization algorithm based on the principle of genetic algorithms, a stochastic optimization method which is very robust and widely used to solve problems usually difficult to handle by traditional methods. Genetic algorithms (GAs) have been used in previous research and proved to be efficient in optimizing heat exchangers networks (HEN) (Dipama et al., 2008). So, HEN have been synthesized to recover the maximum heat in an industrial process. The optimization problem formulated in the context of this work consists of a single objective, namely the maximization of energy recovery. The optimization algorithm developed in this thesis extends the ability of GAs by taking into account several objectives simultaneously. This algorithm provides an innovation in the method of finding optimal solutions, by using a technique which consist of partitioning the solutions space in the form of parallel grids called "watching corridors". These corridors permit to specify areas (the observation corridors) in which the most promising feasible solutions are found and used to guide the search towards optimal solutions. A measure of the progress of the search is incorporated into the optimization algorithm to make it self-adaptive through the use of appropriate genetic operators at each stage of optimization process. The proposed method allows a fast convergence and ensure a diversity of solutions. Moreover, this method gives the algorithm the ability to overcome difficulties associated with optimizing problems with complex Pareto front landscapes (e.g., discontinuity, disjunction, etc.). The multi-objective optimization algorithm has been first validated using numerical test problems found in the literature as well as energy systems optimization problems. Finally, the proposed optimization algorithm has been applied for the optimization of the secondary loop of Gentilly-2 nuclear power plant, and a set of solutions have been found which permit to make the power plant operate in optimal conditions. (Abstract shortened by UMI.)

Corrosion issues in high-level nuclear waste containers

NASA Astrophysics Data System (ADS)

Asl, Samin Sharifi

In this dissertation different aspects of corrosion and electrochemistry of copper, candidate canister material in Scandinavian high-level nuclear waste disposal program, including the thermodynamics and kinetics of the reactions that are predicted to occur in the practical system have been studied. A comprehensive thermodynamic study of copper in contact with granitic groundwater of the type and composition that is expected in the Forsmark repository in Sweden has been performed. Our primary objective was to ascertain whether copper would exist in the thermodynamically immune state in the repository, in which case corrosion could not occur and the issue of corrosion in the assessment of the storage technology would be moot. In spite of the fact that metallic copper has been found to exist for geological times in granitic geological formations, copper is well-known to be activated from the immune state to corrode by specific species that may exist in the environment. The principal activator of copper is known to be sulfur in its various forms, including sulfide (H2S, HS-, S2-), polysulfide (H2Sx, HSx -, Sx 2-), poly sulfur thiosulfate ( SxO3 2-), and polythionates (SxO6 2-). A comprehensive study of this aspect of copper chemistry has never been reported, and yet an understanding of this issue is vital for assessing whether copper is a suitable material for fabricating canisters for the disposal of HLNW. Our study identifies and explores those species that activate copper; these species include sulfur-containing entities as well as other, non-sulfur species that may be present in the repository. The effects of temperature, solution pH, and hydrogen pressure on the kinetics of the hydrogen electrode reaction (HER) on copper in borate buffer solution have been studied by means of steady-state polarization measurements, including electrochemical impedance spectroscopy (EIS). In order to obtain electrokinetic parameters, such as the exchange current density and the cathodic Tafel slope, two stages of optimization have been performed. From the optimization process, the activation energy (Eac) of the HER on copper was obtained as ≈32 kJ mol-1. Moreover, the mechanism of the hydrogen evolution reaction (HER) on copper in mildly alkaline media has been studied by means of EIS over the frequency range of 0.01 Hz ≤ f ≤ 5 kHz. The impedance spectra were modeled using a mechanism based upon the Volmer-Heyrovsky-Tafel steps for hydrogen evolution and by considering the reactions involved in hydrogen atom and hydroxyl group adsorption on the copper surface. A single set of kinetic parameters, including the rate constants and transfer coefficient, have been derived for each pH by optimization of the mechanistic model on the experimental impedance (EIS) data. It is postulated that the HER proceeds through the Volmer-Heyrovsky-Tafel mechanism with the Volmer reaction being the rate-determining step. The kinetics of growth of the passive sulfide film on copper in deaerated aqueous sodium chloride solution as a function of applied potential, sulfide species concentrations and temperature were explored by means of potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The electronic and compositional properties of the passive layer were investigated with Mott-Schottky analysis and X-ray photoelectron spectroscopy (XPS). It is found that metal vacancies are predominant defects in the barrier layer which is in agreement with the p-type character of the film observed experimentally. A point defect model (PDM) for formation and dissolution of the passive sulfide film on copper is proposed. Finally, the behavior of the system interpreted in terms of reaction mechanisms and kinetic parameters extracted from the experimental impedance data by mathematical optimization using a genetic algorithm approach. The diffusion coefficient of cation vacancies is obtained directly from optimization of the proposed model onto the EIS experimental data and was found to be essentially independent from the applied potential within the passive range. The diffusivity of the predominance defects (cation vacancies) found to increase with increase in solution temperature from approx. 10-13 (cm2 s-1 ) at 25 °C to 10-11 (cm2 S -1) at 75 °C.

Corrosion of Continuous Fiber Reinforced Aluminum Metal Matrix Composites (CF-AMCs)

NASA Astrophysics Data System (ADS)

Tiwari, Shruti

The first objective of this research is to study the atmospheric corrosion behavior of continuous reinforced aluminum matrix composites (CF-AMCs). The materials used for this research were alumina (Al2O3) and nickel (Ni) coated carbon (C) fibers reinforced AMCs. The major focus is to identify the correlation between atmospheric parameters and the corrosion rates of CF-AMCs in the multitude of microclimates and environments in Hawai'i. The micro-structures of CF-AMCs were obtained to correlate the microstructures with their corrosion performances. Also electrochemical polarization experiments were conducted in the laboratory to explain the corrosion mechanism of CF-AMCs. In addition, CF-AMCs were exposed to seven different test sites for three exposure periods. The various climatic conditions like temperature (T), relative humidity (RH), rainfall (RF), time of wetness (TOW), chloride (Cl- ) and sulfate (SO42-) deposition rate, and pH were monitored for three exposure period. Likewise, mass losses of CF-AMCs at each test site for three exposure periods were determined. The microstructure of the CF-AMCS showed that Al/C/50f MMCs contained a Ni-rich phase in the matrix, indicating that the Ni coating on the C fiber dissolved in the matrix. The intermetallic phases obtained in Al-2wt% Cu/Al 2O3/50f-T6 MMC and Al-2wt%-T6 monolith were rich in Cu and Fe. The intermetallic phases obtained in Al 7075/Al2O3/50f-T6 MMC and Al 7075-T6 monolith also contained traces of Mg, Zn, Ni, and Si. Electrochemical polarization experiment indicated that the Al/Al 2O3/50f Al-2wt% Cu/Al2O3/50f-T6 and Al 7075/Al2O3/50f-T6 MMC showed similar corrosion trends as their respective monoliths pure Al, Al-2wt%-T6 and Al 7075-T6 in both aerated and deaerated condition. Al2O3 fiber, being an insulator, did not have a great effect on the polarization behavior of the composites. Al/C/50f MMCs corroded at a much faster rate as compared to pure Al monolith due to the galvanic effect between C and Al. According to the mass loss data of Al/C/50f MMCs, corrosion rate was high at marine environments (high Cl-) when compared to a tropical rainforest microclimate and low in a test site with a high SO2 and acid rain. Due to presence of conductive C fiber, the galvanic corrosion was a dominating corrosion mechanism. Due to high volume fraction of C, the corrosion phenomenon was cathodically controlled. The galvanic corrosion between C fiber and Al matrix showed a strong positive correlation with Cl - deposition rate. Lower corrosion rate at volcanic test site was attributed to dissolution of Ni rich phase, a potential cathodic site that promotes corrosion of Al/C/50f MMCs. Based on the mass loss data of Al2O3 based CF-AMCs and the monoliths showed maximum corrosion at volcanic test site when compared to any other test site. Due to the small volume fraction of intermetallic phases, the corrosion was anodically controlled. And hence the maximum anodic dissolution was found at volcanic test site (high SO2 and acid rain). The second objective of this thesis is to study the effect localized deformation on the corrosion of CF-AMCs. Corrosion initiation on Al (2 wt% Cu)/Al2O3/60f (60% fiber), Al 6061/Al2O 3/60f, and Al/Al2O3/60f CF-AMCs was studied in an aqueous environment The CF-AMCs and their monolithic alloys were deformed locally using a 1/16" diameter silicon nitride ball and 15-60 Kg load in a Rockwell hardness testing machine. Corrosion initiated at the deformed sites, and after longer exposures, spread over the entire region. Localized mechanical deformation resulted in micro-crevice formations at the fiber matrix interface. When deformed material is exposed to a corrosive solution, the crevices at the fiber matrix interface likely increased the hydrogen ion concentration lowering the pH at those regions, a process that leads to premature corrosion. The copper (Cu) rich CF-AMCs in aqueous solution resulted in dissolution of Cu rich phase and their subsequent deposition and redistribution as Cu over the deformed CF-AMCs surface. The corrosion rates of deformed CF-AMCs were higher than the non-deformed CF-AMCs.